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Identification of the Mo₃S₄ intercalation system in lithium batteries made with natural MoS₂ Mulhern, Peter John 1982

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IDENTIFICATION OF THE Mo S, 0  INTERCALATION  SYSTEM IN LITHIUM BATTERIES MADE WITH NATURAL MoS by PETER JOHN MULHERN B.Sc,  Simon F r a s e r  U n i v e r s i t y , 1980  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES DEPARTMENT OF PHYSICS We accept t h i s t h e s i s as conforming to the r e q u i r e d  standard  THE UNIVERSITY OF BRITISH COLUMBIA October, 1982 ©  P e t e r John Muihern, 1982  October 7 ,1982  To whom i t may  concern:  Peter Mulhern has used diagrams  i n his thesis  that  have been p r e v i o u s l y p u b l i s h e d e i t h e r by myself or by other members of my r e s e a r c h group. I hearby give my p e r m i s s i o n f o r the use o f these diagrams  for this  Dr. R.R.  purpose.  Haering  In p r e s e n t i n g  t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of  requirements f o r an advanced degree at the  the  University  of B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make it  f r e e l y a v a i l a b l e f o r reference  and  study.  I  further  agree t h a t p e r m i s s i o n f o r e x t e n s i v e copying o f t h i s t h e s i s f o r s c h o l a r l y purposes may department or by h i s or her  be granted by  the head of  representatives.  my  It is  understood t h a t copying or p u b l i c a t i o n of t h i s t h e s i s f o r f i n a n c i a l gain  s h a l l not be allowed without my  permission.  Department of  Physics  The U n i v e r s i t y of B r i t i s h Columbia 1956 Main Mall Vancouver, Canada V6T 1Y3 Date  DE-6  (3/81)  September 24,  1982  written  11  IDENTIFICATION OF THE M o S « INTERCALATION 3  SYSTEM IN LITHIUM BATTERIES MADE WITH NATURAL MoS  2  ABSTRACT  Investigations intercalation  of  battery  the  lithium/molybdenum  showed  that  molybdenite, MoS , from the Endako capacity  naturally  mines  2  disulfide  had  occurring a  type  not found i n s y n t h e t i c MoS . The behaviour of t h i s 2  e x t r a c a p a c i t y was examined and attempts were made i t s source. M a t e r i a l s were s y n t h e s i z e d produce ray  the  same e l e c t r o c h e m i c a l  diffraction  responsible The  watt-hours  determined  for this  M O 3 S 4  that c o u l d  3  to  be  system  was  indirectly  the  found  kilogram  crystal  to  of  be  about  an 275  of cathode m a t e r i a l . Over h a l f of  the c a p a c i t y was a t 2.09V i n a f i r s t order d i d not  find  behaviour, and i n - s i t u X-  b a t t e r y with an energy d e n s i t y  per  to  capacity.  lithium/Mo Si,  intercalation  which  of  greatly alter  remaining c a p a c i t y was d i v i d e d  the host evenly  phase  transition  l a t t i c e . Most of the between  regions  continuous l a t t i c e expansion near 2.46V and 2.05V.  of  iii TABLE OF CONTENTS Page Abstract List  i i  of Figures  v  Acknowledgements  v i i  1 Introduction 1.1 M o t i v a t i o n f o r Research 1.2 The I n t e r c a l a t i o n B a t t e r y  1 .  2  1.3 I n t e r c a l a t i o n M a t e r i a l s  4  1.4 L i t h i u m I n t e r c a l a t e d M0S2  8  2 Experimental  Techniques  2.1 P r e p a r a t i o n of Cathode M a t e r i a l  11  2.2 Cathode P r e p a r a t i o n and C e l l C o n s t r u c t i o n  13  2.3 Constant Current  Cycling  17  2.4 L i n e a r Sweep Voltammetry  . 20  2.5 Constant Current 3 Capacity  Voltammetry  22  i n a-Phase M0S2  3.1 I n i t i a l D i s c o v e r y  o f High Voltage  Capacity  i n Endako M0S2  26  3.2 C y c l i n g the E x t r a C a p a c i t y  32  3.3 E f f e c t of Sample P r e p a r a t i o n  38  4 E l e c t r o c h e m i c a l Examinations 4.1 Attempts t o F i n d an Impurity  i n M0S2  42  4.2 Attempts t o Dope M0S2 with Copper  46  4.3 Attempts t o Dope MoS  50  2  w i t h Other Elements  4.4 Examinations o f X-Phase  52  4.5 Other E l e c t r o c h e m i c a l Studies  58  iv TABLE OF CONTENTS  (CONTINUED) Page  5 X-Ray Examinations 5.1 X-Ray D i f f r a c t i o n  60  5.2 P r e l i m i n a r y Examinations  61  5.3 Attempts  62  t o Dope MoS  2  5.4 Determination of L a t t i c e Parameters  66  5.5 I n t e r c a l a t i o n i n Mo^S^  70  6 R e s u l t s and D i s c u s s i o n 6.1 I n t e r p r e t a t i o n o f R e s u l t s  78  6.2 Suggestions f o r Future Work  83  6.3 Summary  88  Bibliography  90  Appendix 1  93  Appendix I I  94  LIST OF FIGURES Figure  v  Page  1  The E l e c t r o c h e m i c a l  Cell  3  2  Structure  3  T y p i c a l M0S2 Behaviour  4  Flange C e l l  16  5  X-Ray C e l l  18  6  Endako M0S2 a t o 3 Phase T r a n s i t i o n  27  7  Endako MoS  8  D e t a i l of High V o l t a g e a Phase Endako Capacity  9  P a r t i c l e S i z e Dependence of the E x t r a Endako Capacity  o f Layered T r a n s i t i o n Metal D i c h a l c o g e n i d e s  9  -- 6 Phase C y c l i n g  2  10 C y c l i n g 10-20 ym Endako MoS 2.7 V o l t s  9  28  11 C y c l i n g <38 ym Endako MoS 2.7 V o l t s  12 C y c l i n g 10-20 ym Endako MoS~ Powder Between 1.5 and 2.7 V o l t s Z  <38 ym Endako MoS  0  34 36  Powder Between 1.5 and  2.7 V o l t s 14 C y c l i n g  . 31 33  Powder Between 2.0 and :  0  z  30  Powder Between 2.0 and  Z  13 C y c l i n g  . .7  37  a-Phase Endako Powder  15 Unheated Endako MoS  39 41  2  16 C y c l i n g Cu^ S and Cu S g  43  2  17 C y c l i n g CuS and PbS . .  44  18 C y c l i n g CuFeS  45  2  and ZnS  19 Cycle o f MoS2~Copper Mixture Between 1.5 and 2.6 V o l t s . 48 20 C y c l i n g the MoS2~Copper Mixture  . .  49  21 F i r s t Discharge o f MoS2~Iron M a t e r i a l  51  22 C y c l i n g the MoS -Iron M a t e r i a l  53  23 F i r s t Discharge o f "X-Phase"  55  24 C y c l i n g "X-Phase"  56  2  vi Figure  Page  25 (101) D i f f r a c t i o n L i n e Between 2.04 and 2.2V  71  26 (104) and (212) D i f f r a c t i o n L i n e s Between 2.04 and 2.2V  72  27 (104) and (212) D i f f r a c t i o n L i n e s Between 2.4 and 2.6V 28 (223) D i f f r a c t i o n L i n e Between 2.5 and 2.1V  74 75  29 (104) and (212) D i f f r a c t i o n L i n e s Between 1.84 and 2.08V  76  30 X-Ray Scan of C e l l PMX-11 at 2.700V  99  31 X-Ray Scan of C e l l PMX-11 at 2.100V  100  32 X-Ray Scan o f C e l l PMX-11 at 2.050V  101  33 X-Ray Scan o f C e l l PMX-11 a t 1.800V  102  vii Acknowledgments  I would l i k e to thank rny s u p e r v i s o r , Rudi Haering, his  many  suggestions  and  h i s advice d u r i n g the course of  work on t h i s t h e s i s . C r e d i t must a l s o be given to other  members  contributed concepts.  of  many The  the ideas  data  for  lab, Jeff and  helped  for Figure  18  the  many  Dahn i n p a r t i c u l a r , who me was  clarify collected  several by Rod  McMi1lan. Finally, Engineering  I would l i k e to thank the N a t u r a l Sciences and  Research C o u n c i l f o r f i n a n c i a l  support.  1 CHAPTER 1  INTRODUCTION  1.1 M o t i v a t i o n A  good  electric give  f o r Research  battery  cars  system  for  the vehicle  the  demand  capable  of being q u i c k l y  have  life  much  public.  speed,  i n day-to-day  before they  prompted  general  the range,  people  long  i s t h e key t o t h e development  and  driving.  charged, must  into  must  acceleration  that  have  be r e p l a c e d .  research  The b a t t e r i e s  The c e l l s  and  high  of  must  a  be  conveniently  These  energy  also  requirements  density  battery  systems. Investigations system  that  of  appears  lithium/molybdenum Patent  useful  disulfide  4224390).  1.7 v o l t s ,  It  depending  density  of  cathode  material  (~250  MoS  research  several  run  2  energy  about  storage  intercalation  has a v o l t a g e  8.4X10  that  of  charge,  per  --  battery  ranges  joules  6  watt-hours  system  i s underway  distinct be  for  revealed  from and  a the  (U.S. 2.6 t o has  an  per kilogram of  kilogram)  in  this  range.  The  are  intercalation  on t h e s t a t e  energy  voltage  lithium  i s  different  a - phase  not f u l l y  to investigate  electrochemical in  still  MoS  2  understood, and  i t s properties.  phases,  each  with  behaviour. A practical  with  a  large  amount  of  There  i t s own  battery  must  reversible  capac i t y . Examinations  of n a t u r a l l y  occurring  MoS , 2  molybdenite,  2 from near Endako, B r i t i s h Columbia uncovered e x t r a which  was not present  interesting something  i n s y n t h e t i c MoS . T h i s d i s c o v e r y was 2  f o r two reasons. F i r s t , other  than  capacity  MoS  i f the c a p a c i t y was from  then  2  i t might  lead  to  a  potentially  u s e f u l b a t t e r y m a t e r i a l . And second, i f i t were  due  modification  to some  capacity  might  of  the MoS  be l i n k e d with  of i n t e r c a l a t i o n  itself,  2  the  some of the b a s i c p r o p e r t i e s  systems and serve as a  them. T h i s t h e s i s d i s c u s s e s  then  tool  for  studying  the e f f o r t s made to i d e n t i f y the  source of the e x t r a c a p a c i t y i n Endako MoS . 2  1.2 The I n t e r c a l a t i o n B a t t e r y Intercalation  i s the  molecule can be r e v e r s i b l y  process  by  inserted  which  into  a  an host  atom or lattice  without major s t r u c t u r a l changes i n the host. The interest  electrochemical  method  of  intercalation  f o r b a t t e r i e s . L i t h i u m metal can  electrode,  the anode, and the other  be  used  electrolyte  2  the  electronic potential  two  contact of  electrodes  ionically,  i s allowed  (Figure  but  than the chemical  atom,  ,  at  potential  the cathode.  This  of  direct chemical  •, a t the anode an  intercalated  results in a potential  d i f f e r e n c e , V, between the anode and cathode.  where e i s the e l e c t r o n charge.  no  1). The  a l i t h i u m atom i n a metal,  i s higher C  as one  e l e c t r o d e , the cathode,  i s a host m a t e r i a l such as MoS . A l i t h i u m s a l t connects  i s of  3  External load  anion from Li salt Li metal • anode  o  O  N o  Li +  —>•  o  L.  Li;+ cation o  Li MX x  o  2  cathode  o  o  1M Li salt in PC /  F i g u r e 1 -- The E l e c t r o c h e m i c a l C e l l (from Johnson 1982) LiAsF-g was  the s a l t used i n a l l experiments  for- t h i s  thesis-.  4 The  cell  pathway metal  through  the  electron into the  a n d go  solution  preserved  came  the c i r c u i t cell  into  from  A  electrolyte,  and the l i t h i u m  electrical atom  i n the  another  Charge  and cathode  The anode content  ion  neutrality when t h e  of the l i t h i u m  t o go t o t h e c a t h o d e .  discharges,  while  the host.  the ionization  an  lithium  solution  and e n t e r s  i n the anode,  that  by p r o v i d i n g  an e x t e r n a l c i r c u i t .  can ionize  leaves is  c a n be d i s c h a r g e d  passes  disolves  of  the  as  host  increases.  cell  The  host  with  an  electrons the  charge  1.3  applied  from  lithium  replate  the  Intercalation host  process certain  be  the  host  to  reach  of  of the host  anode  will  that  metal.  drop  as the l i t h i u m  ions  can As a  drive result,  and  metal  move  to  will  preserve  that  Materials n o t be g r e a t l y  intercalation,  classes  of  and t h i s  potential  a n d one o u t s i d e . T h e r e these  sites,  so t h e r e  a r e l a r g e enough was  electrochemical through  used  An  studies.  difference  be p a t h w a y s  narrow openings  atoms  in' the host  that  between  must  Lithium  to  electrochemical  be a way  guest  the  the hosts  must  the  during  requirement  f o r the guest  as  altered  restricts  materials.  b a t t e r y has the f u r t h e r  a chemical  Lithium  pass  potential  to the lithium  m a t e r i a l must  intercalation  host  external  the host  content  at  i s d e i n t e r c a l a t e d by r e c h a r g i n g t h e  neutrality.  A  must  material  there  an atom i n  f o r the through  to pass species  the  through. in  are small lattice,  guest  these and can  and  the  5 metal  is  light,  practical  cell.  intercalation crystal This  which  Normally,  host  while  is  then  discharged.  A  guest  can  not  atoms be  can  the  i s important  damage  host  done  often  reversible,  The  atomic  structure  Typically, cell  will  lower  the move  the di  and  which an  into  sits  in  be  the  in  the  host  the  would  host  the  then  the  and  s t r u c t u r e and/or not  be  deintercalated  sites  intercalation atoms  have  a  metal.  If  higher  host  an  inserted.  lithium a  be  creates  can  the  with  little and  electrochemical  than  the  i s charged  lithium  where  an  or c o n t r a c t s .  because  case  sites  of  a  cell  host  in the  sites  metal,  i t would  the  either  environment  of  the  of  throughout  expands  between  alter  in  into  the  as  density  content  applications  host  either  potential  than  anode  the  energy  continuously slowly  reaction  lithium  initially  potential  to  discharge  chemical  lithium  lattice  the lithium  varied  and  system.  the  the  for practical  intercalation  in  be  chemical  local  improves  chemical  m a t e r i a l would  be  as  is  the - c e l l  scharged. The  lithium  mechanisms material cell  other will  moves front  a  through can  content, undergo  have as  a  than  undergo  i s discharged.  representing  content  In  of  a  first  this  crystal.  radically  is usually  chemical  host  can  intercalation. order  type  discontinuity the  a  of  i n the The  the  reaction  case  Often  phase  lithium on  changed a  transition  reaction,  phases  different  be  a  phase  either  (sometimes  host  cathode as  the  front,  concentration, side  s t r u c t u r e s and/or  i f the  by  and  called  a  the  of  the  lithium lithium  displacement  6 reaction).  It  first  phase  is  order  the  host  guest  lattice The  atoms  i s not  materials  by  form  metal  then  together  by  weak  sandwiches form  into  atoms  can  der  be  transition  i t  while  the  dichalcogenides, for  systems phase  on  top  VIB) of  on  the the  the  another,  layer  of  2  be These  chalcogen outside  inside. and  forces. Figure  a  also  transitions.  layers with  or  MoS  intercalation can  t e l l u r i u m ) on  VB,  2a  and  These  are  held  shows  metals  be  tetrahedral  The are  on  shown  a  of  in  the  three  and  in Figure  and  can  these  move  common  octahedral  have  two X  a  in  the  structures  of  the  2b.  The  lattice,  planes.  polytypes  sites  i n the  in  more  sulphurs  and  the  metal  prismatically The  the  as  Van  shown gap  or  sandwiches  orientations through  different  variations  trigonal  different  lithium  basic  triangular  between  two  slight  two  either  The  atoms  of  coordinated  stacked  and  dichalcogenides  because  planes  2c.  lithium  or  Waals  layered  themselves  octahedrally  gap,  one  arrangements.  Figure  metal  M .represents  structures  atomic  then  the  if  a  chalcogens.  Different crystal  Van  simultaneously  and  altered.  these  IVB,  stacked  intercalation  conditions  selenium,  sandwiches,'where of  undergo  sandwich-like  Groups  both  occurring  non-intercalation into  (from  are  the  although  (sulphur,  layer  greatly  have  transition  1980),  complicated  layers  which  satisfy  (McKinnon  the  transition  layered  included,  atoms  i s p o s s i b l e to  shown der  in  Waals  a l l have in  can  which  both the  can s i t .  Intercalation  occurs  than  just  layered  7  (a)  General form  X M  7  z  X X  van der Waals gap  (b) Coordination units for MX2 layer structures  AbA trigonal prism  AbC octahedron  (c)  2H-MoS-  2H-NbS-  -*II20  1120  •1120 AbA BaB  lT-TiS.  AbA CbC  AbC AbC  F i g u r e 2 -• S t r u c t u r e of Layered T r a n s i t i o n Metal Dichalcogenides (from McKinnon 1980)  8 structures. pass  Rutiles,  through,  compounds, (Murphy of  which  and  have  spinels,  also  a r e both  1.4 L i t h i u m MoS  used  1980).  a suitable,  f o r the  lithium  are similar as  Further  p o s s i b l e and  I n t e r c a l a t e d Mos  i s  2  tunnels which  been  1978, E i s e n b e r g  hosts  have  to  to layered  intercalation  hosts  additions to the  list  probable.  2  but complicated,  host  for lithium  intercalation. The  2H-MoS  polytype  2  electrochemical structure. 1.15  purposes  The o-phase  volts  i s  (Figure  i t  the  and  common,  was d e s i g n a t e d  has very  3a)  most  little is  a  and  as t h e a-phase  c a p a c i t y above poor  for  practical  about battery  mater i a l . When it  goes  1T  that  to  0 > 1  a first  shows  2  over  There  a-phase  dependent  high  and i s  not  of  is  i n F i g u r e 3b.  MoS another of  this  2  a p-phase  can also phase  phase  range  voltages, yet  fully  cell  being  be d r i v e n  transition i s unknown,  to  phase  into  1.15  I t i s t h e p-  battery. This  of  ~0.6V  going  a t about  by  0.6 v o l t s .  ~2.6V,  t o be The  going  2  to  p-phase  cycled at constant  r-phase  phase  LiMoS  from  seems  understood.  to  from  conversion  but t h i s  volts,  and forms t h e  (Py 1982).  as a commercial  approximately  about  transition  as p-phase  i s some s l o w  at  below  phase  the voltage  profile shown  order  promise  corresponds  MoS .  i s discharged  designated  metastable  which Li  through  polytype  phase is  t h e a-phase  sample voltage current  through  The s t r u c t u r e  and i t s p r o p e r t i e s have  not  been  0  1  2  3  4  5  Time (hours)  b)  3  Time (hours) 3  c)  0  10  20 Time (hours)  F i g u r e 3 -- T y p i c a l M0S2 Behaviour a) a-Phase b) 3-Phase c) y-Phase Constant Current C y c l i n g o f C e l l PM-94 100 uA c u r r e n t 3.86 mg cathode o f Atomergic MoS 0  6  10 fully  investigated.  Except  7-phase  not be  F i g u r e 3c,  will  for  noting  discussed.  its  existence,  11  CHAPTER  EXPERIMENTAL  2.1  P r e p a r a t i o n of Cathode Both  MoS  synthetically  powders were  2  The  synthetic  Chemicals that  powder  averaged  were  smaller  grinding The from  Placer  until  i t  was  thoroughly allowed The  with  to settle  The  diameter  the  liquid  The  was  under  lost  clean  a  until  r e s i d u e s from t h e  of MoS  was  supernatant washed  less  2  was was  decanted. fluid  i n three  benzene;  i t remained  material  the suspension  the l i q u i d  o f f . The powder of  The Endako  grams  o f t h e powder  because  flow  was o b t a i n e d  two h u n d r e d  the  no  cathodes.  cathode  and then  particles  required  unsuitable  i s primarily  Some  was p o u r e d  t o 750°C  an  chemical  was a l t e r n a t e l y  which  trichloroethylene. in  with  overnight before  powder  powder  into  platelets  A l l  Endako mines d i v i s i o n .  a solvent  was r e p e a t e d  solvents:Solvex,  it  was  This  revealed  shaped  molybdenite,  2  c l e a n e d . About  mixed  process  clear.  MoS ,  the Atomergic  examination  i t was made  occurring Limited,  from  i n diameter.  microns.  before  occurring  materials.  obtained  microns  fifteen  and  naturally  of i r r e g u l a r l y  was c o n t a m i n a t e d  process  and  microscopic  five  than  naturally  concentrate refining  was  2  consisted  or cleaning  Canex  Material  as cathode  MoS  about  TECHNIQUES  prepared  Corporation. A  the  that  used  2  ran  organic  c h l o r o f o r m ; and  than  one  micron  i n suspension  was d r i e d  by  when  heating  argon.  Endako powder  was  sieved  into  the following  12 s i z e f r a c t i o n s : g r e a t e r than  105 microns;  75 to 38 microns; and l e s s than size  fraction  was  s e t t l i n g technique  further  38  105 to 75 microns;  microns.  divided  by  (Allman and Lawrence  using  a  viscous  in  the  separate  in  cylinder powder  water  was  was  (~l90ml). Methanol  water to maintain sample  purity--the  without  also  alcohol.  left  was  The  tube was  left  particles  from  the  effective  that  a  smaller  technique was boundary was  so  20cm  used rather  than  would  not  mix  the  to s i t f o r a given a  certain  settling  times  were  four  times  larger  size  removed  ones.  distinct  often seen d u r i n g the l a s t  which asumed s p h e r i c a l  This  murky/clear  settling.  estimated by using formulas  particles,  but  the  MoS  2  platelets  always w i t h i n a micron or two of the p r e d i c t e d s i z e . A  20 to 38 micron tube  a  i n suspension, and these p a r t i c l e s were siphoned  all  were  to  adding a d i s p e r s a n t . The  three or  The  that  put i n t o a  particles  out. Repeating t h i s procedure the  was  added  time, a f t e r which only p a r t i c l e s l e s s than were  2  covered and then v i g o r o u s l y shaken to  and  Stokes'  principle  a gram ,of MoS  and then methanol  tube  a  than small ones when they are i n  medium. About h a l f  graduate c y l i n d e r depth  faster  smallest  1972).  A Stokes' s e t t l i n g s e p a r a t i o n uses the large p a r t i c l e s f a l l  The  after  siphoning suspension  s i z e f r a c t i o n s e t t l e d to the bottom  of  the  f i v e minutes, and a 10 micron boundary r e q u i r e d after after  twenty an  minutes.  Any  particle  hour and a h a l f was  still  smaller than f i v e  microns. The powders i n a l l Stokes' s e t t l e d f r a c t i o n s p a r t i c l e s any l a r g e r  than the upper  size  in  limit,  and  had  no  very  13 little,  probably  smaller  2.2  than  Cathode The  onto  physical  from  The most  aluminum  foil  Usually substrate,  was  the eight not  was t h e n  liquid  microns  and  cathode  substrate The under  was  material  with  reacting  with  square  0.25mm  i n X-ray  cells,  as the backing used  drops  very was  atmosphere  propylene  mixed  an a r e a  cathodes.  under  into  onto  the  glycol  were  a slurry  which  o f t h e s u b s t r a t e . The an  smaller  argon  flow  until  than  about  thirty  usually  would  and  bumps  larger  that  than  occur  during  thirty  eight  o f fthe metal  carefully. determined  unless the  The e x a c t by  weight of  weighing  the  t h e powder.  cathode  the  were  f o rheavy  was w e i g h e d  of  to flake  and without  finished  an i n e r t  Inch  Powder  handled  made  acid.  t o the metal  tended  were  nitric  by t h e s m a l l  weighing.  substrates  squares  Particles  well  f o rthe cathode  rough  a t 200°C  loose  i n diameter  substrate the  adhered  jarred  handling  baked  both  into  over  evaporated.  microns be  evenly  to provide  contact  cathode  by b a k i n g i t  cut  a n d powder  distributed  was  foil  used  two  cathodes  served  1Omg o f d r y p o w d e r  then  The l i q u i d  cathode  into  was o c c a s i o n a l l y  about and  used  with  were  weight,  Construction  electrical  nickel  and etched  by  limit.  was made  commonly  sheets  percent  The s u b s t r a t e  and  thick  one  and C e l l  powder  support  0.125mm  added.  size  substrates.  beryllium  than  Preparation  1.2cmX1.2cm  and  the lower  prepared  metal  powder.  less  h a d t o be a s s e m b l e d  to prevent  other  cell  water  and  into oxygen  components.  A  a cell from, Vacuum  14 Atmospheres  Company  Pre-purified the  water. a  argon  b o x , a n d was  Matheson  Model  8301  Hydrox  below  usually  was  size  quality  foil, made  bulb  the  bulb  the  the water  were  assembled  0.010  into  slightly  surfaces  the oxygen also  acted  served  and as  a s an  atmosphere.  and oxygen  a  These  c o n t e n t s of the  inches thick,  the c e l l  larger  scraped  to prevent  anode  than clean  Foote  by c u t t i n g  the just  any s u r f a c e  from  the f o i l  cathode. before  coating  Mineral  The the  from  to  lithium cell  was  affecting  the  LiAsF ,  and  performance. The  salt  the  solvent  to  less  plastic with  f o r t h e one m o l a r  was  than film  propylene 20ppm  from  shorts  carbonate  was  used  between  surfactant,  o r C e l g a r d #2500,  surfactant  enter  ones  cells  conf igurations.  could  were  a  either  pores  of  be w e t t e d  usually  6  had been  distilled  and water.  and  did the about  to  porous  #3501, not.  which  in  The had  Electrolyte  separators three  wet  prevent  cathode.  without  atmospheres,  at atmospheric  assembled  A  Products,  separator  Celgard  which  was  Film  anode  i f the p r e s s u r e exceeded  the other The  from  the  glycol  as  the  were  only  made  which  Microporous  separators  would  electrolyte  of p r o p y l e n e  Celgard  electrolyte,  internal  but  t o remove  of  filled  the gas through  3 watt  of  Limited  0.1ppm.  Lithium Company  of a  construction.  of Canada  Purifier  lifetime  kept  for cell  by c i r c u l a t i n g  filament  the  used  Matheson  clean  the  of  procedures  cell  kept  and  indication  a  from  The t u n g s t e n  getter,  box  d r y b o x was  one  pressure. of  two  15 Most  commonly,  cathode  would  tiny  o f vacuum  dab  be  brought  was  p u t on  quickly  lithium would O-ring the  up  into  on  in  cathode  powder  Bolting  place,  could  will  after  be  also  the c e l l  together  scraped  react  with  removed  from  not o n l y  electric  be  pre-greased  was  applies pressure  i n good  would  the top flange  and  that  would  then  the  The  the c e l l  but  would  and b o l t e d on. oxygen  a  electrolyte  Finally, and  The  with  powder  separator  the separator,  place  of  packed  top of the cathode.  and e l e c t r o l y t e  pieces  wet  used.  assembly  o r two  the loosely  was  of the c e l l  the c e l l  box. A d r o p  out the water  box.  then  A  4)  (Figure  t o the base  and  and  be p l a c e d  sealed  cell  the l i q u i d . on  slipped  glove  grease,  the glove  placed  lithium  the  attached  the cathode,  would  be  be  into  soak  carefully  the flange  holds  the  to ensure  contact  the  with  the  substrate. Two one a  types  pictured  of  flange  in Figure  non-conducting  propylene assembly  to prevent  were  and  slightly  a  4 had  viton  carbonate  cells  cell  non-conducting conducting  made  with  plated brass  bolts  the p l a s t i c 4  softer  polypropylene.  A  were  special  required  type  of  The was  to  cell  not  ensure  absorb  no d a n g e r  pass  the  careful flange  of a  short,  be  used.  could cell  components  through  the centre  three a proper  _,.was._ u s e d  steel  requiring  polypropylene  O-ring  which  of  required  t o the a c t i v e  flanges. Six bolts,  Figure  stainless  would  also  neoprene  was  of  and  so t h e r e  contact  The  which  circuits.  Electrical nickel  used.  the disadvantages  O-ring  solvent, short  were  to  as seal  shown  in  with  the  collect  X-ray  F i g u r e 4 - - Flange C e l l (from Von Sacken  1980)  17 diffraction b a t t e r y was  patterns in use  of  the  (Dahn, Py,  cathode and Haering  f e a t u r e of i t s c o n s t r u c t i o n was allowed  copper  working c e l l a  K  X-rays  n  a  (k-1 .54178A) was  to  designed  gasket  2.3  that f o r the flange c e l l s ,  i n s t e a d of an  O-ring.  Constant Current  Cycling  The and  charging and Cyclers  discharging a c e l l made  electronics  shop  that  be  could  milliamperes.  vice The  by  the  supplied varied  High and  from  polypropylene  capacity,  continuously  between set voltage U.B.C.  Physics  a  few  limits.  department  microamperes  current to  100  and  the c e l l  p o t e n t i a l reached these output  of the c e l l  c e l l v o l t a g e as a f u n c t i o n of time was  time base, and  the S o l t e c S-4201. The in F i g u r e 3 was this  except for  a u t o m a t i c a l l y changed from charge to d i s c h a r g e ,  feeding the c y c l e r output  of  by  was  and  when  low  obtained  X-ray  cell  an e s s e n t i a l l y constant  c y c l e r a l s o had an analog  built-in  a  into  t r i p v o l t a g e s c o u l d be chosen  versa,  The  1730  b a s i c information on o p e r a t i n g v o l t a g e s ,  r e v e r s i b i l i t y of a b a t t e r y was  the c e l l  to f i t  X-ray  using b e r y l l i u m as the cathode s u b s t r a t e and  which  pass i n t o the  1050/80 goniometer of a P h i l i p s PW  identical  the  special  window  to  powder d i f f r a c t o m e t e r . C o n s t r u c t i o n of the almost  while  1982). The  beryllium  (Figure 5). T h i s c e l l  m o d i f i e d PW  material  technique  of  voltage. recorded  by  i n t o a s t r i p c h a r t recorder with a the most commonly used recorder  t y p i c a l MoS  obtained  limits.  2  behaviour that was  in t h i s way. recording  The  data  main  was  shown  disadvantage  i s that i t i s o f t e n  7» ANGLE NYLON SCREW  ^  CELLTQP CELL VOLTAGE CONTACT CELL CATHODE ON .010" THICK BERYLLIUM WINDOW  POLYPROPYLENE GASKET  LITHIUM ANODE GLASS SPACER  FLUID INLET THERMISTOR CELL VOLTAGE CONTACT FLUID OUTI CELL BASE  F i g u r e 5 -- X-Ray C e l l (from Dahn, Py, and Haering 1982) 00  19 difficult An  to  see  advantage  voltage  versus  thermodynamics Gibbs  subtle  free  of  constant  time of  of  a  dG  where the  v  is  host,  entropy, p  is  N T  of  charging  equation  or  discharging  a  cathode  during that to  the  content like  between that  of  current  passed  number  of  of  a  cathode 2  where  charge  two  voltage  that  values range.  the  change  the  to  the  in  the  lithium  of  constant time  the  be  The  of  and  omitted chemical  through  number  is  volume,  can  constant.  in  S  i s the term  atoms  Equation  intercalated  time  a  cell  c u r r e n t . At curves  is  constant  reflect  an  cell. of  lithium of  the  transferred  the  flowed.  from  current  The  net  anode  to  lithium  atoms  i s often  w r i t t e n as  x  related  atoms,  v  length  that  (2)  the  last  the  versus  product  been  L i MoS  amount  the  the  of  a  is  dp  potential  and  at  amount  i s the  which  have  of  the  the  cell  to  voltage  state  Ideally, of  related  v  intercalated  chapter,  be  of  +  curves. .  is  temperature,  the  can  the  dT  is essentially  previous  temperature,  material  Usually  to  cycling  differential  - S  of  voltage  directly  potential  absolute  is related  N,  The  y dN  number  pressure  the  atoms,  =  pressure.  the  potential 1  i s the  are  cathode  chemical  i s the  the  because  the  cell.  i n the  current  curves  the  energy  features  i s the  flows  mole  while  is defined  as  i n the  the  a  host.  cell  of  The  time  is  equal  lithium formula  lithium.  potential  c a p a c i t y of  out  electrons  chemical of  or  the  cathode  fraction  the  and  number the  into  the  The  changes cell  in  20 There value  of  are  two  x.  First,  not  connected  to  electrically mole  fraction will  host  material.  associated is  same  the  The  occasionally different  be  problems  be  a l l the  in  determining  the  cathode  substrate,  computed  Second,  with  present.  2.4  major  using  not  a l l  the  detected  amounts  of  if  of  time  a  as  a  wrong  charge  i n t e r c a l a t i o n system presence  material  and  the  the  if a  parasitic  a  reversible  to  charge  may  be  result  the  amount  of  that  flows  side  side  true  reaction  reaction  reaction  and  is  discharge  can  takes at  the  current.  Linear  Sweep  Linear  sweep  battery  capacity  some  the  of The  voltammetry in  a  way  differential dQ/dV,  state  a  The  F  of  active  material,  tells  how  the  dQ/dV  changed, phase  i s the  and  the  Faraday  the  number  in  between  dx dV  constant,  M  m  is  tends  to  is  the  of  will  expresses altered,  compressibility  dQ/dV  the and  .volume  also  change  flow  becomes  gas,  of  a  infinite  at  with  respect  to  equation  and  dx/dV  molecular  mass.  infinity  a  of  of  is  U  completely  of  examination  the  gas a  The  i f the at  a  - ^ as  ;  weight  value  of  voltage  is  first  analogous 1  isothermal  examining  cell.  i s the  its  of  direct  capacity  behaviour  charge  This  method  of  dQ _ F m dV M  and  much  transition.  properties  relation  where  a  permits  change  reflects  cell.  is  that  thermodynamic  voltage, of  Voltammetry  order to  the  d"V 8p^T the  phase  '  which  pressure  is  transition.  21 Other  sources  lattice  gas of  versus  voltage  capacity  current  of  the  or  feature,  dQ/dV  physical  through two  versus  that  and x  associated  will so  can  mechanism  sweep  have  with  a  which  is  the  certain  examinations  occasionally  the  voltammetry  cell  as  potentials.  differential  as  of  be  dQ/dV  used  responsible  for  capacity  the The  technique  voltage  current,  I,  measures  is  slowly  is  related  the  swept to  the  through  i - v$ where  to  cell.  linear  between  such  intercalation,  voltammogram  in a  The  capacity,  model  shape  determine  of  v" i s t h e  rate  at  which  the  UJ  voltage  changes  (Dahn  and  Haer i n g ) . A  PAR  175  Universal  Potentiostat/Galvanostat that as  a  could few  plug-in  change  microvolts for  the  173  a  were  voltage  per unit  flowed.  Current  charge  were  plotted  on  voltammetry. and is  the  X-Y a  Current  flows  p o t e n t i a l of  the  to  applied A  PAR  measured  that  is  used  second.  charge  Diffusion  Programmer  versus  produce to  a  179  the  major to  problem  equalize  voltage  ramp,  but  particles  in  the  cathode.  to  diffuse  at  a  by  as  ramp little  Coulometer and  total  or  current  versus  in  linear  sweep  the  the  be  173  recorders.  lithium concentration  may  PAR  linear  cell  voltage  the  particles  a  current  by  the  a  Digital  determined  through  and  It  takes  crystal,  different  and  potential  the at  time so  cell  the than  cell  the  for  potential voltage  surface  the  surface the  of  lithium of  the  insides  22 of  the  grains.  equalize then of  the chemical  current  voltage  potential swept of  must  lithium.  ramp  2.5  Constant  measuring  of c a p a c i t y ,  capacity  previously  the actual  voltage  that  widths  had  to  be  method  of  the problem.  Voltammetry  current  dQ/dV.  at  at potentials  obscures  but  at a certain  of c a p a c i t y  and the c e l l  to minimize  Current  Constant  smearing  to  concentration  measured  t h e amount  the host  the c r y s t a l ,  the surface  of the capacity  Diffusion  slowly  throughout  the current  i s due t o b o t h  the regions  d i f f u s e through  to maintain  result,  a n d some  very  will  potential  flow  As a  through.  swept  Lithium  This  voltammetry technique  is  another  determines  the  differential  from  (5) where  At  was  potential  by  the  some  time  small  i t took  amount  AV  f o r the c e l l while  a  t o change i t s  current  I  was  flowing. Using preferable on  linear  constant to using sweep  blur  the  long  time.  the  potential  regions, region slowest  linear  slowly  shape  sweep  would  be much sweep  pass  of voltage smaller ramp.  often  took  than  through  change could  in a  usually  Running  problems  c y c l i n g had t h e  quickly  was  voltammetry.  enough so d i f f u s i o n  current  yet the rate  linear  voltammetry  of the f e a t u r e s  Constant  could  current  a  a  did  cell not  prohibitively  advantage low high  be a t t a i n e d  that  capacity capacity with  the  23 The  difference  sweep v o l t a m m e t r y  was  transitions  where,  should  an  be  voltage.  The sharp  Often  linear  much  that  dQ/dV  is  accurate A  than  position  would was  little  often  for be  an  included  of  a  the  versus  this  as  diffusion  to  order a  of  a  tail.  peak  so  'spike'  methods  several  shift,  in-order  measured  each  of  measuring  current  slowly technique  faster  and  more  be  to  If  the  the  by  two  with had  R  was  find  IR,  to  be  MoS  correct fully  on  charge  and  the  2  cell  was  observations. the  the  the  feature  positions  shifted  currents  where  and  correct If  there  p-phase,  then  made,  followed  by  a  extrapolation.  Johnson  Initially, several  of  constant  current  voltammetry  is  (1982). the  constant  pieces  4052 2.3  there  dQ/dV  show  first  both  feature.  detailed analysis  section  be  .IR  case  Tektronix  a  constant  phase  sweep.  i s the  by  the  order  p o t e n t i a l i s changed  the  h y s t e r e s i s , as  current  of  would by  linear  problems,  graph  these  cell  of  at  in  skew  both  i f the  kinetic the  and  first  resemblance  middle  A  used  would  i t can  then  in  with  followed  the  readings  given  to  no  current  technique  in practice  position  discharge  test  linear  had  reversible,  current  bear  correction  voltage  spike  principle,  because  impedance,  zero  sweep  however  were  in capacity  identical  better  were  rise  In  are  enough,  infinite  constant  noticeable  i f there  i t would  capacity.  most  constant  sudden, a  between  ran  of  current  equipment  microcomputer. the  voltammetry  cell,  The and  the  under  the  cycler output  experiments control  of  described was  fed  into  a in a  24 Hewlett read  Packard  both  Digital The  the  Clock  region  from  of  region. computed  debugged  reference or  was  a  then  control  day-to-night  temperature  change  compared  to  cells bath  with  piece  to  system  nV  voltage noise this  of by  be  equipment  the  to  be  paragraph. with  U.B.C.  dedicated  proved  previous 500  in a  transformer  by  In  in  of  a  the  lab  o i l and  The  data This  was  system  need  for  the  massive  apparatus. K  voltage  values.  made  a  was  experiment,  volt--a  Haake  in  capacity  and  the  one  the  voltage  dQ/dV  the  hand.  out  cells.  of  20°C  reference  pointed  hundredths  at  time  Eventually,  variation  high  recent  new  the  the cell  change  Afterwards,  constant  temperature  under  the  c o n t r o l of  for monitoring  the  cycler  a  circulator.  designed  shop  as  in a  and  most  values.  millivolts  again,  plotted  the  resolution  filled  A was  the run  F3  of  two  were  Haake  and and  temperature  voltage  The  until  2.5  would  59309A H P - I B  reference  than  read  repeat.  software  as  millivolts  recorded  teletype  the  1.0  then  then  would  more  computer  Packard  continuously  by  5.  The  Hewlett  numbers  read  Equation  were  on  the  be  capacity,  cycle  and  record  would  from  printed  a  clock  measurements reading  voltmeter  the  low  The  Voltmeter.  and  voltmeter  differed  3455A D i g i t a l  a  to  Physics constant  superior The  device  r e s o l u t i o n of  measurements or  minor  device  was  to  to  45  remove  fluctuations analog  only,  department current  the  one  looked j*V. any in and  for  It  the  described voltage  caused  fed  This  in  changes  averaged  system.  was  electronics  voltammetry.  also  jitter  output  by  The into  sets  the of of  either  output  of  an  X-Y  25  recorder.  26 CHAPTER 3  CAPACITY  I N c - P H A S E ENDAKO  MoS  2  Serendipity--an assumed gift for finding agreeable things not sought f o r -Webster's  3.1  Initial MoS  Discovery  Third  of  New  High  valuable  International  Voltage  or  Dictionary  Capacity  i n Endako  2  A  set  of  experiments  to  investigate  the  diffusion  cells  which had  effects  in intercalation batteries  compared  cathodes  made  particles.  material  was n a t u r a l l y  mines  with  which  had  different  by  constant  current  apparent  differences  the  were  2.4).A  when  feature  Figure  6 shows  The  extra  shown  referred A  by  linear  MoS  2  cell  powder  seemed  7. M o s t  of the c e l l s  showed,  s e t of constant t o examine  t o remain  Endako  current  t h e MoS  2  The  was  sweep  size  simple  shown  no  varied,  so  voltammetry  a t about  2.1  MoS  Atomergic.  2  from  feature  even  volts  through  the  i s indicated.  i n t h e p-phase,  made w i t h  in differing  five  had  discharging  t r a n s i t i o n , and the e x t r a  capacity  2.3  the p a r t i c l e size  i n the synthetic  t o as the "extra  performed  section  cathode  t h e Endako  into  settling.  was d i s c o v e r e d  an E n d a k o  in Figure  occurring  of  The  from  and d i v i d e d  Stokes'  examined  was n o t p r e s e n t  o t o p phase  and  cycling  which  molybdenite  cleaned  sieving  cells  (section  occurring  been  fractions  sized  amounts,  as  the n a t u r a l l y what  will  be  capacity". voltammetry  o to p  phase  experiments transition  were in  27  0.8  1.0  1.2  1.4  1.6  1.8  2.0  V o l t a g e (V) Figure  6 -- Endako M0S2  a to 3 Phase T r a n s i t i o n  L i n e a r Sweep Voltammogram of C e l l PM-19 15 yV/sec Voltage Ramp 9.35 mg cathode o f 10-20 ym Endako powder The arrow i n d i c a t e s the e x t r a c a p a c i t y found i n Endako powders.  usually  100  <  3.  80  h  60  \-  c CD  40 h  3  o  20  0 0.8  1.0  1.2  1.4  1.6  1.8  2.0  V o l t a g e (V) F i g u r e 7 -- Endako MoS,  3 Phase C y c l i n g  L i n e a r Sweep Voltammogram o f C e l l PM-19 15 yV/sec Voltage Ramp 9.35 mg cathode of 10-20 ym Endako powder The two small arrows i n d i c a t e the e x t r a c a p a c i t y u s u a l l y found i n Endako powders.  29 cells  made  with  measurements extra the  Atomergic two  all  smaller  i n a-phase  2  so t h e c a p a c i t y  amount size  in  micron  Figure  powder,  bigger of  powder.  than  this,  extra  smaller  than  thirty  by  making  a heavy  cathode  accurate  was i n  as  would  powders  of a c t i v e  measurements  function  was  the ten  micron  a  not  a good  that  f o r both  volts.  than  of  of the  accurately line  smaller  there  (~60mg  discharge  The dashed  i t i s also  eight  Almost  9. T h e c a p a c i t y  the  was a  8).  was  since  capacity  The r a t i o s  the  more  and  of  above  volts  (Figure  capacity  powder  the capacity  capacity  1.0 a n d 1.2  a n d s o was n o t p l o t t e d .  amount  allowed  between  as  of the c e l l .  2.0 a n d 2.1  on t h e f i r s t  Endako  shown  five  micron  unsized  transition  of the  was e x p r e s s e d  capacity  feature  of the c e l l  is  than  material  feature  between  o f t h e new  of e x t r a  represents  eight  o f t h e new  These  of the magnitude  h a s no a p p r e c i a b l e  determined, graph  estimates  particles.  MoS  capacity  particle  cathode  to the total  a t o p phase The  the  The s i z e  of the size  the  crude  sized  of i t s capacity  volts,  measure  the  allowed  capacity.  ratio  different,  on  this  than  thirty  very  little  indication be f o u n d to  and  determined  material)  did  inthe  twenty  were  of  the  which earlier  exper iments. Eventually, problems  were  discovered  the  suspended  capacity.  investigations i n favour  of  of studies  the of  diffusion the  newly  30  0.70  o > CL  CO _Q  E _o Z3 O  o  > O  0.00  F i g u r e 8 -- D e t a i l  1.8  2.0  Voltage  (V)  o f H i g h V o l t a g e a Phase Endako C a p a c i t y  C o n s t a n t C u r r e n t Voltammogram o f t h e F i r s t D i s c h a r g e o f C e l l PM-30 25 yA c u r r e n t -- m i c r o c o m p u t e r c o n t r o l l e d apparatus 8.8 7 mg c a t h o d e o f 5-10 ym E n d a k o Powder  0.6 0.5 0.4 0.3 0.2 0.1 \0.0 ' 5  ' 10 Particle Size  1 20  u 40  (microns)  gure 9 -- P a r t i c l e S i z e Dependence of the E x t r a Endako Capacity  u 80  32 3.2 G y c l i n g The  extra  different always  kept  peak  of  also  lower  than Most  This  thirty  (Figure amount  different small,  was  of cathode first from  cell  was  which  current  twenty  micron  type  MoS  particles.  The  cell  that  on  the  was  shift,  made  from  11). This  a t 2.085±0.005V,  was  four  millivolts  discharge  capacity  peaks.  near  2.45V.  i t was n o t c l e a r l y  with  was  corresponding  (Figure  centred  o f some  but  f o r t h e IR  of the subsequent  was made  cell  The  particles  discharge  small  of the 2  discharge,  Another  evidence  i f the  i n t h e voltammogram,  capacity  first  so  was t h e t y p e  voltammogram  Correcting  micron  ten times  the  seen  normal  material. discharges  the later  shown  discharges  capacity  of the substrate  of a  to the capacity  o f most  in  Endako  was  powder  i n Figures because, fresh  so  cells. small  10 a n d 11 i n part,  substrate.  i s not seen  compared the  the  potential.  a s a peak  eight  a cell  irreversible  capacity  this  a t 2.085V.  showed  11) u n t i l  The  i f  and another  on t h e f i r s t  the p o t e n t i a l  capacity  to  i t s major  on t h e  cells  two  volts,  was a t 2 . 0 9 3 V .  had  t h e peak  have  type  section;  seen  was c e n t r e d than  to  i t was a t 2 . 0 7 8 ± 0 . 0 0 5 V .  on r e c h a r g e peak  found  2.0 a n d 2.7V o f a n E n d a k o  ten  discharges  cell  1.8  a constant  between  was  one  below  a t 2.070+0.005V  smaller  the  shows  capacity,  located  and  10  a cathode  largest  the  discharged  few c y c l e s  later  about  i n the previous  Figure  with  capacity  of behaviour:  above  was e v e r  first  Capacity  Endako  types  discussed cell  the Extra  because  The that  were  of the  Normally, i t i s tiny  extra the  capacity substrate  33  2.20 > CD CL  1.10  h  CO -Q  E O O  >  0.00  1.10  TJ  -2.20  |-  2.00  2.15  2.30  2.45  2.60  Voltage (V) F i g u r e 10 -- C y c l i n g 10-20 ym Endako MoS and 2.7 Volts'  ?  Powder Between 2.0  Constant Current Voltammogram o f C e l l PM-85 10 yA c u r r e n t . 58.80 mg cathode o f 10-20 ym Endako MoS Powder 2  The arrows i n d i c a t e the f i r s t cell.  discharge o f the  34  2.00  2.15  2.30  2.45  2.60  V o l t a g e (V) Figure  11 -- C y c l i n g <38 ym Endako MoS~ Powder Between 2.0 and 2.7 V o l t s Constant Current Voltammogram o f C e l l PM-96 5 yA c u r r e n t 100 mg cathode of <38 ym Endako M0S2 powder The arrows i n d i c a t e the f i r s t cell.  discharge o f the  35 capacity  was  The  a  comparable  electrochemical  capacity  changes  about  volts.  1.8  first  as A  discharge  of  smooth,  and  The  1.5V.  about  Atomergic amount  About  a  three centred  near  2.460V.  and that  the  The one  1.9 test and  and  cathode. loss  of  cathode  between  of  loss 2.2  of  a  seven  volts after This capacity  may  material,  disconnected,  or  Endako  most  of  of  the eight  was  five  after  more  day  percent cycles test  been  cathode  than  of  was  powder  indicated Endako  reversible.  to  100 A  there  more  capacity  a  cell  a  two  with months,  becoming  In no  between accurate  between  degradation  l i t h i u m or  was  cycles  of  over  material the  capacity  extra  percent,  loss  due  1.8V.  size.  period.  lasted  The  roughly  micron  the  extremely  only  13.  below  powder  of  the  remainder  twenty  micron  particle  four  to  to  behaviour  of  a  ten  the  2.0  in  was  of  have  damage  volts  an  capacity  and  type  100  second  12  second  to  over  a  the  and  show  present  in Figures 2.7  of  cell  capacity  volts  not  the  between  evidence  was  below  of  would  the  capacity  accurate  cell  2  discharging  thirty  Endako  cell  of  independent  extra  MoS  and  2.088V,  than  the  Endako  voltammogram  showed  2.0  extra  in capacity  which  electrochemical was  rise  indicated  comparison  detected 3.1  as  around  smaller  test,  observed  1.84V  the  discharging  Atomergic  powder  result  above  the  capacity  and  quarters  was  The  1.8V  of  of  current  monotonic  Endako  capacity as  result  an  material,  of  doubled  a  behaviour  constant  essentially  between  size.  a  1.5  heavy and  the  of  the  electrically  e l e c t r o l y t e due  to  36  1.5  1.7  1.9  2.1  2.3  2.5  2.7  V o l t a g e (V) Figure  12 -- C y c l i n g 10-20 ym Endako MoS and 2.7 V o l t s  0  Powder Between 1.5  Constant Current Voltammogram o f C e l l PM-85 10 yA current 58.80 mg cathode o f 10-20 :m Endako MoS Powder 2  The arrow i n d i c a t e s the e x t r a c a p a c i t y not normally seen on the f i r s t discharge o f an Atomergic M0S2 c e l l . The graph shows the f i r s t discharge from 2.05 to 1.5V, and then one c y c l e between 1.5 and 2.7V.  37  1.6  1.8  2.0  2.2  2.4  2.6  V o l t a g e (V) Figure  13 -- C y c l i n g <38 ym Endako MoS and 2.7 V o l t s  9  Powder Between 1.5  Constant Current Voltammogram o f C e l l PM-96 5 yA c u r r e n t 100 mg cathode o f <38 ym Endako M0S2 Powder The arrow i n d i c a t e s the e x t r a c a p a c i t y not normally seen on the f i r s t discharge o f an Atomergic M0S2 c e l l . The graph shows the f i r s t discharge from 2.05V to 1.5V, and then one c y c l e between 1.5 and 2.7V.  -  38  slow leakage of water and oxygen through the O - r i n g s e a l . loss  of  period  c a p a c i t y of more than ten percent over a two month  i s not uncommon because  designed f o r long term Figure  14  the  flange  cells  be a f i r s t  phase  is  lithium  of  times. The c a p a c i t y near 2.087V  capacity,  and  symmetric  suggestive  at  of  ~1.83V,  phase t r a n s i t i o n was The capacity  a  on  charge  single  but i t was  is  some  and  seemed  to  were  not c l e a r  be  s u p e r i o r to the f i r s t  greater.  This  for  the  2.0V  spurred  capacity  was order  capacity.  behaviour  above  discharge,  if a first  of  capacity  The  phase i n t e r c a l a t i o n of  responsible for t h i s  second type  both the t o t a l c e l l voltage  indicated  there  i n t o the host. A very small amount of  detected  been  c a p a c i t y on both s i d e s of the t r a n s i t i o n .  f e a t u r e at 2.463V i s which  had  2  order phase t r a n s i t i o n , as  by the very sharp spike single  not  shows a voltammogram taken a f t e r a c e l l made  c y c l e d more than one hundred to  are  experiments.  with smaller than t h i r t y e i g h t micron Endako MoS  appears  A  and  efforts  extra  Endako  type  because  the  average  to  t r y and  i d e n t i f y the source of the second type of c a p a c i t y .  3.3  E f f e c t of Sample P r e p a r a t i o n The  it  was  sample p r e p a r a t i o n procedure was  r e l a t e d to the e x t r a observed  Atomergic  MoS  trichloroethylene observed this  2  was and  capacity.  cleaned i n Solvex, then  baked  a-phase c a p a c i t y between 2.0  treatment.  examined to see i f  at and  chloroform,  and  750°C. There was 2.1  volts  no  after  1  1  1  1  1  1  1  1  1  Discharge  _  A .  —  r  "  -  Y Charge  1 .6  1 1.8  1  1  1 2.0  1  2.2  1 2.4  V o l t a g e (V) Cycling  a-Phase Endako Powder  Constant Current Voltammogram 25 yA c u r r e n t vL50 mg o f <38 ym Endako MoS  of C e l l PM-60 2  Powder  1  40 An not •  Endako  baked.  a t 2.75V  This  capactity,  2.0  a n d 2.1  was  sample  was c l e a n e d  had a very  potentials  but there  volts  capacity  or around  was n o t p r e s e n t temperature.  The  source  of  reaction  that  impurities  the  the  Endako  involved  where  amount  other  1.83V ( F i g u r e  a t high  in  small  i n the solvents, but of  capacity  samples  h a d shown  was n o s i g n i f i c a n t  baked  naturally  the  sample  2  a n d 2.35V,  no  extra  MoS  MoS . 2  capacity It  some c o m b i n a t i o n  i n t h e powder.  was  between  15). In b r i e f , the  i n t h e Endako  extra  capacity  powder  does  until i t  not  produced  of the  MoS  2  occur i n some and/or  41  3.00  O >  0) CL  2.50 First Discharge Below Two Volts  2.00  co _Q  E _o  1.50  First Discharge  D O O  >  O I  1.00  0.50  0.00 1.6  1.8  2.0  2.2  2.4  2.6  2.8  3.0  Voltage (V) F i g u r e 15 -- Unheated Endako MoS  2  Constant Current Voltammogram o f C e l l PM-83 5 yA c u r r e n t on f i r s t discharge, 10 yA c u r r e n t on l a t e r discharge 77.07 mg cathode o f u n s i z e d Endako M0S2 P ° ^ w c  e r  The f i r s t discharge of the c e l l from 3.0V to 2.0V at 5 yA i s shown i n the graph. The c e l l was then c y c l e d between 2.0 and 2.7V a t 10 yA, but the f e a t u r e l e s s c y c l e s are not shown. The t r i p v o l t a g e was then lowered and the f i r s t discharge below two v o l t s i s a l s o i n c l u d e d i n the graph.  42 CHAPTER  4  ELECTROCHEMICAL EXAMINATIONS  4.1  Attempts There  capacity material which may  to Find  were in  two  the  been  Tests  quartz  (CuFeS ), Most  through capacity. capacity  galena  None  capacity. doped  increase chemical number have  have  been  some  the  MoS  from  o r t h e MoS as  to  extra  2  itself  2  change  i t s  curves  (ZnS), (Cu  u 8  because  minerals  from  chalcopyrite  S),  a r e shown  made  may  and c o v e l i t e  in  Figures  i t h a d no  explained  16  observed  the  extra  2  then  directed  be a l t e r e d  and that  the  C e l l s were  sphalerite  2  which  MoS .  could  p-type,  cell  the chemical potential  be  the  of the minerals  (Cu S),'digenite  these  were  and type to  (PbS),  I t was p o s t u l a t e d  Discharging  way  powder.  i s n o t shown  of  of Endako  semiconductor,  some  i n t h e Endako  Quartz  Efforts  might  capacity,  on s e v e r a l  of the c y c l i n g  18.  There  of  and d i s t i n c t  the observed  chalcocite  2  (CuS).  separate  made  present 2  explanations 2  in  2  behaviour.  were  (Si0 ),  i n MoS  MoS .  modified  electrochemical  be  Endako  contributed  been  possible  or materials  have  have  an I m p u r i t y  reduce  a  to  the  i f  to  2  give  an  i t  the  MoS  n-type  t h e measured  in  t h e MoS ,  t h e Endako  semiconductor  of i m p u r i t i e s  added  that  l i t h i u m was  potential  see  i n a way  both  would  of  to  crystal  to  but  lithium  make  could  2  voltage  i s related  N-type  extra  impurity.  crystal,  present.  a  and the  to the would  the chemical  20  40 Time (hours)  b)  Time (hours) F i g u r e 16  C y c l i n g Cu-^ gS and C ^ S a) Constant Current C y c l i n g of C e l l PM-84 50 yA current 9.80 mg cathode of D i g e n i t e , Cu-^ gS b) Constant Current C y c l i n g of C e l l PM-100 25 yA current 7.52 mg cathode of C h a l c o c i t e , C ^ S  60  a)  3 2 a) cn o 1 o > 0  l-Ax=.2-l  J  1  1  0  I  I  I  4  I  6  I  J L 10  8  12  Time (hours)  b)  3 2 cn o 1 o > 0  —  y  —  r-Ax= 3 H  I  i 5  F i g u r e 17  —  •- C y c l i n g CuS and PbS  —  i  i  1  10  1  I  15  20  Time (hours)  a) Constant Current C y c l i n g of C e l l PM-77 500 yA current 10.26 mg cathode of C o v e l i t e , CuS  •  '  b) Constant Current C y c l i n g o f C e l l PM-33 The arrow i n d i c a t e s an i n c r e a s e i n current from 20 yA t o 200 yA. The time scale of the part of the graph showing the 20 yA discharge was d i v i d e d by ten t o allow the h o r i z o n t a l s c a l e t o be p r o p o r t i o n a l to A x . 24.85 mg cathode of Galena, PbS •  a)  Time (hours)  b) rji D  O >  Figure  0  18 -- C y c l i n g CuFeS  100  50  0 2  and ZnS  Time (hours)  a) Constant Current C y c l i n g o f C e l l RSM-7 100 yA current %10 mg cathode of C h a l c o p y r i t e , CuFeS 2  b) Constant Current C y c l i n g o f C e l l RSM-3 The arrow i n d i c a t e s an i n c r e a s e i n c u r r e n t from 0.2mA t o 1.0mA. The time s c a l e o f the part o f the graph showing the 0.2mA discharge was d i v i d e d by f i v e to allow the h o r i z o n t a l s c a l e to be p r o p o r t i o n a l to Ax. 67 mg cathode o f S p h a l e r i t e , ZnS  4>  46 potential around  rise,  the  ionize  and l i t h i u m  impurities  on  made  found  list.  approximate into  was t h e n  and  then  heated  cooled  the  metal  was  not stable  into  react  2  the MoS , above  t h e powder  MoS .  The c o p p e r  they  were  blackened  p r o b a b l y never  would  found  t h e dopant  material  i n an  was  put  and s e a l e d .  over  two  The  days,  a seven  hour  transport  learned  1 9 7 8 , Moh  that  of  MoS  2  1978) a n d i t  the metal.  with  Copper attempt  two n i n e s p u r e  turnings  t o dope  copper  were  still  melting  After  associated  present,  indicating  t h e 1063°C  Atomergic  turnings.  grey-black lustre  and b r i t t l e ,  reached  of  metals  be v a p o u r  later  list  and attempts  for usually  temperature  h a d t h e same  with  had  1100°C  i n the f i r s t  Products  with  The  (Tsigdinos  with  2  various  mixed  impurities  a  powder,  2  t o 10"" t o r r ,  there  610°C  used  with  b u t i t was  2  metal  2  that  t o Dope M o S  was A l f a  baking,  room  2  MoS  centred  them.  prepared  ratio.  t o about  chemically  4.2 A t t e m p t s  MoS  was  2  evacuated  to  I t was h o p e d  The  MoS  MoS  be  acceptor  compensate  Endako  two t o o n e a t o m i c  tube  could  the  would  the  Vancouver  Atomergic The  which  charge  of  in  a quartz tube,  period.  at  could  Limited  t o dope  this  of the capacity  potentials  Cantest  were  a n d most  that  though the tube  temperature of  copper. The capacity  first  discharge of the MoS ~copper  a t 2.46V,  assuming 2.02±0.02V.  the There  mixture  2  and only  a  cathode  was  was a  first  small  amount  (Ax o f a b o u t  essentially order  had  phase  MoS ) 2  at  no 0.02  about  transition  at  47 ""1.86V  (AX = 0.1)  Figure cycle  2.08  size  as  and  material,  the  1.85  shows  a  cycled  between  but  and by  volts.  The  largest  phase  transition  capacity  at  capacity these  in  the  Figure  14.  mixture  was  1.836V  and  capacity  in  the  were  their  batch  near two  1.6V  the  about  in  the  discharge to  Cu S.  Figure  2  the  be  the  same  chalcocite  be  a  a  features  first There  smaller to  the  be  was  amount  capacity  as  a of  phase  transition. error  1.7  order  single  experimental  20 cell  p o t e n t i a l above  to  1.83V  There  appear  of  a  relative  on  All  of  the  shown  in  in  the  MoS -copper  features,  one  centred  1.808V. M e a s u r e m e n t s  powder  lacked  below  Endako  into  Endako  estimate  volt  at  appear  2.089±0.005V.  within  at  not  what•appeared  extra  other  but  Another  a  capacity  structure, of  of  gone  powder.  charge  2.461V,  and  resolved  the  at  had  Endako  cell  at  the  The  the  of  and  at  The  made  features  voltammogram volts.  cell.  cell  chalcocite,  centred  tenth  of  of  the  shape  did  on  appeared  observations  measurements  the  capacity  ~1.83V,  were  capacity  keeping  centred  the  in  features  2.7  the  same  which  broad  current  1.7  There  the  capacity  signature  eliminated  peak  had  of  voltammogram  after  observed  2.36V  constant  symmetric  volts  that  behaviour  sweep  transition.  of  and  electrochemical  were  2.6  features  regions  the  linear  and  1.83V  the  changed  a  phase  and  other  Endako  is 1.5  the  2.45,  were  19  between  through  which  were  suggestive  clarity  to  make  of a  2  at  of  the  1.83V  a  two  peak  quantitative  position.  of  Atomergic  MoS  2  and  copper  was  prepared  48  I. 5  1.7  1.9  2.1  2.3  2.5  V o l t a g e (V) F i g u r e 19 -- Cycle o f MoS~-Copper Mixture Volts  Between 1.5 and 2,6  L i n e a r Sweep Voltammogram o f C e l l PM-65 5 yV/sec Voltage Ramp I I . 49 mg cathode o f 1100 C MoS -Copper m a t e r i a l 2  The  s o l i d l i n e corresponds to the discharge and the broken l i n e to the charge. The c e l l was not f u l l y e q u i l i b r a t e d at 2.6V before the discharge began. L i t h i u m was d i f f u s i n g out of the host, so the c u r r e n t was i n i t i a l l y negative. The charge c y c l e had been p r o p e r l y e q u i l i b r a t e d .  49  30  1  1  1  1  i  i  i  r  i  20 O > CD CL  10  -  0  -  CO  _o D O O  > X5  Discharge  1 .  J  —  -10  O  A  R  Y  Charge  -20  1 1 .6  1 1.8  1 1 2.0'  1  1 2.2  1  1  I  2.4  V o l t a g e (V) F i g u r e 20 -•  C y c l i n g the Mc^-Copper Mixture Constant Current Voltammogram of C e l l PM-65 25 yA c u r r e n t 11.49 mg cathode of 1100 C Atomergic MoS2~Copper material  50 in the  t h e same way a s t h e m a t e r i a l quartz  which  tube  the  was o n l y  Endako  The c o n s t a n t  material  between  electrochemical baked  4.3  at  Two  was  mixed  a  active  sample  used  iron  the MoS . 2  first  of the at  at  the cleaning  the  resulting  the exact which  same  had  been  as a dopant, contaminated grey  symmetric  peak  was  transition,  the  from  2  powder  but t h i s with  MoS ,  so  Spex  from  FeO. MoS .  2  MoS  later  resulting  A later  only  Industries  was  The  2  with  2  Atlantic  powder  unlike  material  (Ax=0.04  attempt  ten  atomic  I n c o r p o r a t e d was  in  a  first  a t 2.461V, single  b u t none  had  powder  was  phase  that  MoS  phase  2  at  just  the  that  of  i s the only (Ax=0.2)  1.5 a n d 2.7  2.089V  and  There  was n e a r below  a n d 2.3 v o l t s .  first  amount  1.86V  between  capacity  capacity  2.1  at  transition.  a n d some  between  small  cycles  centred  with  a  transition  21. In l a t e r  order  prepared  assuming  and a phase  capacity  some  Atomergic  This-batch resulted  MoS -iron  main a  dope  dope  2  2.02V  resembled  powder  Elements  t o MoS .  in Figure  the  2  d i s c h a r g e of a c e l l  material),  shown  There  to  powder  identical  capacity  volts  made  dull  iron  The batch  of  material  were  to lightly  with  looked  as the  that  temperature  produced  Other  Engineers  was  made  2.7V  except  t o remove  cycling  with  t o be s l i g h t l y  percent  as  t o Dope M o S  first  Equipment  batch  was b a k e d  and  behaviour  attempts  The  found  t o t h e 750°C  current  1.8V  above,  1100°C.  Attempts  iron.  heated  powder  solvents.  described  i t  was a 1.82V.  t h e phase  The o b s e r v e d  51  40  h  E _o 20  h  O >  CL CO JD  D O o  > O  0  h  1 .6  1.8  2.0  2.2  Voltage  (V)  2.4  2.6  F i g u r e 21 -- F i r s t Discharge of M c ^ - I r o n M a t e r i a l Constant Current Voltammogram of C e l l PM-95 10 yA c u r r e n t 6.62 mg cathode of Atomergic MoS2~Iron m a t e r i a l The arrow i n d i c a t e s a v o l t a g e r i s e during discharge. This i s analogous to supercooling,  52 positions sample made  and shapes  (Figure  22)  on t h e Endako  sample  after  of t h e major  i t  were  within  powder  (Figure  had  gone  features error 14)  of the  2  of t h e measurements  and  through  MoS -iron  the  MoS -copper 2  i t s phase  transition  (Figure 20). The  second  behaviour. volts,  There  and  transition first  having  MoS  significant  went  around  any s i g n i f i c a n t  4.4 E x a m i n a t i o n s Reacting materials  Atomergic MoS ;  5 ) . I t was a s s u m e d  was made  similar ratios variety and found  Moh  been  2  unidentified  source  that  of  t o produce  materials have  i n a-phase  and  was  volts.  magnesium  and  Endako  any e v i d e n c e  copper  two  which  of  volts.  several  a material  other  Endako  some p u r e  X-phase.  as  form  in  X-phase,  1 9 7 6 , Moh  1978).  The X-ray  pattern led  capacity,  and  them  mixture  than  A  MoS  2  so an  group  of  non-stoichiometric  to describe  MoS -copper  X-  (as described i n  the extra  can  described  2  yielded  crystals  used  the  capacity  above  of formulas  in  another  the extra  showed  phase  the copper-molybdenum-sulphur  2  Chapter  attempt  other  MoS  and  the  with  1.5  of X-Phase  including:  be  was  1.3 a n d 2.7  t o produce  materials  capacity  phase;  might  t o 750°C  attempts  Neither of these  order  there  between  different above  first  1.75V. No o t h e r  was c y c l e d  i n other  a  recharge,  was h e a t e d  2  capacity  through  1.35V. On  the c e l l  sulphur  capacity.  no  transition  when  had a r a d i c a l l y  2  cell  a t about  Atomergic with  of MoS -iron  was  the  order  present  batch  there  (Grover  are  a  1 9 6 5 , Wang  of the substance to  Cu  1 > 3  8  Mo S„--a 3  53  1  O >  1  1  1  J  00  _Q  0  1  1  1  Discharge  X  r  3 O U  > "D  O  1  10  CD CL  _o  1  v  ~  Charge  -10  1 1.6  1  1 1  1.8  2.0  2.2  Voltage  (V)  1  1  1  1 1 2.4  2.6  F i g u r e 22 -- C y c l i n g the MoS2~Iron M a t e r i a l Constant Current Voltammogram o f C e l l PM-95 10 yA current 6.62 mg cathode of Atomergic MoS2~Iron m a t e r i a l  54 material  which  copper  turnings,  Industries from  different  result  parts  was  the  a  the  in  a  the  tube  was of  features,  that  The  region  capacity  near  of  transition on  the  at  transition.  The  also  showed  these  •1.6V  attributed  almost  two  to  identical There  order  phase  of  the  to  the  was  a  with  the  of  capacity capacity".  the  p  total  (Ax=~1.5  the  days.  The  of  2  for  many  Atomergic had  order  the  a  phase  capacity the  phase material  2  other  MoS .  23,  with  behaviour  at  capacity  but  Li Cu x  the  a  and of  the  Mo S„) 3  24)  extra  near  were  Endako  2.457±0.005V, a  MoS  smaller 2  was  discharge  accounted  of 1 > 3  in  (Figure  pe"ak a t  amount  transition capacity  of  2.087V,  small  X-phase,  in  material  symmetric  present  percent  X-phase  transition  to  two  in  shaken  MoS -copper  some  The  2  be  o  associated  plus  1.84V. A  2  of  .  after  were  first  t t  colours  Figure  a  the  3  amount  cycling  also  Mo S  accounted  quarters  features  near  MoS  small  Spex  but  different  and  of  1 f 3  1100°C,  discharge,  Three  Cu  another  when  discharge  capacity  the  make  X-phase  seen  was  of  0.8V  the  a  from  sulphur  powders  for  Alfa  Cu S.  cycles  capacity. first  first  The  2.00V  discharge  to at  and  first  1.856±0.005V.  first  Later  of  were  material.  pure  distinctly  X-phase  MoS -copper 2  ratio  reheated  structure.  3  nines  tube.  behaviour  Mo S„  molybdenum  days  two  of  mixture  battery  six  two  had  in a  pure  and  for  powder  and  The  nines  mixed  heated  the  together  four  were  was  cooling,  inserted  Incorporated,  Spex  mixture  of  i s copper  for  amount  known from  less  a  2.7  to to  than  five  of  the  cell.  The  rest  was  the  "extra  Endako  55  O >  CL  00 XI  E  O O  > O  1.5  1.7  1.9  2.1  Voltage F i g u r e 23  2.3  2.5  2.7  (V)  F i r s t Discharge of "X-Phase" Constant Current Voltammogram of C e l l PM-91 10 yA c u r r e n t 12.02 mg cathode of M:u, ,Mo S,--"X-Phase" ° 1.434 0  The arrow i n d i c a t e s a v o l t a g e r i s e during d i s c h a r g e . This i s analogous to s u p e r c o o l i n g  56  1  1.6  I  1.8  I  1  1  2.0  1  1  2.2  1  [  2.4  V o l t a g e (V) F i g u r e 24 -- C y c l i n g "X-Phase" Constant Current Voltammogram of C e l l PM-91 15 yA c u r r e n t 12.02 mg cathode of %Cu- M o S -- "X-Phase" L 4  3  4  2.6  57 This  highly  capacity other  allowed  sources The  (or  order  phase  MoS  _ 2  iron  was  transferred  the  transition  battery.  The  capacity  around  l i t t l e  2.46  percent  of  volts.  Between  2.3  the  error,  cell  on  an  equal  discharge  Constant  current  of  feature  on  the was  1OmV  hysteresis  Just what  percent i t was  without  until  the  X-  through  a  of  lithium  the  brought by  through  extra  in  first  charging  the  lithium  centred  slightly  over  half  of  2.088V. in  voltammograms, feature  of  such  was  the  Endako  i t when  the  22  first  The  sharp  i t  was  24),  including  increased  Figures  the  cell  the  was  width  discharge  which  indicated  not  perfectly  diffusion..  order  1.5  and  phase  followed  t r a n s i t i o n s was  within  transferred  the  were  centred to  that  and  between  rise  was,  when  20mV  by  was  lithium  features  capacity a  there  showed  and  skewed  be  capacity  removed  about  The  were  expected  amount  was  but  at  2.7V  voltammetry  cell.  to  extra  and  (Figures  the  appeared  the  as  charge  wide  in  symmetric,  this  driven  removed  no  made  results.  produced  or  Endako  be  appear  as  later  which  charged.  tail  was  cell  twenty  experimental  in  not  to  extra  charged. About  peak  the  the  ninety  the  be  material had  did  mixture) About  could  probably  obscuring  into  of  measurements  capacity  transition.  that  into  capacity  Endako  the  source  detailed  of  extra  phase  fully  concentrated  clearly  by  2.7V  was  transition a  shown  diffusion in  many  22  and  24.  The  width  proportionately  with  the  current,  of as  expected. The  Endako  powder  had  what  appeared  to  be  single  phase  58 capacity the  both  MoS -copper the  transition  originally  had  disappeared  to  i s not  the  percent  cycled  many  order  transition  both  charge  accounted  and  for  There  Endako  ninety  eight being  very  recovered  4.5  Other  extra  combination  extra  of of  copper,  order,  electrochemical  energy  percent  major phase about  which the  was  the  near  had  first same  1.83  on  volts  capacity.  in  the  cycles  required This  the  showed to  i s much  efficient  of  about  charge  the  better  than  0-phase  MoS . 2  Studies capacity  was  molybdenum,  initially,  appeared. behaviour  and  but  non-reversible  capacity  the  of  is above  for  cell  it  It  single  voltammograms  iron,molybdenum,  compounds  of  discharge.  ninety  region  but  the  accounted  features  hysteresis  the  on  Endako  The  material  capacity  The  capacity  did  capacity  range,  with  X-phase  phase  Many  Electrochemical  combination  first  of  an  combined  percent  little  phase  capacity.  in  had  cycles.  associated  single  five  percent  approximately  ternary  the  capacity.  the  The  The  2.2V  dozen  transition  as  X-phase  to  single  Endako  discharge.  about  was  extra  cell  and  the  capacity  times.  2.1  one  directly  the  sample  i t . The  the  than  order  transition,  2  above  that  first  phase  MoS -iron  in  extra  of  the  The  not  less  the  below  twenty been  of  but  assume  transition  features  below  capacity  after  reasonable  region  and  material.  2  below  the  above  of  produced  and  sulphur.  they  phase  had  to  as  Both go  transition  The the  sulphur  two  from well these  a as  were  through before  a  a the  nearly  identical  materials  indicated  59 that  the extra  Endako  molybdenum-sulphur The  first  could  order  have  molybdenum  been  sulfide this  above  (Jellnik  1961,  capacity  above  Attempts and  with  sample.  transition  HN0  3  reaction  a n d some o t h e r  sequisulfide, was made  i s  2  from  to  the  metal.  h a d t o go t h r o u g h which  produced  a  substance.  Mo S ,  essentially  de J o n g e  related  and not t o the other  these materials  a displacement  610°C,  material  was p r o b a b l y  environment  sulfide  Molybdenum  capacity  3  which  i s the stable  t h e e l e m e n t s . Even a  1970),  layered i t h a d no  though  compound significant  1.3V. t o make M o S 3  (Chevrel  4  by e t c h i n g  1974)  failed  some X - p h a s e to  produce  with a  HC1 pure  60 CHAPTER  X-RAY  5.1  X-ray  EXAMINATIONS  Diffraction  X-ray  diffraction  techniques Incident  5  for  X-rays  determined  by  is  one  determining  of  the  the  between  spacing  X-rays  size  the  of  the  determine pattern  The can  be  of  the  then  be  at  atoms,  positions. to  with  to the unit  directions  of atoms.  The  shape  and  and the type  data  and  formula  of  c a n be u s e d  X-ray  "fingerprint"  diffraction an  unknown  beams  are detected  o f t h e c r y s t a l . The  and the s p a c i n g  relation  between  planes  d, i s  X = 2 d sin 9  where rays,  29  in  terms  These  i s the angle  a n d X. i s  indices,  to  materials.  intense X-ray  angle  in  empirical  The  known  cell  a crystal.  on t h e  crystal  the intensity  which  the s c a t t e r i n g  the  used  f o r comparison angles  depends  important  of  planes  i n i t . I f the  atomic  also  related  between  cell  i s known,  can  substance  unit  o f t h e atoms  crystal  structure  by t h e m a t e r i a l  of the s c a t t e r e d  positions  most  are scattered  intensity of  the  (hkl),  the  reciprocals  are  the incident  wavelength  can then  of the three  indicies  between  (6)  of  be u s e d  the  radiation.  to express  lattice  vectors  defined  by  of the f r a c t i o n a l  and s c a t t e r e d  of  Cullity  intercepts  the d  the  which  Miller spacings  unit  (1959)  X-  as the  cell. "the plane  61 makes  with  indexed thesis  as  part  will  particular  5.2  the c r y s t a l l o g r a p h i c axes."  only  X-ray  cleaned  smaller  angles.  Standards' be  nearly  visible. examined PbS, MoS  2  were of  the  find  CuS,  may  this to  a  have  been p r e s e n t  were  Search  masked  Diffraction  lines pattern  impurities.  The  2  amount. when  and  3R  X-ray  was  galena,  polytype  of these  to  still  diffraction  b u t none  stopped  present.  Manual proved  extra  Cu S,  the  a t t h e same  Powder  the  chalcocite,  powder  on  File  expected  detectable  lines  first  in  s i g n a l s would have  Endako  a l lchecked,  of the  impurity  diffraction  Committee  i n any  fruitless.  major  identifying the  t o t r y and  present  of  referring  the subject  the  other  Diffraction  Instead,  was  and q u a r t z  2  which  in  were  was  many  Joint  useless  patterns  be  were  the MoS  covelite,  of  were  line.  Quartz  Powder  the Endako  would  t h e i n d i c e s a s a way  lines  Using  a n a l y s i s , but the text  Endako powder  but there  Unfortunately,  patterns  Examinations  examinations.  sample,  any  use  diffraction  Preliminary The  of the data  Several  of  materials  investigations  i t looked  as  i f  they  62 5.3  Attempts The  heating  t o Dope  first  MoS  i s  2  with  the copper  the  X-ray  the  Powder  with  t o form  Diffraction used  new  File  pattern  1 > 38  to synthesize  references  class  of m a t e r i a l s  system MoS  2  attributed  are heated and  found  called  by  Cu S.  not  may  a diffraction  crystalline  were S,  or  Mo,  pattern i f  the  diffraction  dozen  degrees  lines  made Mo S  with 3  was  lines  prompted  the  elements.  X-ray  lines  to a  in a  of MoS  However,  b u t may  i f the material  were  2  other  had  either  too small  i n a scan  from  although  of Cu S, 2  Cu  A  evident poorly t o be a n  f o r t h e X - r a y s . The s o u r c e  detected  been  material. n o t be  is  are  the  Cu S  2  sample,  and X-phase  2  but  MoS -copper  particles  X-  2  pattern,  the  when c o p p e r a n d  p r o d u c t s a r e MoS ,  2  in  that  lines  t h e known p a t t e r n s 3  results  from  showed  n o t be i d e n t i f i e d ,  and M o S „ .  There  of the extra  same  to Cu S.  grating  that  o f 2e c o u l d  2  (1978)  correspond  be p r e s e n t  Alphabetical  copper-molybdenum-sulphur  2  electrochemically  one  the  i n the the MoS -copper  found  effective  compound  in  2  and  and these  The d i f f r a c t i o n  2  reacts  t o MoS , and  the others.  several  together the expected  did  in  of  Moh  lines  material  attributed  these  and  X-phase.  diagram  prepared  phase, were  phase  this  failed  Many o f t h e l i n e s  Search Manual  3  involved  2  This  temperatures  were  Mo S„,  MoS  1100°C.  compounds.  between  f o r Cu  Other  The  to  t o t r y and i d e n t i f y  and  attempt  Atomergic  at high  pattern  correspondence  the  dope  copper  unstable  excellent the  to  diffraction  were  2  attempt  i t together  because  Index  MoS  of  10 t o 90  comparisons 1 < 8  S,  CuS, Cu,  63 The to  later  750°C  this  mixture  showed  material  of  only  also  MoS MoS  and  2  behaved  and  2  as  copper X-phase  i f  which  was  heated  lines,  even  though  there  were  some  Cu S  i n the  literature  which  2  present. There can  be  used  are  used  by  to  a  sulphur.  variety  identify  Grover  describe  a  the  (1965),  reports X-phase.  Wang  ternary  Other  of  and  system  of  researchers  compounds.  Comparisons  information  and  Moh  were  then  made  collected  investigations  of  the  extra  all  parameters  is  presented Wang  with  i n Appendix  and  Moh  parameters  composition  of  that  the  this  formula.  et.  to  two,  and  hexagonal  with  the  X-phase led  and  to  a=9.73&  Cu Mo S  the  lattice  be not  published of  the  summary  of  thesis  hexagonal  lattice  n  parameters  as  (1977)  a = 9.713A  and  a=9.735A  and  2  of  a  large  agreement  mixture  hexagonal number  by  of  with  Chevrel  three  or  four.  from  one  hexagonal  with  described  C=10.221A.  the  indicated  varied  was  C=10.213A,  i n the MoS -copper 2  5  was x  claimed  but  3  performed where  n +  also  in perfect  was ^,  a  2  C=10.22A. A  and  prepared  course A  to  this  CuMo "S ,  C=10.2A. Yvon  determination  (1978)  the  of  They  Cu Mo„S  found  and  n  on  showed  with  the  text  graph  parameters  the  X-phase  was  on  the  was  molybdenum,  capacity.  i n the  to  work x  Moh  between  C=10.22A.  and  material  Other  graphed  a=9.73A  the  stoichiometry  a l . (1971)  Chevrel  as  this  used  and  similarly  during  Endako  "X-phase"  I.  indexed a=9.73A  (1976)  described  data  lattice  term  copper,  the  the  The  Cu  and The were unit  1 < 3 8  Cu  Mo  1 > 4 7  lines  3  S^  Mo S„ 3  of  the  indexed,  and  cell  materials  with  a l l have  64 approximately difficult material  Mo S  had  also  3  other  characterized  the  chemical  material,  and  slight  Usually, but  not  the the  The  the  to  had  that  of  the  parameters to  were  very  small  other  amount  weak,  the  of  of  3  MoS  unidentified  errors may  X-phase, pattern  C=10.218A,  lines  in  and the  the  to  same be  due  samples. published,  ' the  initial  a  material  very  hexagonal  which  close lattice  corresponded  There  there scan  the  analysis.  was  1971).  (Chevrel  the  led  could  produced  The  he  of  the  are  was  that  but  have  of  the  in  to  chemical which  were  quality  material  f l  present,  2  The  sample  material.  and  Mo S«  the  parameters  a  or 3  diffraction  1 > a  identify  indexed,  stoichiometry  the  expected  only  attributed  lattice  3 8  Cu  it  materials  that  a  make C u , . M o S ,  a=9.729A  approximately  not  of  patterns  of  to  positions.  parameters  made  X-ray  had  being  of  in  diffraction  above  is possible  variety  an  Yvon  formulas  to  the  composition  lattice  attempt  of  atom  It  difference  identification which  the  i s unknown.  different  a  which  alone  making  mixture.  2  of  parameters,  diffraction  determined  data  lattice  MoS -copper  compounds  4  measurement  to  same  X-ray  the  best  Cu _ 9  for in  The  the  was  were  from  also  only  10  to  a two  90°  of  26. Two  attempts  first  attempt,  extra  Endako  evidence second had  which  of  either  in  which  made  produced  capacity,  attempt,  lines  were  to a  resulted MoS did  2  or not  material in  iron. show  its diffraction  dope  a  MoS  the  pattern  with  which  pattern The  2  extra that  The  showed  which  material  iron.  the  showed  made  capacity,  in  no the  only  corresponded  to  65 either  MoS  first  material.  of  four  strong  pattern. with  or the strong  2  However,  lines  The four  which  lines  had  could  of a m a t e r i a l  was  the  attributed et.  a=9.564A  a l . (1976)  Fe .66Mc>3S«,  and  0  and  C=10.30A.  the  four  Endako  used  It i s likely  extra  capacity  capacity.  because similar  for  scan  FeS p y r i t e ,  (Wilson  1963),  (Guillevic  are  lines.  from  way  of the source  did  have  determined  the only  of the MoS -iron 2  1974), Except  t h e JCPDS  3  Mo S , 2  3  where Powder  3  indicated,  cell one iron-  3  Guillevic  4  describe  h a d a = 9.55A  which  produced  produced  the extra  X-phase not  6  (1971)  to  FeMo S  led  allow  to  a  lattice from  this  positive  diffraction  lines  parameters  very  the l i n e s .  material  FeS, F e S , 7  and Mo S«  File.  the  identified  mixture. Published  (Grover  2  5  also  other  FeS m a r c a s i t e , c u b i c Fe Mo  are within  FeMo S ,  of the four  of materials  F e S , was  said  that  first  Chevrel  to  lines  the  C=10.27A) b e c a u s e i t  the material  diffraction  to the parameters  the  extra  i n t h e same  a variety  Troilite, from  diffraction  X-ray  identification  that  in  parameters  (1977)  the  no e v i d e n c e  called  Also,  same  of  on a h e x a g o n a l  (1978)  C=10.273A  Schollhorn  showed  seen  (a=9.52&,  these  scan  parameters  X-phase.  and  the  scan  be i n d e x e d  Moh  Y-phase  to  in  been  These  that  molybdenum-sulphur analogous  seen  the second  and C=10.37£.  a=9.5lA  percent  lines  8  Fe S ,  1975),  failed a l l the  patterns 3  4  FeMo S„ 2  to identify iron  FeMo  the  patterns  66 5.4 D e t e r m i n a t i o n Neither behaviour through the  t h e X-phase  of  a  of L a t t i c e  the  first  cell  described  in  technique  provided  pattern  The  transition  was c y c l e d  to  insure  which  produced  cell  was a t t a c h e d allowed cell  flowing  through  x  of  3  a  states  lines.  a  i n turn  was  fully  observed  and  calculated  and  order  phase  t h e 1.86V p h a s e  conversion  to the material Afterwards,  the  This  when  the M i l l e r  as g u i d e s .  was  was u s e d  indexed.  The  made.  indicies  A  least  was  made  indices.  A  using  guess  repeated  was  the  squares  generated  agreement  spacings  of the  and u s i n g  to help  was  PAR.  microampere,  assumed then  and  the current  of the c r y s t a l  procedure  d  s e t on t h e  o f one  and t h e i r  pattern  pattern  the  lattice.  t o be h e x a g o n a l 3  o f more  X-ray  charge,  p a t t e r n was t h e n  and M o S „  indices  using the  obtain  first  capacity.  t o guess  diffraction which  of  of the  to the order  of the l i n e s  parameters,  to  of  through  the a and c parameters  the angles  made  in-situ  to the potential  the c r y s t a l  f o r Cu2_ Mo S  calculated these  made  i t h a d gone  173 P o t e n t i o s t a t / G a l v a n o s t a t  of the d i f f r a c t i o n were  The  t o be e q u i l i b r a t e d  i t reduced  by a s s u m i n g  estimate from  t o a PAR  were  possible  few t i m e s phase  until  showed t h e  Investigations  between  Endako  was c o n s i d e r e d  2.  expansion  full  the extra  Attempts  patterns  a  to equilibrate  the scan  lines  i t  various  and a continuous  cell  mixture  capacity  Chapter  a way o f d i s t i n g u i s h i n g  transition  iron  transition  made  at  _ 2  transition.  in this  diffraction  and  phase  formed  diffraction  The  Endako  material  X-ray  was  or the MoS  extra  order  Parameters  until  the the  between  the  estimated  by  67 computing two  values.  fit the  the  to  a  A  of  I t was x  number  sum  the  then  squares possible  distribution  2  of  indexed  correction  had  to  before the  The  diffTactometer  relative the  to the  X-ray  cell  measuring  plane  of  forces a  be  the the  distance  m  R  173mm,  9  angle. the  is  i s the  m  The  known A  their  the  out  and  Miller  capacity  was  0.00978  showed  calculated reported for  Mo S„ 3  lattice phase data  by  the  for a Mo S„ 3  these of  the  squares  by  construction  by  B  MoS  i n Appendix  which  charged  to  The  only  lattice  a=9.202A about  calculated  Chevrel scan,  2.700V.  from  (1974) and  the  extra x  the  the  phase  cell  were Endako of  observed  and  Mo Si,,  as  for  published  X-ray  and  value  2  3  numbers  percent different  also  the  lines  C=10.877A. T h e s e  and  using  C=10.891A  parameters  0.1  by  II.  The  between  Bragg  lines.  2  and  produced  agreement  true  diffraction  a=9.l96A  the  detector--  determined  are  material  the  the  of- t h e  given  of  of  (7)  to  is  the  out  m  sample  of  angles  6 }  9^ c o s  the  estimated.  The  6 given  - tan  be  line  measure  material  from  of  observed  to  positions  were  parameters  of  active  positions  excellent  Yvon,  material.  goniometer.  was  patterns.  sum  could  aligned  correction  plane  fully  are  parameters  of  the  of  comparison  the  G-g  parameters  when  to  a n g l e , and  of  a  the  measured  indicies  Lattice obtained  distance  measured  summary  made  was  6 = R {sin 0 where  differences  t o make  dividing  lattice  axis  by  by  the  lines.  positions powder  of  from  the  .converted  X-  the  intensity  data  is  in  68 qualitative intensity  agreement data  preferential The  with  were  small  orientation  lattice  that.  of  The  enough powder  parameters  only  were  differences  to  in  be  the  also  in  the  attributed  to  cell.  computed  above  and o  below and  the  phase  c  axis  the  indicating phase at  a  transition. was  f i t .  t r a n s i t i o n and a  2.100V  10.725A.  fair  2.050V. H e r e  At  in  was  The  The  the  x  cell  region  9.754A  the  and  axis  value  2  potential  of c  a  single  was  was  9.358A  was was  0.020,  below  phase  10.589A  the  capacity  with  a  x  of  2  0.00955. The 1.800V with  extra and  a  x  lattice  a  of  2  Endako was  poorly  defined,  of  Observed  and  lattice  parameters reported  a=9.728A lattice  was of  the  3  had  a  L i Mo 2  2  3  .  of  tenths  to  cell  were  Chevrel  have  and  of  no to  a  et.  no  the  were  at  (1971)  It 2  2  It  the  it  from  of  cell by The  a  percent  of  for  Li Mo S 2  size  2  the  on  the  unlikely Mo S 2  possible and  size  --  3  of  be  material same  and  26.  because  was  arose  the  published  3  the  differed  would  Li Mo S  of  broad  60°  the  was  discharged  approximately  either  at  10.553A  and  half  only  was f i t  lines  degree  al.  capacity.  c  positions  data  be  and poor  with  lines.  would  discharged  data,  within  however  diffraction  corresponded  unit S  two  listed, the  lines  line  by  9.795A  observed  coincided  obtained  fully  rather  predicted  1.800V m a t e r i a l  discovered Li Mo S(,  as  be  a  the  C=10.525A,  and  intensity  2  much  was  they  was  to  diffraction  or  as  those  to  the  almost  that  This  parameters many  case.  calculated  0.0398.  because  capacity  was  3  that  that as  it did  69 There expand  as  was the  and  i t grew  in  the  order  to  the  least  cell  as  was  volume Many n  same  sized  one  of  as  the  intensity  hoped,  explained  for  the  fully  with  of  by  in  same c o n c l u s i o n :  was  Mo S„. 3  on  the  showed  charged  on  Cu„  behaviour (1977).  collection 6,  the  but  the  source  of  Mo S„ 3  identify lattice the  agreement  with  produces can  was  extra  the  also  be  structure  Eventually,  were  the  and  3  information the  metal  Mo S«  techniques, his  is a  the  capacity  3  There  as  unit  to  which  Mo S„.  of  M  of  excellent  Endako  not  the  parameters  material  extra  work  basis  lattice  were  the  approximately  difficult  i n t e r c a l a t i o n in  Chapter  the  the  The  Yvon's  data  it  At  discharged  that  where  s i x , have  solely  3  Schollhorn  Schollhorn's  to  first  added.  MMOnSn+i'  makes  Mo Si,  capacity. terms  type  the  though  parameters  is  increase  capacity.  fully  indicate  to  2.700V  large  3  does  at  3  876.97A . E v e n  lithium  two  both  the  of  crystal  through  The  lattice  more  materials  electrochemical  discussed  data  for  analogy  paper  the  which  a  went  3  the  the  797.5A  was  872. 4A" .  to  as  the  i t s s i n g l e phase  volume  from  However,  in  of  battery  was a  of  integer  Endako  the  cell  data  data  extra  some  lattices,  parameters.  the  and  of  I t was  volume  fits  these  cell  2.100V. T h e r e  increases  i s an  unit  at  materials  and  the  discharged.  1.800V h a d  squares  precise  was  for  3  unit  at  trend  813.4&  transition  material  on  cell  crystal  2.050V  by  a  "found problems  data in  a  with  as  will  also  indicated  Endako  be  capacity  70 5.5  Intercalation Further  the  extra  the  in Mo S„ 3  X-ray  Endako  Mo S„  examinations  capacity.  indicated  3  intercalation transition  and  either  where  2.700V  a s i x hour  were  taken  o f two  Figure cell  As  (104)  changes  line  33.90°.  line  from  one o f t h e s e  of  is a  same being  at  line  lithium  first  greatly  such  the reversible  also  shows a  small  in  an  1,800V t o  as the  2.20V,  be  t h e same at  while the  Similarly,  35.72°  the  t o 35.43°  and  reappear  at  order  transition,  different  parameters  the c r y s t a l  with  same  lattice  Miller  is  i s inserted,  intercalation.  which  side  approximately  the host  the lithium  though  on e i t h e r  the  have  changes  Y e t , even  the l i n e s  lines  a t 33.30°  13.92°  range.  first  with  i s an  voltage  26  to  indexed  as  Figure  33.01°  in a  that  and  dropped.  transition,  insertion line  o r an  of t h e (101) l i n e  to the other.  T h i s means  altered  from  ten  i s altered  and the c o r r e s p o n d i n g  intensities.  charged  appeared  lattices  structures  can  reaction  scans  over  from  content  order  phase  minutes  to  13.67°  be e x p e c t e d  the t r a n s i t i o n  indices,  2.04V  a  a  confirmed  and every  (104) l i n e s  a r e two d i f f e r e n t the  was  d i s c o n t i n u o u s l y from  would  as  there  from  was  was  angles.  disappeared  and  were  the behaviour  rose,  moved  As  of  2.09V  of of  capacity  a displacement  cell  period  o f t h e beam  (212)  there  shows  voltage  intensity  X-ray  ranges  t h e (212) and  the  the  25  voltage  shows  an  2.45V  near  predictions  experiment over  the  capacity  These  properties  electrochemical behaviour  that  the  involving  intercalation.  The  explored other  is  caused  the not  and as  Figure by  26 the  I I I I I I  13.0  14.0 20(°)  13.0  14.0 20(°)  I 1I I 1I 1  13.0  14.0  I I I I I I I  13.0  20(°)  14.0 20(°)  I I I I I I  13.0  14.0 20(°)  F i g u r e 25 -- (101) D i f f r a c t i o n Line Between 2.04 and 2.2V C e l l PMX-11 ^10 mg cathode of "X-Phase" m a t e r i a l The diagrams correspond to 2.04V, 2.103V, 2.109V, 2.128V, and 2.20V respectively.  to c D -•-» D  0) C  Figure  26 -- (104) and (212) D i f f r a c t i o n Lines Between 2.04 and 2.2V C e l l PMX-11 ^10 mg cathode o f "X-Phase" m a t e r i a l The diagrams correspond to 2.08V, 2.108V, and 2.20V r e s p e c t i v e l y , N3  73 cell  case  and  Figure lines  as  27  the  2.1V.  These  the  o f 29 a s  3  structures  near  continuously is  changed.  2.46  vary This  intercalation. transition  was  potential  was  lines  because  crystal  have  lattice X-rays  flow be  order  the  the l a t t i c e  The  can  lithium with  the phase shows  as  the  the cell  positions  20,  while  of  which  is  current  is  parts  and thus  of the c r y s t a l  of the  different  then  diffracts  angles.  and  a s on d i s c h a r g e ,  c l a s s i f i e d as an  29  Different  contents,  i s not g r e a t l y  phase- t r a n s i t i o n ,  charge  effects.  part  different  crystal  of  below  of  are broadened  lithium  Each  degrees  The  lattice  (212) l i n e s region.  such  see.  associated  Figure  The  figure.  lines  different  this  0.05  of d i f f u s i o n  at s l i g h t l y  on  from  to  the  capacity  (104) and  about  i n some,  different  normally  phase  through about  two  and  varied.  as the c o n c e n t r a t i o n  intercalation.  by  parameters.  Since first  instead  of the  but  28  2.5V by  was  hard  and  diffraction  flowing  and  volts,  single  to detect  The  effect  have  swept  shifted  difficult  lines,  not  also  movement  positions  in a l l  (212)  Figure  between  of l i t h i u m  i s the behaviour The  2.6V.  cycle  their  system. (104) and  to  does  i t s size  continuous  the  2.3V  t h e amount  subtle  system  4  changed  i s present  i t is a  from  of the  on a d i s c h a r g e  slowly  change  lithium/Mo S  positions  i s charged  lines  (101),  of the i n t e r c a l a t i o n  the  (223) l i n e  a degree  position as  shows  the c e l l  shows  half  i s not part  distorted,  since  as  many  the lithium/Mo S„  intercalation  3  battery.  even  i n the  coulombs system  can  1  1 1  I  I  I  _ CO  _  (212)  o *JQ  (104)  D  CO C CD  LA;  "/Ay I 33  I  I 34  I  -  I I 35 36  20(°) Figure  27  --  (104)  and  (212)  D i f f r a c t i o n Lines Between 2.4  C e l l PMX-11 ^10 mg cathode of "X-Phase" m a t e r i a l The diagrams correspond to 2.4V, 2.44V, and  and  2.6V  2.6V  respectively,  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  I  CO  o o CO  c  46  47  48  20(°)  46  47  48  46  20(°)  47 20(°)  I  48  46  I  I  I  47  I  I  I  48  20(°)  F i g u r e 28 -- (223) D i f f r a c t i o n Line Between 2.5 and 2.1V C e l l PMX-11 ^10 mg cathode of "X-Phase" m a t e r i a l The diagrams  correspond to 2.507V, 2.44V, 2,41V, and 2.12V r e s p e c t i v e l y ,  111111111111111  33  34 35 20(°)  36  111111111111111  33  34 35 20(°)  36  III  1111111 33 34 35 36 20(°)  F i g u r e 29 -- (104) and (212) D i f f r a c t i o n Lines Between 1.84 and 2.08V C e l l PMX-11 ^10 mg cathode o f "X-Phase m a t e r i a l The diagrams correspond to 1.84V, 2.04V, and 2.08V r e s p e c t i v e l y .  77 The been  MoS  driven  extra  _ 2  iron  through  Endako  conversion  Mo S„.  However,  could in  be  the  the  capacity,  phase 3  mixture  pattern, the  phase and  few  the  of  because and  estimate  of  lattice  observed  were  within  patterns  from  the  of  so  also  lines  the  to  i t  the  lines  the  was  with  the  after  appeared  the  number  difficult The of  the  after  the  intercalated Mo S„ 3  of  those  system  other  to get  lines  X-phase  i t had  produced  lithium  from  large  parameters.  made  which  that  experimental error  cells  X-rayed  transition  corresponded  very  detected  was  lines a  that seen  good were  in  material.  the  78 CHAPTER  R E S U L T S AND  6.1  Interpretation The  discovery  experiments source.  materials  iron  or copper, These  or  the material  was  probably  was  present.  MoS  with  irrespective  been that  formed was  copper  a  binary  as a result seen could  with have where  remains  and reproduce i t s could  o f MoS  were  structure  iron  could  have  as  seemed  of the f i r s t the  been  produced  analogous  essentially  i t  gave  order  to  phase  the  i s altered  environment  of  the  to this in  could  two have  transition Second, MoS  2  the  a to p  although the  I t was  needed  was  rise  phase  t h e same.  lithium  result  that  materials.  the structure  capacity  t o b e t h e same  that  molybdenum-sulphur  a  indicating  when  a  X-  through  Endako  produced  environment  the molybdenum-sulphur  either  t h e same  1.8 v o l t s ,  I t was o b v i o u s  been  produced  with  2  brought  the extra  crystal  or  both  be  essentially  around  capacity  environment  transition  composition that  This  they  produced  of the metal.  First,  transition phase  2  motivated  copper-molybdenum-sulphur  after  molybdenum-sulphur  capacity. ways.  the  preferred  Endako  capacity  a l l produced  which  the  capacity  the heating  transition  extra  reacting  local  from  phase  this  during  behaviour  that  The  that  powders  order  Endako  t o t r y and i d e n t i f y  made  electrochemical first  of the extra  learned  from  DISCUSSION  Results  designed  I t was  phase.  of  6  possible  f o r the extra  79 Endako the  capacity  could  only  exist  metal  stabilized  crystal. X-ray  diffraction  understanding found were  to  greatly  were  also  alter  The  a complex  regions  was  of a  Endako  intercalation  first  percent  of  source  o f t h e c a p a c i t y . Many  that  the  these.  There  measured for  insufficient  lattice  source  of  was  Mo S„  and  3  materials The  data  i t  could  the  was  not only  expansion, which  but  d i dnot  material  published  for Mo S„, 3  identify  o f t h e m e t a l - M o S -^ n  and there  extra  and that  was  charged  t o unambiguously  Endako  excellent  was  n+  a  capacity  published that  compounds  was  one o f  between  by C h e v r e l one  the  possibility  agreement  unlikely  be a b e t t e r  literature  fully  those  sizes,  also  intensity  better  where  transition  of the  this  similar  a  lattice.  however  very  was  system  lattice  order  parameters  0.1  permitted  c a p a c i t y . The c a p a c i t y  continuous  the host  lattice  within  experiments  of the e x t r a  be  there  there  had  i f another  of  the  (1974)  the other  f i t to the data.  contained  references  to  metal-Mo  S ,.,  n n+1 materials  which  Schollhorn's Mo S„  partially  (1977)  3  Mo S„  was  3  (1979)  was  which  (1977)  claimed  came  from  similarly  had  been 3  on  copper  data  from  Yvon's  in Cu  be  later  prepared  Mo S„ 3  Mo S„ 3  of  samples in  metals  Confirmation  in that  Schollhorn's  were  used.  establishing  and S c h o l l h o r n ' s  i n reasonable  crystals.  compounds.  3  work  compounds, was  Mo S«  on a l k a l i  interest.  successful  of s e v e r a l M o S „  work  to  s u c c e s s f u l work  of p a r t i c u l a r  the host  in  properties  were  agreement  Yvon the 1979 with  80 The  quality  primarily clear  because  data  can  voltammogram yet  i f  ten minutes  work.  The  although It  of  was  of  severe  only  be  one  cycle  from  was  obtained  cycle  constant  to  two  were  were  followed was  by a d r o p  a second  as  large  the  Mo S .  Endako  Mo S .  9  3  building the by  These  a  blocks  blocks, sitting  crystal type  be  one and type  features. general  the data,  similar  but  discharge of  capacity  and then  two t o  there  three  and X-ray  Endako  times  similar  on  of  forming atoms  faces.  conclusion  i n which  be  came  of the extra  description groups  of  a rhomboid  forming  Each  to  data.  Yvon's  unit  of s i x equivalent  two s i t e s ,  with  analyses  capacity  of t h i s  consist  the sulphurs  sets  better,  the  of the behaviour  based  t h e rhomboid  two  Schollhorn's  capacity.  i n support  and t h e molybdenum  near  had  roughly  Endako  crystals  with  a  of a v o l t ,  of Schollhorn's  can  days,  i s i n q u a l i t a t i v e agreement  q u a l i t a t i v e explanation capacity  several  was a r e g i o n  of the extra  evidence  sweep  of from  of electrochemical  the source  the discovery  A  Cu  of the extra  Further  a  few t e n t h s  This  combination  established  There  of capacity  as the f i r s t .  The  with  of a  region  behaviour  3  different.  Usually,  c y c l i n g was  cell  t o show  poor,  linear  in  some  3  considerably  a  time  determine  supposed  problems.  b l u r r i n g of the  of the lithium/Mo Si,  that  quite  lasts  current  characteristics graphs  was  from  of the c e l l  some d i f f u s i o n  possible  data  diffusion  was a t y p i c a l  data  there  Schollhorn's  an  the copper  Mo S 6  8  inside  octahedron  cell  sites,  of  of  the  c a l l e d the could s i t .  81 The  type  one  sites  concentrations. the  amount  forced  out  The  the  by might  the  one  type  the  will  drop  one  when  occupied,  the  and  can  f i l l .  The  a  one  and  type  repulsion might two  be  between  adding ions  more  if  already  the  host  structure.  with  the  adding it  two  lithiums  than  which add  the  two  then  has ion  to  to  as  copper  was  drop  lithium  into  intercalated  atoms  ions  of  could  i s put  into  one  one  two  two  would  be  each  half and  cell  capacity  this  Mo S 6  to  lithiums  the  would  unit  8  add  a  i n type  which  not  has  If the  order  phase  greatly  alter  is  associated  I t may  lithium  a  of  correspond  cell.  two  type  site.  this  i t need  the  into  redistribution  and  in  repulsion  major  atoms,  ions  than  sites  first  of  type  this  a  one  are  This'  type  of  sites  between  greater  a  the  potential  the  sites.  in type  of  cell  type  repulsion  prevent  filling  The  be  be 2.46V  until  two  may The  with  the  might  favourable  a  copper  rose  system  quarter  cell. of  in type  About  two  One  unit  site  ions  to  the  repulsion  possible  transition,  is energetically  cell  as  guest  low  system.  the  associated  i n each  causes  of  phase  that  sites.  be  t o move  transition  at  sites  of  copper  electrostatic  present, the  claimed  lithium  lithium  some  intercalation  continue  two  sufficient  positions  the  could  i t will  a  the  first  many  two  3  with  sites  as  type  lithium/Mo Si,  electrostatic  sites type  the  Yvon  capacity  s i x type  the  filled  positions.  of  so  a l l s i x of  total  the  first  sites.  of  i n c r e a s e d , and  represent  ionized,  filling  was  analogy  capacity  preferentially  occupancy  behaviour  explained  are  The  copper of  were  to  be  that  a  unit  positions type  to  one  rather site  82 occupied.  The  transition to  the  would  limit,  1.83V  may  cells  then  Li  represent  is  some  no  phase  capacity  represent  probably  imposing  there  single  the  Mo S .  f t  6  filling  The  8  interactions  sort  of  evidence  order  below of  small between  on  available  the to  the  the  phase  unit  cell  features  near  different  unit  lithium  guests,  support  this  but last  supposition. Cells MoS -iron  material  2  the  made w i t h  battery  pointed  out  always  kept  below 1.8V  this  capacity  above  potential  above  terms  of  Mo S .  The  metal  present  3  in  a  a  the  type  entering  This  one  type  site,  have  sites.  would  behaviour The  not  be  formed  If  cause  at  the  maximum  the to  the  the  and  to  to  lithium  displace  second  sites is  the  from  in  be  prevented the  from  extra volts.  the  vacant  energetically  impurity metal, the  sat  2.46V  the  2.1  entering is  metal  of  the  another  this  and  it  total  If  types  2.0  voltage  transition  lithium  second  the  explained in  eliminate  between the  the  there  would  would  be  3  cells  through  filling  unless  until  discharged  and  can  the  Chapter  been  2.46V  atoms  or  Endako  brought  structure.  This  some  the  had  cells  lithium  capacity  for lithium  to  guest  first  correspond  that  near  of  positions.  capacity  between  increased. This  then  the  two  that  stabilize  Both  favourable this  to  these  would  were  capacity  1.8V.  about  and  those  X-phase, behaviour  3  below  the  the  Mo S„  1.8V  volts  can  the  differences  same m o d e l 3  capacity. Endako  two  powder,  main  had  Mo S„  show  discharged the  transition  Endako  d i d not  was that  the  first  type  then of  type.  content  per  unit  cell  is  not  83 determined that  by  the t o t a l  "the Mo S 6  acting  a s an  cluster  8  electron  to  f i l l  This  be  modeled  molybdenum bands has  five  corners  by  are  approximately  other  degeneracy the  can  band  two  which  This  can  The  be  an  of  essentially  produced  leaves  be  intercalation  directly  make m e t a l - M o S „ 3  thirty  ions.  Each  of the  neighbours:  unit  from  cell.  d-orbitals  atoms.  seeing  four  unoccupied  2  energy  d-band  material  by  one o f and  Sixteen  i t  of the  a r e used  enter  the  lowest  in  from  to  this  ionized  represent  the  of the M o S . 6  raised  by  8  can only  the d i s c o v e r y be a n s w e r e d  i s obtained.  the elements,  compounds.  that  states  would  u  lifted  Work  host  from  3  be  cell  eight  sits;  The  electrons  Li Mo S  the  molybdenum.  others,  i n each  with  form  ions  would  the  the  A l l five  It i s likely  than  how  molybdenums  four  the  are  atomic  t h e molybdenum  other  filled  f o r Future  pure  the  which  pseudo-atom  completely...".  and  near  stated  electrons  orbitals  the  of the q u e s t i o n s  to  four  cell  d-electrons and  of the lowest  Many  as a  unit  energy  composition  Suggestions  (1977)  e l e c t r o n s p e r molybdenum.  sulphur  d-band.  filling  face  lower  molybdenum  the  lithium.  6.2  nearest  of the sulphur  accomodate  ionize  Only  equidistant  has a  twenty-four  regarded  i s i n the adjacent  orbitals  energy  i n each  as  Yvon  considering  of t h e molybdenum's  presence  these  by  of the rhomboid  one  be  the sulphur  sulphurs  and  should  t h e Mo-Mo b o n d  d-orbitals  are s p l i t  of s i t e s .  acceptor.  necessary can  number  These  but  ternary  Mo S„ 3  of  i f a  Mo S„ 3  source  cannot  be  i t i s possible to compounds  can  then  • be  either  acid  (Schollhorn  etched  (Chevrel  1977,1979)  should  be  done  to  find  most  convenient  to  to  1974)  remove  which  of  84  the  these  produce  or  extra  two  M03S  deintercalated metal.  methods free  fl  Work  is  the  from  metal  contamination. Schollhorn's Mo S 3  should  a  work  be  on  repeated  ray  s t u d i e s . Much  of  is  inconsistent  (1979),  diffusion exist  problems  in  metals.  his  x  This Mo S„ 3  3  should  first  from  finding  because  of  work  (1977) w i t h  lithium  x  cannot  predicted x  easy  to  determine  3  f l  large  problems and  exceed  would  X-  Mo S  the  Similar  that  and  intercalated  h i s methods.  implicitly  two  difficult,  sites. one  phase  other  1.8  in  equal  with  two.  a  transition  to  a  the  X-rays.  regards  suggested  site  of  be  was of  diffraction  i t may  It  question  type  increased. This  scatter  so  neutron  behaviour  a  positions  weakly  Other  more the  X-ray  the  scatterer,  i.e.  copper  by  claimed  filled  underwent  concentration  from  and  occupies  lithium  only  on  voltammetry  of  pure  sample.  lithium  data  accurate  probably  relatively  Another,  then  also  Yvon  be  work  earlier  and  a  his  electrochemical properties  using  induced  Schollhorn  Li Mo S ,  the  be  examined.  would  not  be  p o s s i b l e to  very  because i s an  find  - that  site  must  Lithium  the the  preferentially  different  lithium  how  as  the  Intensity  effective these  effective  the  and  in  atoms neutron  atom  positions  might  also  diffraction. metals  similar  intercalated to  regions'  that of  in  Mo S«  associated  capacity  with  3  with  show  lithium/Mo^n,  continuous  lattice  85 expansion  and  an  intercalation first  If  the metal  is a  good  of  the atoms  could  be  scattered  beams.  several  singly  lithium  would  Another Mo S„ have An  good  ionized  NMR  if  the  line  of  3  t o use  Other 3  work  for a  naturally  on  an  directly metal  make  to  stabilize  The  phase  on  the  that  X-phase  Li Mo S 2  other directly  3  u  two into  more  does  system. Mo Se„  signal,  intercalated Mo Se« 3  also  be  battery  so  example,  is  must  would  likely The  to  Li Mo S 2  i t would  3  than 4  be  could  produce  not  of a  found of  possible would  to  have  a  temperatures.  m i x t u r e seems  form  of  be e c o n o m i c a l  be  at high  be  i n the electrochemical 2  that  studies.  3  this material  the MoS -iron  see  might  i n NMR  Mo S„  i t may  structure  3  and  that  to  the a p p l i c a t i o n s  a method  way  because  seen  on  material.  in a  For  done  i t  the  directly  same a s  so  not.  has  3  the  in  convenient  examined  NMR  that  molybdenum  be  materials. a cell,  and  sulphur  t o be  is  with  lithium  should  the Mo S„  i s more  lithium  prove  the  way.  material  3  and  argued  prepared  mineral,  transitions  be  be  Li Mo S/, 2  are obtained  b e h a v i o u r of  behaviour  scale.  positions  i t can  this material  industrial  the  and  should  occurring  synthesizing  might  good  commercial  same  the  transition.  i n t e n s i t i e s of  unfortunately,  3  lithium  the  because  Mo S„,  a  then  i t could  lithium/Mo^,,  electrochemical  possible  Mo S„  as  S e l e n i u m has  a  but,  study  the  then i n the  NMR  phase  results  finding  use  elements. This  i t s  Mo S .  behave  signals,  structure  from  metals,  to  to  understanding  same  consistent  approach  alternate  for  If  be  scatterer,  d e t e r m i n e d from  probably  would  3  X-ray  order  work  done  to  indicate  either  o f . the  be  assembled  the Mo S„ 3  as  i t  86 was  charged.  made  i.n t h e p r e s e n c e  processing  There  would of  be a p r o b l e m  other  the material  i f Mo S 3  transition  t o remove  can only  a  metals,  the other  be  because  metals  could  be  expensive. If  the  lithium/Mo S 3  commercial  cell,  from  lithium/MoS  the  approximately kilogram) Mo S„  system  The  Mo S„  cells  and  the  fully  2  be  3  can  operated  a  but MoS  2  volt.  Yet,  the Mo S„  must  brought  a t room  3  be  produced,  other  three  t h e MoS  applications  system.  MoS  2  then  unlikely  is  3  f l  Mo S„ 3  known  not  and t h i s  designed system  that  i f must  to  be  has about  of  a  volt  o f a p-  by a t l e a s t  half  t o be s u p e r i o r f o r  o f t h e many  can  is  is  tenth  prove  i s naturally Mo S  voltage  of the c a p a c i t y  in spite  when i t  not phase  are  one  than  and w i l l  3  might  If  efficient  p-phase.  The M o S „  in a  synthesized. i t  i t  ones,  2  i t s high  the potential  cell  2  applications.  materials,  quarters  change  per  do t h e MoS  into  devices  of i t s capacity  would  back  voltage.  watt-hours  0 to a transition  However,  into  have  more  temperature  practical  drawing  general-purpose of  i s  a constant  cell  them  a l l of  Many  at  than  and i t  batteries  o f 2.7 t o 1.3V, b u t  a  lose  a  come  in certain  makes  as  likely  these  c a n go t h r o u g h so  would  (~250  voltage  hysteresis  developed  range  be s u p e r i o r  decompose  quarters  range, phase  voltage  to another material. a  Both  density  a higher  t o be s t a b l e  studied.  three  2  until  believed  Li Mo S  MoS  charged,  capacity  convert  have  smaller  molybdenite. is  might  is  competition  system.  2  a practical  the  3  i t s main  t h e same e n e r g y  in  3  then  system  a  occurring, not  be  i t  will  advantages but  Mo S„ 3  economically have  many  '  commercial The Mo S„ of  coefficient  these  high  drain  other in  al.  and of  have  These  in  convenient  Chevrel  than  phases  temperature  the  way  will  MoS  indicate  be a b e t t e r  host.  of  could For  shown  structure  critical  metal  number  likely  structure.  different  the  would  investigations  the  inserted.  This  i n both  and  2  which  battery  in a  application.  (1976,1976)  slightly is  be d e t e r m i n e d .  current Many  et.  of l i t h i u m d i f f u s i o n  two m a t e r i a l s  metals  7  applications.  should  3  8  be  on  example,  that  lead  other  Guillevic  i n Mo S 3  forms  a  a  i f nickel,  iron,  are often  superconductors  varies  with  Intercalation  changing  based  differing can  the  amount  experiments  could  or cobalt  amounts  serve  of  as  metal  a  i nthe  sample. Another  branch  of  metal-molybdenum-oxides sulfides.  Work  intercalation oxides  has of  (Jacobson  earlier,  the  rather  already  Mo0  than been  (VonSacken  2  the  t h e metal-molybdenumdone  on  1980)  1979, a n d C h r i s t i a n  molybdenum  investigate  are  lithium  and v a r i o u s  1980).  selenides  the-  A s was also  other  mentioned  potentially  useful.  have use  The  investigation  of  been  i n t h e Endako  MoS  for  materials can this  be  the 2  intercalation. are often  used  technique  impurities.  is  the  The e x t r a  minerals  high-lighted  and so  i t s source. sensitivity  Endako  capacity  which  another  Electrochemical  distinctive,  to identify  various  a  The major to  important  signatures voltage  of  profile  advantage of  detect  was o n l y  may  small  one t h i r d  of  88 one  percent  of the t o t a l  Electrochemical not  be  with  studies  identified  with  the c h a l c o c i t e  pattern shows  which  promise  materials.  development library  of  The  of data  that  the  detect  as  d i d not appear mixture.  which can  was  i n the  Lithium  powder.  the  case  diffraction  intercalation  f o r the i d e n t i f i c a t i o n  biggest  single  technique  Endako  materials  diffraction,  as a method  this  electrochemical  is  characterizes  problem  the  need  in  of the  to produce  known  samples  Endako  capacity  by  a  their  behaviour.  Summary Investigations  discovery  of  material. first  below  of the e x t r a  Mo S„  to  3  About  order  percent  half  phase  potential.  i s centred  percent  of  battery  the  i s an  near  cells  cycled  MO SK 3  well, cells  cannot  was  discovered  be  used  battery  A  single  further  2.46V, near  their  operating  copper  or  under  iron  i t indirectly.  with  one  and  twenty  of these  another  phase  is  similar  of the  another  five  lithium/Mo S 3  an e n e r g y  no  a  slightly  percent  of cathode  from  region  The  capacity  b e made d i r e c t l y  that  t o make i s made  losing  battery with  1.83V.  per kilogram  .useful  twenty  with  l e d to the  i s associated  and there  i n t e r c a l a t i o n system  275 w a t t - h o u r s  p-phase  potentially  is in a  capacity  around  2  a  of the c a p a c i t y  of the c a p a c i t y this  be  t r a n s i t i o n a t 2.088V,  capacity  MoS  X-ray  2  great  Of  can a l s o  of the MoS -copper  unknown  6.3  capacity  density  material. faster  a  of The  than d i d  conditions.  the elements,  but i t  intercalated Mo S„  could  3  I f the cathode materials,  of a  then  the  lithium metal  89 would  be d i s p l a c e d  would  show  the  as the c e l l  was  electrochemical  discharged.  behaviour  Later  of  cycles  lithium  in  Mo S . 3  a  The  lithium/Mo S 3  offers  a chance  order  phase  to  battery. might  of  research  The m a t e r i a l  prove  t o be  i s also  an  interesting  one  of  was  useful  i n which  the  the  physics  prime  the development  which  gives  f o r such  because i t  intercalation.  understanding  However,  intercalation  is  to investigate a material  transition  the problem  process.  system  4  a This  of  of  a  purpose.  leads  such  motivations  the extra-Endako a  first  a  for  practical capacity  90 Bibliography A l l m a n , M., a n d L a w r e n c e , D . 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(1977)  93  APPENDIX I Summary o f L a t t i c e Parameters Hexagonal Parameters  ed i n t h i s  Thesis Source  Formula  a  c.  9. 73  10. 22  CuMo S  9. 73  10. 2  Cu Mo S  9.713  10. 213  C u  1.38  M o  3 4  9. 735  10. 221  C u  1.47  M o  3 4  9. 73  10. 22  1100°C MoS ~copper  9. 729  10. 218  "X-phase" m a t e r i a l  9..52  10..27  Y-phase  Moh 1978  9..564  10.,273  FeMo S  Chevrel e t . a l . 1971  9..564  10.,273  9..55  10..30  9,.51  10,.37  9 .202  10 .877  Mo S  9 .728  10 .525  Li Mo S  2  2  Wang and Moh 1976  3  4  Chevrel  5  S  S  e t . a l . 1971  Yvon e t . a l . 1977 Yvon e t . a l . 1977 2  5  F e  0.66  FeMo S 3  6  M o  3 4 S  Guillevic  material  19 76  S c h o l l h o r n 1977  4  F i r s t Batch M o S ~ i r o n m a t e r i a l 2  3  2  Yvon e t . a l . 1977  4  2  3  Chevrel e t . a l . 1971 E x t r a Endako Capacity  at 2.700V  E x t r a Endako Capacity  at 2.100V  9 . 754 10 .589  E x t r a Endako Capacity  at 2.050V  10 .553  E x t r a Endako Capacity  at 1.800V  9 . 196 10 .891 9 .358  9 .795  10 . 725  94 Appendix  The at  following is a  four  cathode  different of  figures  the  which  collected cell  part  the  fully  four  clearly of  the  obscured  marked  with  a  by  the  lithium),  relative  remained  the  These  charged  tables  The  cell;  the  which  and  four  data  was  2.100V,  the  2.050V,  transition;  through  ~1(3mg  phase  transition  i t ; and  1.800V,  comparison The  a  and  parameters  mark  line  of  from  the  list  of  the  material. sources  diffraction  lines  components  (such  the  The  intensities  case.  diffraction were  in  (?}.  cell  lines  an  used  other  the  (101)  with  were  contamination, cell  positions  marked  positions  diffraction  is  the  numbers  lattice by  of  line  present  of  are  quoted  the  i n a l l the  Mo S„ 3  scans  and  constant.  The  line  obtained  by  number  position  2  and  to  material.  table  MoS  with  intensities  phase  defined  question  second  cell  two  c a p a c i t y below  charge.  were  caused  The  is a  that  The  as  had  a  collected  cell.  s t a t e s of  (*)  the  data  patterns.  fully  phase  table  determination  Lines are  single  are  and  is discharged  first  asterisk the  the  the  X-ray  PMX-11,  diffraction  above  discharged  The the  cell  of  the  just  the  of  positions  2.700V,  at:  the  and  at  show  of  m a t e r i a l . There  line  potential  where  voltages  "X-phase"  summarize  summary  II  of  was  position  collecting X-rays  and data  detected  recorded.  The  intensity at  0.01  in ten  information  degree  intervals  seconds  intensities  quoted  at  was of  2e.  each  angular  i n the  tables  95 were  determined  counts  from  strongest in  two  (I  /I p  the  ways:  );  and  than  then  line.  ratio,of  as -  the  lines  The  K„  data  intensities  of  Peak  0  this  intensity  maximum  (/I/I ).  number  n o r m a l i z i n g the  ratio  copper  above  The  quoted  the  true above  correction Three  data  and  the  total  positions  refer  background  data was  to  expressed lines  under  the  ~43°  refer  below  (k=1.54178A)  to  copper  the  i n two  areas  radiation  angle  of  K^j  and  radiation  .54433A) .  microns  was  a  average  positions U=1  data,  as  o  the  subtracting  diffraction  diffraction to  . by  used  to  for  readable  peak the  needed of  form, scan  positions  positions measuring  figures the  2.700V so of  are  the the  peak  at  plane  of  were  cell.  the  plotted  powder  angles  was  The  data  that  intensities.  The  stored by  325  7. from  and not  higher  diffTactometer.  plotted  positions  was  the  in Equation  m a t e r i a l was graph  slightly  because  is described  the  obtain the  continuous  peak  the  in a  digitizing  machine a  slow  SUMMARY  OF P E A K  POSITION (29)  INTENSITIES  /I/I 0  P  o  POSITION (20)  1 .800V  2 .050V  2 .100V  2 .700V LINE  P O S I T I O N S AND  nn o  I /I P o  POSITION (26)  /I/I o  I 11 P o  POSITION (20)  nn o  I 11 P <  (101)  14.00*  100  100  13.91*  100  100  13.63*  100  100  13.61*  100  100  (110)  19.52  <1  <1  19.17*  <1  <1  '18.40*  6  6  18.30*  5  5  (201)  24.01 • '  <1  1  23.70  <1  <1  -  -  -  -  (003)  24.73*  3  4  25.08  4  4  25.44*  6  4  25.51*  6  4  (202)  27.95*  6  4  27.81*  5  6  27.21  3  3  27.19*  3  4  (211)  31.02*  17  16  30.55*  16  13  29.41*  15  13  29.44  4  6  (212)  34.23*  41  29  33.88  39  29  32.95*  25  21  33.01  26  11  (104)  35.02*  15  14  35.43  21  13  35.73*  15  12  35.79*  14  10  (220)  39.37*  16  11  38.71*  15  9  37.04*  18  12  36.83  10  5  (204)  40.30*  3  2  40.28  3  2  -  -  (311)  41.90*  37  26  41.26*  37  25  47  29  (303)  42.34*  42  24  42.08*  17  15  -  39.57* 1  ?  -  -  39.46*  17  12  ?  1  SUMMARY  OF P E A K  (105) (312)  POSITION (20) 43.22* ?  SI/I  INTENSITIES  I /I o - p o  17?  18?  1  1  POSITION (20) 43.85* ?  fl/l  1  o  (CONTINUED)  1 ,800V  2 • 050V  2 . 100V  2 .700V LINE  P O S I T I O N S AND  P  o  1  7  1  ?  (214)  45.05*  28  21  45.09*  21  18  (223)  46.93*  83  53  46.55*  72  50  (402)  48.88  <1  <1  48.08*  1  ?  24  15  POSITION (20)  /I/I o  I /I p o  7  7  33  26  7  7  68  47  ?  ?  47.85  21  13  50.28*  51  33  ?  42.35* ?  45.36* 7  (321)  ?  7  ?  (322)  ?  ?  ?  ?  ?  ?  ?  ?  ?  7  ?  7  -  -  -  49.99  POSITION (20)  fill o  I /I P o  7  7  42.20*  26  13  44 .'7 9*  33?  20?  45.47  55  20  7  7  47.49  14  7  50.13*  25  18  ?  ?  -  -  7  7  (314)  53.54  4  3  (116)  54.48*  2  2  55.06  3  2  (324)  61.20  17  12  60.72  18  14  59.20*  21  14  59.25  5  6  _  —  -  -  56.44*  8  6  56.25  13  3  (413)  _  -  -  DIFFRACTION LINES PRESENT IN ALL SCANS  POSITION (2 6)  INTEGRATED INTENSITY  14.62  103  17.19  5  18.72  1  20.49  <1  25.79  3  28.76  2  29.22  9  33.29  5  36.18  29  37.00  3  39.77  12  41.50  47  43.51  25  44.34  66  45.90  13  50.50 t o 52.50  612  53.00  14  60.28  71  COMMENTS  MoS (002) 2  MoS (004) 2  L i (110)  MoS (103) 2  S e v e r a l Peaks  MoS (008) 2  66  100  > o o  CNJ  P4  u  0)  M-l  o  c o  CO  I  X  ro CM  ro CM  s^unoQ  s j u n o o  n a) }-< • H  fe  101  11111111  CM CO  o CO CO  m CO  m CM o  o S' m 'S CM  > o m o  co  CN 4 J CO  co fe CU C_>  CM  m o  c O ^*  ro  CM  sjunoQ  o o o o  I I I 1 I 1 11  o o o o  o o o o  K)  o o o o  CM  o o o o o  sjunoQ  00 to  cd a  cn  cd  Pi i  X i i CNl OO CD  u faO  • H fe  102  I I I I I I I I I  CM CD O CO  CO  m CO  m ^ *  m CM  m o <^ io CM 00  >  o o oo 4-J  Cd  CO fe CD  CM  c  o  t o  CN  s^unoQ  ?s  o o o o m  I 1 I I I I 1I  o o o o  o o o o  o o o o  to  o o o o  CM  s^unoo  CO t o  cd  o  CO cd Pd O  i X! i co CO CD  bO •rl  fe  


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