CA1302490C - Method of making a cathode for use in a rechargeable lithium battery, cathode so made, and rechargeable lithium battery including the cathode - Google Patents
Method of making a cathode for use in a rechargeable lithium battery, cathode so made, and rechargeable lithium battery including the cathodeInfo
- Publication number
- CA1302490C CA1302490C CA000551965A CA551965A CA1302490C CA 1302490 C CA1302490 C CA 1302490C CA 000551965 A CA000551965 A CA 000551965A CA 551965 A CA551965 A CA 551965A CA 1302490 C CA1302490 C CA 1302490C
- Authority
- CA
- Canada
- Prior art keywords
- cathode
- weight percent
- lithium battery
- rechargeable lithium
- lixcoo2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052744 lithium Inorganic materials 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims 3
- 229910001091 LixCoO2 Inorganic materials 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- 239000003738 black carbon Substances 0.000 claims 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 13
- 230000001351 cycling effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 241000651994 Curio Species 0.000 description 1
- 241001176357 Imber Species 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000001720 action spectrum Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
ABSTRACT
A cathode is made for a rechargeable Li/LixCoO2 cell using an aqueous cathode preparation. The Li/LiAsF6 -MA/LixCoO2 system can deliver between 230-170 Wh/kg at current densities of 2-10mA/cm2.
A cathode is made for a rechargeable Li/LixCoO2 cell using an aqueous cathode preparation. The Li/LiAsF6 -MA/LixCoO2 system can deliver between 230-170 Wh/kg at current densities of 2-10mA/cm2.
Description
~3~
This invention relate~ to a method o making l.i~CoO2 ~O<x<l) a~ the cathode for use in a rechargeable lithium battery, to a cathode so made, and to a rechargeable lithium ~at~ery including the cathode.
The use of r~ixco~ (O~x<l) a~ the catho~e in a rechargeable l.ithium cell was first proposed by Mizushima et al in;
-~he article "~ New Cathode Material For Batteries of High Energ~
Density" .~y K. Mizushima, P.C~ .Jones, P.~J.Wiseman and J.B~
Goodenough, Mat. Res. ~ull., 15, 783 (198~). Tlle layered roclc salt structure of.LixCoO2can theoretically intercalate one mole oE
lithium per mole of oxide at cell voltages of qV or ~reater; and deliver energy densities in exces~ of 1000 Wh/kg. Since the initial report on this high energy cathode by Mi~ushima et al, the Li/LixCoO2 cell remained a curio~lty, due undoubtedly, to its characteristically high cathode potential~ which results in solvent oxidation. Mendibour~ et al in the a~ticle "New ~ayered ~tructure Obtained by Electrochemical ~eintercalation of the ~3~2 ~' Metastable LiCoO2 (02) Variety" by A. Mendiboure, C. Delmas and P.
Hagenmul]er/ Mat. Res. null., 19, 1383 (19~4) reported some cycling data for this high energy couple in lithium perchlorate-propylene carbona~e sol~tions, but their work mainly focused on the phase transitions occurriny within LixCoO2.
Mendiboure et al reported the upper stability of their electrolyte as 4V wh.icl- is not sufEiciently high enou~ll to be used prac~ically in.the Li/LixCoO2.
The general object of thi~ inven~ion i~ to provide a universal lithium battery that can be used in a l~rge n~Imber of .conigurations thereby reducing battery proliEeration. ~ moLe particular object of the invention is to provide a rechar~eable lithium battery capable oE delivering superior cell pe~forman~e over previously described cell system~ witII LixCoO2 as the cathode.
It has now been found that the aforementioned objects can . ;
be attained by providing an electrochemical cell comprised o~ an.
alkali metal anode, a cathode including 80 weight percent l.ithium cobalt dioxide (LixCoO2 where o<x<l) as the active material wi-tll l~ weight percent polytetrafluorethylene (P~FE) as the binder with an electrolyte containing 1.5 to 2.0M lithium hexafluoroarsenate tLi~sF6) as the solute and methyl acetate ~M~) as the solvent.
. The cathode mixture including the active material, ; conductive diluent, and emulsified binder is prepared as a dough , ~3t?~
wi~h additions of a wetting agent of 3:1 water-isopropyl alcohol solution. The cathode dou~h is roll pressed l~etween two L~olymer .sheets as for example~ Mylar* onto both sides o~ an expanded aluminum scree~ and is sintered at 280OC under VaCU~1m for 1 hour.
~his cathode preparation produces a cathode structure ~laving ~excellent flexibility and a high porosity o~ at lea~t 50 percent.
This LixCoO2 cathode prepara~ion in conjunction with the LiAsFG-MA
electrolyte enables tlle electrochemical cell oE Li/Li~sF~ -MA/LiX
. CoO2 to be used as a practical rechargeable ~atteryO The use o~
an aqueous cathode preparation has not been suggested heretofore in the manuEacture of a LixCoO2 cathocle. X-ray di~ action spectra o~ both water soaked LixCoO2 and the untreate~ material . are identical showing the insensitivity oE moisture oll the material~ Also, since the LixCoO2 is prepared in air, tlle cathode preparation can be perEormed under non-specialized ma~ actu~ g environments tllus eliminating the requirement oE a costly low humidi~y.room or inert gas filled glove box.
The results using MA solutions with Li/~ixCoO2 indicate rake capabilities, low temperature performance, and cycle liEe to be excellent. In all cycling studie~ presented hereina~ter, cells are always charged at 0.5 mA/cm2 at 25C while tlle discllarge ra~e and temperatures are varied.
* denote~ trademark for a polye~ter film ~3~
In the drawing which illustrates embodiments of the invention:
Figures 1-4 are gr~phs which illustr~te the cycling efficiency of rechargeable lithium cells according to the invention.
E'igure 1 show~ the initial ch~r~e~di.~cha.rge of Li/~i,CoO2 in 2.4 M LiAsE'~-MA at 25C and a discharge rate of 2.0 mA/cm2. The potenti~1-c~pacit,y curve for lower rates are identical to j ~
~3(~2~
~ .
those for the 2m~/cm2 discharge rate. The initial oCV is 307V.
Figure 2 shows the ratio capability o~ the Li/2.4 M
~i~sF~, -M~L~ Co~ cell at 25OC. ~11 curves are initial di~charges except ~or 10 m~c~ which is measure~ Oll the second dischar~e cycle, ~ u~e 3 shows the effec~ of temperatuLe at a cons~an~
discharge rate of 2.0 mA/cm2. 25C and -10UC res~lts are Eor tlle initial discharge, and -40C results are obtained on the second discharge.
A numerical summary of the data shown in Fi~ures 1 to 3 is given in Table 1. The ~ata ln this table ~hows that the Li/Li~sF6-M~/LixCoO2 system is not only capable oE delivery rates up to 10 m~cm2 , hut can do so over the wide tempera~ure ran~e~of _40uC to 25Co Table 1. I)ischarge result~ for firs~ and ~L'OIl~ cycLe a discharge cutofaverage energy rate capacity voltagedischarge density ,t/oC 1.~ Vpotential (V) ~ 8 ?.5 5-0 a.62 . 2.5 . 3.70 633 l~.a 0.53 2.5 3.6~ 517 -10 2 ~ 0 ~ . 60 2.~ 3.30 603 -4~ 2~0 0.~0 ~.0 2.50 ` 135 .
aExpeximental energy densities are based on mass of active material.
Figure 4 shows the relation between capacity an~ cycle i.
number for a Li/1.7M LihsF6-MA/L~ Co~ cell where the'temperature is constant at 25C and the discharge rate is fixed- at 2.0 m~/cm2.
The potential limits are set at 4.'3V to 2.5V with no inte~ruptions during cycling, The cell d~livers better than 98 percent cycling 'eEficiency based on the initial charge capacity over 20 cycles.
No significant ~QSSeS in capacity are observed over these ~onditions su~ges~ing excellent electrochemical ~A~ility of th~
systems at these potentials.
The cell components are al~o tested for cllemical stability by high temperature storage at 71C over a 3~-day '!
period. No visible degradation of any component is observed, and atomic absorption studie~ Eor cobalt solubilities are Eavorable~ '~
with only trace amounts of cobalt ~10 ppm) found present in I' solution.
These results far exceed those reported for LlLixoO2 in other electrolytes and delnons~rat~ the superior performance o-the Li~ sF6-MA/LixCoO2 systems. Using the experimenta] energy densities based on active materials (Table 1) and assuming an additional 33 percent loss when going to a practical rechargeable cell, it is estimated that the Li~Li~sF6-MA~Li~CoO2 syst~n can deliver between,230 to 170 Wh/kg at c~rrent densities of 2 to 1~
mAJcm2 . At a dischar'ge rate of 20 mA/cm2 , it is estimated that ' practical energy densities of 200 Wh/kg and 45 Wh/kg are feasible at temperatures o -10C and -40C respectively.
~ We wi~h it under6tood that we do not desire to be limited ' to the exact detailed described for obvious modifications will occur to a per~on skilled in the art.
'
This invention relate~ to a method o making l.i~CoO2 ~O<x<l) a~ the cathode for use in a rechargeable lithium battery, to a cathode so made, and to a rechargeable lithium ~at~ery including the cathode.
The use of r~ixco~ (O~x<l) a~ the catho~e in a rechargeable l.ithium cell was first proposed by Mizushima et al in;
-~he article "~ New Cathode Material For Batteries of High Energ~
Density" .~y K. Mizushima, P.C~ .Jones, P.~J.Wiseman and J.B~
Goodenough, Mat. Res. ~ull., 15, 783 (198~). Tlle layered roclc salt structure of.LixCoO2can theoretically intercalate one mole oE
lithium per mole of oxide at cell voltages of qV or ~reater; and deliver energy densities in exces~ of 1000 Wh/kg. Since the initial report on this high energy cathode by Mi~ushima et al, the Li/LixCoO2 cell remained a curio~lty, due undoubtedly, to its characteristically high cathode potential~ which results in solvent oxidation. Mendibour~ et al in the a~ticle "New ~ayered ~tructure Obtained by Electrochemical ~eintercalation of the ~3~2 ~' Metastable LiCoO2 (02) Variety" by A. Mendiboure, C. Delmas and P.
Hagenmul]er/ Mat. Res. null., 19, 1383 (19~4) reported some cycling data for this high energy couple in lithium perchlorate-propylene carbona~e sol~tions, but their work mainly focused on the phase transitions occurriny within LixCoO2.
Mendiboure et al reported the upper stability of their electrolyte as 4V wh.icl- is not sufEiciently high enou~ll to be used prac~ically in.the Li/LixCoO2.
The general object of thi~ inven~ion i~ to provide a universal lithium battery that can be used in a l~rge n~Imber of .conigurations thereby reducing battery proliEeration. ~ moLe particular object of the invention is to provide a rechar~eable lithium battery capable oE delivering superior cell pe~forman~e over previously described cell system~ witII LixCoO2 as the cathode.
It has now been found that the aforementioned objects can . ;
be attained by providing an electrochemical cell comprised o~ an.
alkali metal anode, a cathode including 80 weight percent l.ithium cobalt dioxide (LixCoO2 where o<x<l) as the active material wi-tll l~ weight percent polytetrafluorethylene (P~FE) as the binder with an electrolyte containing 1.5 to 2.0M lithium hexafluoroarsenate tLi~sF6) as the solute and methyl acetate ~M~) as the solvent.
. The cathode mixture including the active material, ; conductive diluent, and emulsified binder is prepared as a dough , ~3t?~
wi~h additions of a wetting agent of 3:1 water-isopropyl alcohol solution. The cathode dou~h is roll pressed l~etween two L~olymer .sheets as for example~ Mylar* onto both sides o~ an expanded aluminum scree~ and is sintered at 280OC under VaCU~1m for 1 hour.
~his cathode preparation produces a cathode structure ~laving ~excellent flexibility and a high porosity o~ at lea~t 50 percent.
This LixCoO2 cathode prepara~ion in conjunction with the LiAsFG-MA
electrolyte enables tlle electrochemical cell oE Li/Li~sF~ -MA/LiX
. CoO2 to be used as a practical rechargeable ~atteryO The use o~
an aqueous cathode preparation has not been suggested heretofore in the manuEacture of a LixCoO2 cathocle. X-ray di~ action spectra o~ both water soaked LixCoO2 and the untreate~ material . are identical showing the insensitivity oE moisture oll the material~ Also, since the LixCoO2 is prepared in air, tlle cathode preparation can be perEormed under non-specialized ma~ actu~ g environments tllus eliminating the requirement oE a costly low humidi~y.room or inert gas filled glove box.
The results using MA solutions with Li/~ixCoO2 indicate rake capabilities, low temperature performance, and cycle liEe to be excellent. In all cycling studie~ presented hereina~ter, cells are always charged at 0.5 mA/cm2 at 25C while tlle discllarge ra~e and temperatures are varied.
* denote~ trademark for a polye~ter film ~3~
In the drawing which illustrates embodiments of the invention:
Figures 1-4 are gr~phs which illustr~te the cycling efficiency of rechargeable lithium cells according to the invention.
E'igure 1 show~ the initial ch~r~e~di.~cha.rge of Li/~i,CoO2 in 2.4 M LiAsE'~-MA at 25C and a discharge rate of 2.0 mA/cm2. The potenti~1-c~pacit,y curve for lower rates are identical to j ~
~3(~2~
~ .
those for the 2m~/cm2 discharge rate. The initial oCV is 307V.
Figure 2 shows the ratio capability o~ the Li/2.4 M
~i~sF~, -M~L~ Co~ cell at 25OC. ~11 curves are initial di~charges except ~or 10 m~c~ which is measure~ Oll the second dischar~e cycle, ~ u~e 3 shows the effec~ of temperatuLe at a cons~an~
discharge rate of 2.0 mA/cm2. 25C and -10UC res~lts are Eor tlle initial discharge, and -40C results are obtained on the second discharge.
A numerical summary of the data shown in Fi~ures 1 to 3 is given in Table 1. The ~ata ln this table ~hows that the Li/Li~sF6-M~/LixCoO2 system is not only capable oE delivery rates up to 10 m~cm2 , hut can do so over the wide tempera~ure ran~e~of _40uC to 25Co Table 1. I)ischarge result~ for firs~ and ~L'OIl~ cycLe a discharge cutofaverage energy rate capacity voltagedischarge density ,t/oC 1.~ Vpotential (V) ~ 8 ?.5 5-0 a.62 . 2.5 . 3.70 633 l~.a 0.53 2.5 3.6~ 517 -10 2 ~ 0 ~ . 60 2.~ 3.30 603 -4~ 2~0 0.~0 ~.0 2.50 ` 135 .
aExpeximental energy densities are based on mass of active material.
Figure 4 shows the relation between capacity an~ cycle i.
number for a Li/1.7M LihsF6-MA/L~ Co~ cell where the'temperature is constant at 25C and the discharge rate is fixed- at 2.0 m~/cm2.
The potential limits are set at 4.'3V to 2.5V with no inte~ruptions during cycling, The cell d~livers better than 98 percent cycling 'eEficiency based on the initial charge capacity over 20 cycles.
No significant ~QSSeS in capacity are observed over these ~onditions su~ges~ing excellent electrochemical ~A~ility of th~
systems at these potentials.
The cell components are al~o tested for cllemical stability by high temperature storage at 71C over a 3~-day '!
period. No visible degradation of any component is observed, and atomic absorption studie~ Eor cobalt solubilities are Eavorable~ '~
with only trace amounts of cobalt ~10 ppm) found present in I' solution.
These results far exceed those reported for LlLixoO2 in other electrolytes and delnons~rat~ the superior performance o-the Li~ sF6-MA/LixCoO2 systems. Using the experimenta] energy densities based on active materials (Table 1) and assuming an additional 33 percent loss when going to a practical rechargeable cell, it is estimated that the Li~Li~sF6-MA~Li~CoO2 syst~n can deliver between,230 to 170 Wh/kg at c~rrent densities of 2 to 1~
mAJcm2 . At a dischar'ge rate of 20 mA/cm2 , it is estimated that ' practical energy densities of 200 Wh/kg and 45 Wh/kg are feasible at temperatures o -10C and -40C respectively.
~ We wi~h it under6tood that we do not desire to be limited ' to the exact detailed described for obvious modifications will occur to a per~on skilled in the art.
'
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Method of making a cathode having a porosity of at least 50 percent for use in a rechargeable lithium battery from a cathode mixture of active material, conductive diluent and emulsified binder comprising preparing the cathode mixture as a dough with additions of an aqueous wetting agent and roll pressing the cathode dough between two polymer sheets onto both sides of an expanded aluminum screen and sintering at about 280°C under vacuum for 1 hour.
2. Method of making a cathode according to Claim 1 wherein the cathode mixture is of about 80 weight percent lithium cobalt dioxide (LixCoO2 where 0?x?1) as the active material, about 10 weight percent Shawinigan black carbon as the conductive diluent and about 10 weight percent polytetrafluoroethylene as the binder.
3. Method according to Claim 2 wherein the wetting agent is about 3:1 water:isopropyl alcohol solution.
4. A rechargeable lithium battery comprising lithium as the anode, a cathode having a porosity of at least 50 percent and prepared from a cathode mixture of about 80 weight percent lithium cobalt dioxide (LixCoO2 where 0?x?1) as the active material, about 10 weight percent Shawinigan black carbon as the conductive diluent and about 10 weight percent polytetrafluoroethylene as the binder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US028,169 | 1987-03-20 | ||
| US07/028,169 US4818647A (en) | 1987-03-20 | 1987-03-20 | Method of making a cathode for use in a rechargeable lithium battery, cathode so made, and rechargeable lithium battery including the cathode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1302490C true CA1302490C (en) | 1992-06-02 |
Family
ID=21841959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000551965A Expired - Lifetime CA1302490C (en) | 1987-03-20 | 1987-11-10 | Method of making a cathode for use in a rechargeable lithium battery, cathode so made, and rechargeable lithium battery including the cathode |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4818647A (en) |
| CA (1) | CA1302490C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0626138B2 (en) * | 1987-11-20 | 1994-04-06 | 昭和電工株式会社 | Secondary battery |
| DE3826812A1 (en) * | 1988-08-06 | 1990-02-08 | Heitbaum Joachim | NONWATER, RECHARGEABLE GALVANIC LITHIUM ELEMENT WITH INORGANIC ELECTROLYTE SOLUTION |
| GB2242898B (en) * | 1990-04-12 | 1993-12-01 | Technology Finance Corp | Lithium transition metal oxide |
| US4983476A (en) * | 1990-06-18 | 1991-01-08 | The United States Of America As Represented By The Secretary Of The Army | Rechargeable lithium battery system |
| JP3077218B2 (en) * | 1991-03-13 | 2000-08-14 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| US5587253A (en) * | 1993-03-05 | 1996-12-24 | Bell Communications Research, Inc. | Low resistance rechargeable lithium-ion battery |
| US5464706A (en) * | 1994-03-02 | 1995-11-07 | Dasgupta; Sankar | Current collector for lithium ion battery |
| JP3427570B2 (en) * | 1994-10-26 | 2003-07-22 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| US5587133A (en) * | 1995-02-03 | 1996-12-24 | Bell Communications Research, Inc. | Delithiated cobalt oxide and nickel oxide phases and method of preparing same |
| US5667660A (en) * | 1995-09-12 | 1997-09-16 | Alliant Techsystems Inc. | Synthesis of charged Lix CoO2 (0<×<1) for primary and secondary batteries |
| US5582935A (en) * | 1995-09-28 | 1996-12-10 | Dasgupta; Sankar | Composite electrode for a lithium battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3317347A (en) * | 1962-07-02 | 1967-05-02 | Servel Inc | Nickel electrode and method of making same |
| US3415687A (en) * | 1966-03-29 | 1968-12-10 | Honeywell Inc | Electric current producing cell |
| DE2600638A1 (en) * | 1975-01-09 | 1976-07-15 | Gte Laboratories Inc | PRE-SHAPED CATHODE, METHOD OF MANUFACTURING IT AND EQUIPPED WITH IT, ELECTRO-CHEMICAL ELEMENT |
| JPS5543761A (en) * | 1978-09-21 | 1980-03-27 | Hitachi Maxell Ltd | Method of manufacturing anode |
| JPS5776752A (en) * | 1980-10-31 | 1982-05-13 | Toshiba Corp | Manufacture of positive electrode for organic solvent battery |
-
1987
- 1987-03-20 US US07/028,169 patent/US4818647A/en not_active Expired - Fee Related
- 1987-11-10 CA CA000551965A patent/CA1302490C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4818647A (en) | 1989-04-04 |
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