CA1143002A - Organic electrolyte for rechargeable lithium cells - Google Patents
Organic electrolyte for rechargeable lithium cellsInfo
- Publication number
- CA1143002A CA1143002A CA000354948A CA354948A CA1143002A CA 1143002 A CA1143002 A CA 1143002A CA 000354948 A CA000354948 A CA 000354948A CA 354948 A CA354948 A CA 354948A CA 1143002 A CA1143002 A CA 1143002A
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- Prior art keywords
- lithium
- electrolyte
- sulfolane
- rechargeable cell
- cell
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- 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
-
- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
ORGANIC ELECTROLYTE FOR RECHARGEABLE LITHIUM CELLS
ABSTRACT OF THE DISCLOSURE
A rechargeable lithium cell employing an organic electrolyte of sulfolane or its liquid alkyl-substituted derivatives thereof, a cosolvent such as dimethoxyethane and an ionizable solute such as lithium tetrafluoroborate and/or lithium perchlorate.
S P E C I F I C A T I O N
1.
ABSTRACT OF THE DISCLOSURE
A rechargeable lithium cell employing an organic electrolyte of sulfolane or its liquid alkyl-substituted derivatives thereof, a cosolvent such as dimethoxyethane and an ionizable solute such as lithium tetrafluoroborate and/or lithium perchlorate.
S P E C I F I C A T I O N
1.
Description
~ 3 ~ ~ 2 12253 Field of the Invention A rechargeable nonaqueou~ Li/TiS2 c~ll employing a nonaqueous elec~rolyte comprising at least one solvent selected from the group co~si8ting of sulfolane and its liquid alkyl-substitu~ed derivatives, a cosol~ent of the formula CH30(CH2CH20)nC~3 where n varies between 1 (dime~hoxyethane) and 4, and an ionizable solute selected from ~he group consisting of lithium tetrafluoroborate, lithium perchlorate and mi~turesthereof.
Back~round of the Invention Lithium cells have the possibility of high energy density because of the low equivalent weight of ehe metalO As a result, several primary high energy density nonaqueous systems have been developed in the past few years. Secondary lithium cells, however, have been difficult to produ~e since many of the known solvents employed in the electrolyte solution foster dendritic deposits during the charging mode of operation which subsequently causes cell shorting. I~ is also known that the plated lithium is reactive toward the commonly used solvents and impuritles contained therein, thus giving rise to subs~antial corrosion rates. These corrosion reactions may result in form~tion of isolated, electrochemically unusable lithium that, in some instances, may result in lithium deposits that separate from the substrate material, This would result ln poor cyclability characteristics of the lithium anode.
.~
Back~round of the Invention Lithium cells have the possibility of high energy density because of the low equivalent weight of ehe metalO As a result, several primary high energy density nonaqueous systems have been developed in the past few years. Secondary lithium cells, however, have been difficult to produ~e since many of the known solvents employed in the electrolyte solution foster dendritic deposits during the charging mode of operation which subsequently causes cell shorting. I~ is also known that the plated lithium is reactive toward the commonly used solvents and impuritles contained therein, thus giving rise to subs~antial corrosion rates. These corrosion reactions may result in form~tion of isolated, electrochemically unusable lithium that, in some instances, may result in lithium deposits that separate from the substrate material, This would result ln poor cyclability characteristics of the lithium anode.
.~
2~ ~
~,.6~3~S.~Z
12~53 It ~6 been dl~clo~ed ~n the prior art th~t exten~lve purlf~c~tion of ~olve~tfi ~nt ele6trolyte~5 are required ~o pr~duce a ~olvent~electrolyte ~uleable for electrodepo~ition of lithium on a ~ub~trate.
~owever~ ev~ lf lithlum caQ be deposited OQ ~ ~ubstrate u~ng ~ part~cular solvent-electrolyte, lt ~ not ~lways ~rue that the solvent-electrolyte can ~e,used with a llthium-cathode couple ~o produce a rechargeable cell.
While the theoret~cal energyj i.e., the electrical energy potentially ~vail~ble from a ~electet snode-cathode co~ple, i~ relatively ea6y to calculate, there i8 a need ~o choose a ~onaqueous electrolyte for such a coupie ~chat permits ~he actual energy produced by an asse~bled battery to approsch the theoretical energy. The problem usually encou~tered is that it i~ practically Impossible to predic~ in atvance how ~ell, if at zll, a nonaqueous electrolyte will function with a ~olected couple. Thus a cell m~t be considered as a unit havi~g thxee parts a cathode~ an anode and an electrolyte, ant it $6 to ~e understood ~h~t the part6 of one cell are not predlctably inter-changeable w*th parts of another cell to produce an efficient and ~orkable cell.
U. S. Patent ~umber 4~167,458 filed ~hrch 28, 1978 in the name of D. V. loU208 et al9 di~clo~e~ olvent-electrol~te use in ~ proce~s for the electrodepo~ition of lithium comprising lithi~mfluoroborate dissolvet ln a sixture of methylene chloride and ~ulfolane ~nd/or itR alkyl-6ubstituted derivatives thereof.
~,.6~3~S.~Z
12~53 It ~6 been dl~clo~ed ~n the prior art th~t exten~lve purlf~c~tion of ~olve~tfi ~nt ele6trolyte~5 are required ~o pr~duce a ~olvent~electrolyte ~uleable for electrodepo~ition of lithium on a ~ub~trate.
~owever~ ev~ lf lithlum caQ be deposited OQ ~ ~ubstrate u~ng ~ part~cular solvent-electrolyte, lt ~ not ~lways ~rue that the solvent-electrolyte can ~e,used with a llthium-cathode couple ~o produce a rechargeable cell.
While the theoret~cal energyj i.e., the electrical energy potentially ~vail~ble from a ~electet snode-cathode co~ple, i~ relatively ea6y to calculate, there i8 a need ~o choose a ~onaqueous electrolyte for such a coupie ~chat permits ~he actual energy produced by an asse~bled battery to approsch the theoretical energy. The problem usually encou~tered is that it i~ practically Impossible to predic~ in atvance how ~ell, if at zll, a nonaqueous electrolyte will function with a ~olected couple. Thus a cell m~t be considered as a unit havi~g thxee parts a cathode~ an anode and an electrolyte, ant it $6 to ~e understood ~h~t the part6 of one cell are not predlctably inter-changeable w*th parts of another cell to produce an efficient and ~orkable cell.
U. S. Patent ~umber 4~167,458 filed ~hrch 28, 1978 in the name of D. V. loU208 et al9 di~clo~e~ olvent-electrol~te use in ~ proce~s for the electrodepo~ition of lithium comprising lithi~mfluoroborate dissolvet ln a sixture of methylene chloride and ~ulfolane ~nd/or itR alkyl-6ubstituted derivatives thereof.
3.
~.~
1~4300Z 12253 U. S. Patent 4,009,052 discloses a battery utilizing lithium as the ~node-sctive material, titanium disulfide as the cathode-active material and lithium perchlorate dissolved in tetrahydrofuran plu8 d~methoxyethane solvent as the electrolyte.
U. S. Patent 3,907,597 discloses a nonaqueous cell utilizing a h~ghly active metal anode such as lithium, a 601id cathode ~uch as fluorinated carbon, copper sulfide, copper oxide, manganese dioxide, lead dioxide, iron sulfide, copper chloride, silver chlor~deand sulfur, and a liquid organic electrolyte comprising sulfolane or its liquid alkyl-substituted derivativ~ i~ combination with a cosolvent such as dimethoxyethane and an ionizing solute such as lithium perchlorate and lithium cetrafluoroborate.
It is an object of the present invention to provide a rechargeable lithium cell.
Another object of the present invention is to provide a rechargeable lithium/titanium disulfide cell.
Another ob~ect of the present inveo~ion is to provide a nonaqueous electrolyte for rechargeable lithium c~lls consisting of sulfolane, dimethoxyethane and a solute of lithium tetrafluoroborate andlor lithium perchlorate.
The foregoing and additional ob~ects will become more fully apparent from the description hereinafter.
.j 3~
SummarY of the Invention The lnvention relates to a rechargeable ~ell comprising a lithium anode, a cathode such a~ a titanium disulfide cathode,and a nonaqueous electrolyte comprising at least one solvent selected from the group consisting of sulfolane and its liquid alkyl-substituted derivative ~hereof, a cosolvent of the or~ula CH30(CH2CH2O)nCH3 where n varies between --1 (dimethoxyethaneS and 4, and a solute selected from the group consisting of lithium tetrafluoroborate (LiBF4),lithium perchlorate tLiC104) and mixtures thereof. Preferably, the sulfolane and/or the alk~l-substituted derivatives thereof should consist of between about 20 and about 80 volume per cent of the electrolyte solvent mixture with the remainder being the cosolvent and most preferably between about 50 and 80 volume percent of the electrolyte solvent mixture.
Thepreferredcosolvent is dimethoxyethane.
It has been found that using the above electrolyte solution in a lithium cell, a rechargeable lithium cell is produced that does not require the tedious purification procedures that were usually necessary in the prior art in the production of rechargeable lithium cells. The rechargeable cells of this invention have been found to operate eficiently dur~ng numerous charge and discharge cycles without effectively producing dendrltic deposits during the char~ing mode of operation. It has also b4en observed that using the electrolyte solution of this invention .
~ 3Q~2 12253 along with ~ lithlum/tit~nium d~sulfide c~uple, lithium can be efficiently electrodeposited on the li~hiu~ electrode gubstrate during char~ing thus making th$s cell ~y~tem an e~cellent rech~rgeable lithium cell.
Sulfolane for u~e ln ~hi$ ~e~tion ~ a 1, l-d~o~otetrahydrothiophene (~ometi~es callet tetra-~hylene ~ulfo~e) ~nd ls ~ ~aturated heteroc~cl~c cozpound of the ~tructuse:
~2l CIH2 ~2C~e/C~2 0~) Som~ of the phy~cal prGperties of sulfol~ne ~re ~ho~n ~n T~ble 1:
r~ 1 Melting Point ~-C.~ . 28 Boiling Point (-C.) ~ 283 Sp. Cond., 25C. ~ohm~l -1) 2 ~ 10-8 20 Dieleetric Con,~tant, 25C. 44 Densiey, 30UC. (g/cm3) 1.2615 Vi~cos$ty, 30C. (centipoise) 9.87 ~rcezlng Point DepresYion Constant 66.2 5he 3-m~thyl sulfolane, which ~ a liquld alkyl-~ubstituted terivative of the ~bove ~tructure and i ~l~o ~uieable for u~e ~n thi~ lnvention9 ba~ the following ~tructure: .
~2 ~ ~ 2 0~0 . .
1 1 ~30 ~ 12253 Sulfolane and lts liqu~d alkyl-substituted derivat$ves, such as ~-me~hyl sulfolane, are good nonaqueous ~olvents but have the tisadvantage in that they have a relatively high vlscosity. Thus when metal ~alts are dissolved in these ~olvents for the purpose of improving ~he conductivity of the solvents, the viscosity of the 801utlon becomes too high for its efficient use as an electrolyte for nonaqueous cell applications. Consequently the addition of a l~w viscosity cosolvent is necessary if sulfolane and its liquid alkyl-substituted derivatives are to be used as an electroly~e for nonaqueous cells which can operate or perform at a high energy density level.
Although many cosoLvents and metal salts are disclosed in the prior art, it has been found t~at when a cosolvent, such as dimetho~yethane, is used along with lithium tetrafluoroborate,lithium perchlorate or mixtures thereof in conjunction with sulfolane and/or its liquid al.kyl-substituted derivative, a solvent-electrolyte is produced that is admirably sui~ed for use in the electrodeposition of lithium. This discovery makes this solvent-electrolyte ideally suited for use in rechargeable lithium cells using various cathodes.
Thus in accordance with the present invention, the electrolyte solvent mlxture ls preferably c~mposed of from about 20 to about 80 volume per cent of sulfolane and/or the alk~l-substituted derivatives thereof, with the remainder being a cosolvent such as dimethoxyethane along with lithium ~etrafluoroborate, lithium perchlorate or mixtures thereof su~stantially dissolved in said solvent mixture. ThiS solvent-7.
1~253 ~ 3 ~ Q Z
eL~ctrolyte when used ~n a lithium cell will producea coherent layer of nondendritic lithium deposited on the anode during the cell's charging mode of operation~ When the concentration of the sulfolEne and/or the alk~l-substituted derlvatives thereof are below 20 volume per cent of the electrolyte solvent mixture, then using the electrolyte mixture in a re hargeable lithium cell ~ill result in a slightly t~ndritic deposit of lithium on the anode during the cell's charging mode of operation. When the sulfolane and/or the alkyl-substituted derivatives thereof are presen~ in a concentration of above 80 volume per cent, then the electrolyte would be too viscous for efficient high currer~t drain applications.
The concentration of the metal salts lithium tetrafluroborate and/or lithium perchlorate c~n vary in the solvent aithough it has been found thQt a 1.5 molar concentrat~on is preferable.
... ..
3 ~ ~ Z 12253 EXAM~'LE I
To study the effects of various electrolytes upon the morphology of lithium electrodepo its 5 glass test cells were constructed using two spaced-apart, essentially parallel lithium electrodes in about 20 to 30 ml of an electrolyte shown in Table 1. Each : electrode was one-centimeter by 2-centimeters thereby providing two square centimeterR of lithium area a~ailable on each side. A current density of 2 milliamperes per square centimeter was used to discharge (lithium stripping) and charge (lithium plating) the cells. Each cell was discharged for four hours, followed by being charged for four hours ant this cycle was repeated for each cell a number of times as shown in Table 1. The adherent lithium plate, determined by use of the conventional hydrogen evolution test, was evaluated as per cent of the coul~mbically calculated deposit e~pressed as efficiency for both electrodes. The data 80 obtained,including the con~uctivity of each electrolyte~are shown in Table 1.
~3~)()2 _~ ~ . ~ ~ ~ ~ ~D O ~,~
g ~ o~ U`~ ~ ~ ~ ~ U~ ,, o C7 ~. .
~_ ~ U ~ ~ U~ ~ 4 ~ ~ ~ .~
C ~7 . ~.
c~ ~ I~ ~ x a: ~D O
~1 ~ 3 ~ t ~ o ~31 ~o~
0~ 0~ o~ ~ O ~
C ~ ~ U ,~ U ~ ~ 0~ o ~
U ~ X ~ gO .~
O ~ U~
*
~ ~ ~ X ~ ~
O O O O
U~ Q a ~
10.
~3~ ~2 As sh~wn in Table 1, the obtained adherent depocit rom 2.5-M LiC104-dioxolane (DIOX) electrolyte was only h7~/o Of the calculated plate for the five cyclec. Plating from 1.5-M LiC104-DlOX-sulfolane (SULF) solution was somewhat improved on the electrode. Uslng the identical procedure and 707. a~-butyrolactone (~-BL)-30~/~ 1,2-dimethoxyethane (DME) with l-M LiC104 also gave an improvement of the plating on the electrode. The best plating efficiencies were obtained in DME-SULF cosolvent mixtures with either LiBF4 or LiC104 salt or mixtures thereof, EXAMPLE II
Sealed cells were produced using a lithium anode, a titanium disulfide cathode and an electrolyte solution as shown in Table 2. The cells were tested as in Example I and the data obtained are shown in Table 2.
11.
3 ~O 2 12253 Table 2 Electrol~te Solution Efficienc (%~
Solvent Salt; Anode cathode CYcle8 *DME-SULF 1.5-M LiBF4 85 95 5 94 96 ~0 **80DME-20SULF 1.5-M LiBF4 94 96 17 *equal volume of 801vent8 --**80 vol % DME-20 ~ol.% SULF
~XAMPLE III
A sealed ~ell was produced employing a 11thium Enode, a titanium disulfide cathode and En electrolyte solution consisting of 1.5 molar LiBF4 in 50 volume per cent 1,2-dimethoxyethane-50 vo~umeper cent ~ulfo~an~. The .. cell was discharged at a current density of 2 milliamperes per square i~ch for 3 1/2 hours and the~ charged at 0.5 milliampere per.square inch for 16 hours. This discharge-charge cycle was continued for 126 times and the total output for the cell was calculated to be 885 milliampere.-Z0 hours. These results show that more than three times the primary capacity of the lithium anode had been delivered and more than 27 times the primary capacity of the titanium disulfide cathode at a voltage above l. 6 volt~.
It is to be understood that other modifications and changes to the preferred embodiments of this invention herein shown and described can also be made without departing from the spirit and scope of the invention.
lZ.
~.~
1~4300Z 12253 U. S. Patent 4,009,052 discloses a battery utilizing lithium as the ~node-sctive material, titanium disulfide as the cathode-active material and lithium perchlorate dissolved in tetrahydrofuran plu8 d~methoxyethane solvent as the electrolyte.
U. S. Patent 3,907,597 discloses a nonaqueous cell utilizing a h~ghly active metal anode such as lithium, a 601id cathode ~uch as fluorinated carbon, copper sulfide, copper oxide, manganese dioxide, lead dioxide, iron sulfide, copper chloride, silver chlor~deand sulfur, and a liquid organic electrolyte comprising sulfolane or its liquid alkyl-substituted derivativ~ i~ combination with a cosolvent such as dimethoxyethane and an ionizing solute such as lithium perchlorate and lithium cetrafluoroborate.
It is an object of the present invention to provide a rechargeable lithium cell.
Another object of the present invention is to provide a rechargeable lithium/titanium disulfide cell.
Another ob~ect of the present inveo~ion is to provide a nonaqueous electrolyte for rechargeable lithium c~lls consisting of sulfolane, dimethoxyethane and a solute of lithium tetrafluoroborate andlor lithium perchlorate.
The foregoing and additional ob~ects will become more fully apparent from the description hereinafter.
.j 3~
SummarY of the Invention The lnvention relates to a rechargeable ~ell comprising a lithium anode, a cathode such a~ a titanium disulfide cathode,and a nonaqueous electrolyte comprising at least one solvent selected from the group consisting of sulfolane and its liquid alkyl-substituted derivative ~hereof, a cosolvent of the or~ula CH30(CH2CH2O)nCH3 where n varies between --1 (dimethoxyethaneS and 4, and a solute selected from the group consisting of lithium tetrafluoroborate (LiBF4),lithium perchlorate tLiC104) and mixtures thereof. Preferably, the sulfolane and/or the alk~l-substituted derivatives thereof should consist of between about 20 and about 80 volume per cent of the electrolyte solvent mixture with the remainder being the cosolvent and most preferably between about 50 and 80 volume percent of the electrolyte solvent mixture.
Thepreferredcosolvent is dimethoxyethane.
It has been found that using the above electrolyte solution in a lithium cell, a rechargeable lithium cell is produced that does not require the tedious purification procedures that were usually necessary in the prior art in the production of rechargeable lithium cells. The rechargeable cells of this invention have been found to operate eficiently dur~ng numerous charge and discharge cycles without effectively producing dendrltic deposits during the char~ing mode of operation. It has also b4en observed that using the electrolyte solution of this invention .
~ 3Q~2 12253 along with ~ lithlum/tit~nium d~sulfide c~uple, lithium can be efficiently electrodeposited on the li~hiu~ electrode gubstrate during char~ing thus making th$s cell ~y~tem an e~cellent rech~rgeable lithium cell.
Sulfolane for u~e ln ~hi$ ~e~tion ~ a 1, l-d~o~otetrahydrothiophene (~ometi~es callet tetra-~hylene ~ulfo~e) ~nd ls ~ ~aturated heteroc~cl~c cozpound of the ~tructuse:
~2l CIH2 ~2C~e/C~2 0~) Som~ of the phy~cal prGperties of sulfol~ne ~re ~ho~n ~n T~ble 1:
r~ 1 Melting Point ~-C.~ . 28 Boiling Point (-C.) ~ 283 Sp. Cond., 25C. ~ohm~l -1) 2 ~ 10-8 20 Dieleetric Con,~tant, 25C. 44 Densiey, 30UC. (g/cm3) 1.2615 Vi~cos$ty, 30C. (centipoise) 9.87 ~rcezlng Point DepresYion Constant 66.2 5he 3-m~thyl sulfolane, which ~ a liquld alkyl-~ubstituted terivative of the ~bove ~tructure and i ~l~o ~uieable for u~e ~n thi~ lnvention9 ba~ the following ~tructure: .
~2 ~ ~ 2 0~0 . .
1 1 ~30 ~ 12253 Sulfolane and lts liqu~d alkyl-substituted derivat$ves, such as ~-me~hyl sulfolane, are good nonaqueous ~olvents but have the tisadvantage in that they have a relatively high vlscosity. Thus when metal ~alts are dissolved in these ~olvents for the purpose of improving ~he conductivity of the solvents, the viscosity of the 801utlon becomes too high for its efficient use as an electrolyte for nonaqueous cell applications. Consequently the addition of a l~w viscosity cosolvent is necessary if sulfolane and its liquid alkyl-substituted derivatives are to be used as an electroly~e for nonaqueous cells which can operate or perform at a high energy density level.
Although many cosoLvents and metal salts are disclosed in the prior art, it has been found t~at when a cosolvent, such as dimetho~yethane, is used along with lithium tetrafluoroborate,lithium perchlorate or mixtures thereof in conjunction with sulfolane and/or its liquid al.kyl-substituted derivative, a solvent-electrolyte is produced that is admirably sui~ed for use in the electrodeposition of lithium. This discovery makes this solvent-electrolyte ideally suited for use in rechargeable lithium cells using various cathodes.
Thus in accordance with the present invention, the electrolyte solvent mlxture ls preferably c~mposed of from about 20 to about 80 volume per cent of sulfolane and/or the alk~l-substituted derivatives thereof, with the remainder being a cosolvent such as dimethoxyethane along with lithium ~etrafluoroborate, lithium perchlorate or mixtures thereof su~stantially dissolved in said solvent mixture. ThiS solvent-7.
1~253 ~ 3 ~ Q Z
eL~ctrolyte when used ~n a lithium cell will producea coherent layer of nondendritic lithium deposited on the anode during the cell's charging mode of operation~ When the concentration of the sulfolEne and/or the alk~l-substituted derlvatives thereof are below 20 volume per cent of the electrolyte solvent mixture, then using the electrolyte mixture in a re hargeable lithium cell ~ill result in a slightly t~ndritic deposit of lithium on the anode during the cell's charging mode of operation. When the sulfolane and/or the alkyl-substituted derivatives thereof are presen~ in a concentration of above 80 volume per cent, then the electrolyte would be too viscous for efficient high currer~t drain applications.
The concentration of the metal salts lithium tetrafluroborate and/or lithium perchlorate c~n vary in the solvent aithough it has been found thQt a 1.5 molar concentrat~on is preferable.
... ..
3 ~ ~ Z 12253 EXAM~'LE I
To study the effects of various electrolytes upon the morphology of lithium electrodepo its 5 glass test cells were constructed using two spaced-apart, essentially parallel lithium electrodes in about 20 to 30 ml of an electrolyte shown in Table 1. Each : electrode was one-centimeter by 2-centimeters thereby providing two square centimeterR of lithium area a~ailable on each side. A current density of 2 milliamperes per square centimeter was used to discharge (lithium stripping) and charge (lithium plating) the cells. Each cell was discharged for four hours, followed by being charged for four hours ant this cycle was repeated for each cell a number of times as shown in Table 1. The adherent lithium plate, determined by use of the conventional hydrogen evolution test, was evaluated as per cent of the coul~mbically calculated deposit e~pressed as efficiency for both electrodes. The data 80 obtained,including the con~uctivity of each electrolyte~are shown in Table 1.
~3~)()2 _~ ~ . ~ ~ ~ ~ ~D O ~,~
g ~ o~ U`~ ~ ~ ~ ~ U~ ,, o C7 ~. .
~_ ~ U ~ ~ U~ ~ 4 ~ ~ ~ .~
C ~7 . ~.
c~ ~ I~ ~ x a: ~D O
~1 ~ 3 ~ t ~ o ~31 ~o~
0~ 0~ o~ ~ O ~
C ~ ~ U ,~ U ~ ~ 0~ o ~
U ~ X ~ gO .~
O ~ U~
*
~ ~ ~ X ~ ~
O O O O
U~ Q a ~
10.
~3~ ~2 As sh~wn in Table 1, the obtained adherent depocit rom 2.5-M LiC104-dioxolane (DIOX) electrolyte was only h7~/o Of the calculated plate for the five cyclec. Plating from 1.5-M LiC104-DlOX-sulfolane (SULF) solution was somewhat improved on the electrode. Uslng the identical procedure and 707. a~-butyrolactone (~-BL)-30~/~ 1,2-dimethoxyethane (DME) with l-M LiC104 also gave an improvement of the plating on the electrode. The best plating efficiencies were obtained in DME-SULF cosolvent mixtures with either LiBF4 or LiC104 salt or mixtures thereof, EXAMPLE II
Sealed cells were produced using a lithium anode, a titanium disulfide cathode and an electrolyte solution as shown in Table 2. The cells were tested as in Example I and the data obtained are shown in Table 2.
11.
3 ~O 2 12253 Table 2 Electrol~te Solution Efficienc (%~
Solvent Salt; Anode cathode CYcle8 *DME-SULF 1.5-M LiBF4 85 95 5 94 96 ~0 **80DME-20SULF 1.5-M LiBF4 94 96 17 *equal volume of 801vent8 --**80 vol % DME-20 ~ol.% SULF
~XAMPLE III
A sealed ~ell was produced employing a 11thium Enode, a titanium disulfide cathode and En electrolyte solution consisting of 1.5 molar LiBF4 in 50 volume per cent 1,2-dimethoxyethane-50 vo~umeper cent ~ulfo~an~. The .. cell was discharged at a current density of 2 milliamperes per square i~ch for 3 1/2 hours and the~ charged at 0.5 milliampere per.square inch for 16 hours. This discharge-charge cycle was continued for 126 times and the total output for the cell was calculated to be 885 milliampere.-Z0 hours. These results show that more than three times the primary capacity of the lithium anode had been delivered and more than 27 times the primary capacity of the titanium disulfide cathode at a voltage above l. 6 volt~.
It is to be understood that other modifications and changes to the preferred embodiments of this invention herein shown and described can also be made without departing from the spirit and scope of the invention.
lZ.
Claims (9)
1. A rechargeable cell comprising a lithium anode, a cathode and a nonaqueous electrolyte comprising at least one solvent selected from the group consisting of sulfolane and its liquid alkyl-substituted derivatives thereof, a cosolvent of the formula CH3O(CH2CH2O)nCH3 where n varies between 1 and 4, and a solute selected from the group con-sisting of lithium tetrafluoroborate, lithium perchlorate and mixtures thereof.
2. The rechargeable cell of claim 1 wherein the cosolvent is 1,2-dimethoxyethane.
3. The rechargeable cell of claim 1 wherein the cathode is titanium disulfide.
4. The rechargeable cell of claim 3 wherein the cosolvent is 1,2-dimethoxyethane.
5. The rechargeable cell of claim 1, 2 or 3 wherein the at least one solvent selected from the group consisting of sulfolane and its alkyl-substituted derivatives thereof is between about 50 and about 80 volume per cent of the electrolyte solvent mixture.
6. The rechargeable cell of claim 1, 2 or 3 wherein the at least one solvent selected from the group consisting of sulfolane and its alkyl-substituted derivatives thereof is between about 50 and about 80 volume per cent of the electrolyte solvent mixture.
7. The rechargeable cell of claim 1 wherein the cathode is titanium disulfide, the solvent is sulfolane, the cosolvent is 1,2-dimethoxyethane and wherein the sulfolane is between about 20 and about 80 volume per cent of the electrolyte solvent mixture.
8. The rechargeable cell of claim 7 wherein the solute is lithium tetrafluoroborate.
9. The rechargeable cell of claim 7 wherein the solute is lithium perchlorate.
14.
14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5272679A | 1979-06-28 | 1979-06-28 | |
| US052,726 | 1979-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143002A true CA1143002A (en) | 1983-03-15 |
Family
ID=21979518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354948A Expired CA1143002A (en) | 1979-06-28 | 1980-06-26 | Organic electrolyte for rechargeable lithium cells |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS567362A (en) |
| CA (1) | CA1143002A (en) |
| CH (1) | CH644473A5 (en) |
| DE (1) | DE3024151C2 (en) |
| FR (1) | FR2460550A1 (en) |
| GB (1) | GB2054948B (en) |
| IT (1) | IT1131555B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5887778A (en) * | 1981-11-20 | 1983-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous electrolytic solution for lithium secondary battery |
| JPS5951465A (en) * | 1982-08-16 | 1984-03-24 | アライド・コ−ポレ−シヨン | Conjugate polymer battery with improved electrolyte |
| US4482613A (en) * | 1983-02-16 | 1984-11-13 | Duracell Inc. | Cell with safe venting electrolyte |
| JPH0636370B2 (en) * | 1984-01-24 | 1994-05-11 | 日本電信電話株式会社 | Electrolyte for lithium secondary battery |
| US5219684A (en) * | 1990-05-16 | 1993-06-15 | Her Majesty The Queen In Right Of Canada, As Represented By The Province Of British Columbia | Electrochemical cells containing a safety electrolyte solvent |
| US6166899A (en) * | 1997-12-18 | 2000-12-26 | Nippon Chemi-Con Corporation | Electrolyte for electrolytic capacitor and electrolytic capacitor having the same |
| JP2002075446A (en) * | 2000-08-02 | 2002-03-15 | Samsung Sdi Co Ltd | Lithium-sulfur cell |
| KR101108945B1 (en) * | 2004-12-02 | 2012-01-31 | 옥시스 에너지 리미티드 | Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same |
| US20080076029A1 (en) * | 2006-07-27 | 2008-03-27 | Bowden William L | Battery |
| US7648798B2 (en) | 2006-07-27 | 2010-01-19 | The Gillette Company | Battery with electrolyte containing aluminum salt |
| US20080026296A1 (en) * | 2006-07-27 | 2008-01-31 | Bowden William L | Battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907597A (en) * | 1974-09-27 | 1975-09-23 | Union Carbide Corp | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof |
| US3953235A (en) * | 1974-12-23 | 1976-04-27 | Union Carbide Corporation | Nonaqueous cell having an electrolyte containing crotonitrile |
| US4009052A (en) * | 1975-02-24 | 1977-02-22 | Exxon Research And Engineering Company | Chalcogenide battery |
-
1980
- 1980-06-26 CA CA000354948A patent/CA1143002A/en not_active Expired
- 1980-06-27 GB GB8021055A patent/GB2054948B/en not_active Expired
- 1980-06-27 CH CH498580A patent/CH644473A5/en not_active IP Right Cessation
- 1980-06-27 FR FR8014386A patent/FR2460550A1/en active Granted
- 1980-06-27 DE DE3024151A patent/DE3024151C2/en not_active Expired
- 1980-06-27 JP JP8768280A patent/JPS567362A/en active Pending
- 1980-06-30 IT IT23148/80A patent/IT1131555B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2460550B1 (en) | 1984-10-12 |
| FR2460550A1 (en) | 1981-01-23 |
| GB2054948A (en) | 1981-02-18 |
| GB2054948B (en) | 1983-05-11 |
| DE3024151C2 (en) | 1983-12-01 |
| JPS567362A (en) | 1981-01-26 |
| CH644473A5 (en) | 1984-07-31 |
| DE3024151A1 (en) | 1981-01-08 |
| IT8023148A0 (en) | 1980-06-30 |
| IT1131555B (en) | 1986-06-25 |
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