CA1066766A - Reversible lithium battery using a dioxolane based solvent system - Google Patents
Reversible lithium battery using a dioxolane based solvent systemInfo
- Publication number
- CA1066766A CA1066766A CA250,060A CA250060A CA1066766A CA 1066766 A CA1066766 A CA 1066766A CA 250060 A CA250060 A CA 250060A CA 1066766 A CA1066766 A CA 1066766A
- Authority
- CA
- Canada
- Prior art keywords
- electrochemical cell
- lithium
- anode
- active material
- dioxolane
- 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
Links
Classifications
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved rechargeable, high energy density electrochemical cell comprises an anode having as its ac-tive material an alkali metal, a cathode having as its active material a transition metal dichalcogenide and a nonaqueous electrolyte containing at least one ionizable salt of the anode-active material dissolved in dioxolane.
A specific example is an electrochemical cell with an anode-active material of lithium or alloys thereof, a cathode of titanium disulfide and an electrolyte of lithium perchlor-ate dissolved in dioxolane.
An improved rechargeable, high energy density electrochemical cell comprises an anode having as its ac-tive material an alkali metal, a cathode having as its active material a transition metal dichalcogenide and a nonaqueous electrolyte containing at least one ionizable salt of the anode-active material dissolved in dioxolane.
A specific example is an electrochemical cell with an anode-active material of lithium or alloys thereof, a cathode of titanium disulfide and an electrolyte of lithium perchlor-ate dissolved in dioxolane.
Description
BAC~CGROUND OF THE INVh'21TION
2 The present invention relates to high energy den-
3 sity electrochemical cells and more particularly to a non-
4 aqueous electrolyte for a rechargeable, high energy density electrochemical cell having anode-cathode couples of alkali 6 metals and lamellar transition metal dichalcogenides.
7 A recently developed rechargeable, high energy den-8 sity electrochemical cell consists of an electronegative g material as the anode-active material, a transition metal tichalcogenide as the cathode-active material, and a non-11 aqueous electrolyte. More specifically, the cell consists 12 of a lithium anode, a titanium disulfide cathode and a non-13 aqueous electrolyte consisting of lithium salts dissolved in -14 organic solvents, such as propylene carbonate, tetrahydro-15 furan, and a mixture of dimethyoxyethane and tetrahydro- `
16 furan. ~
17 An important feature of these cells is their abil-` 18 ity to be discharged and charged. Theoretically, cycling 19 by discharging and charging should be possible indefinitely~
but in practice indefinite cycling is not realized. Dendri-21 tic growth on the anode during charging and degradation of 22 the cathode material are usually the limiting factors in the 23 amount of cycling a cell can be subjected to; but the elec-24 trolyte~ particularly with nonaqueous electrolytes, can at times be the limiting factor. The effects of a particular 26 solvent on the electrochemical performance of a cell cannot 27 be determined o~ theoretical grounds, but must be ascertain-28 ed empirically. A particular organic electrolyte might be 29 highly efèctive with a given anode-cathode couple but be . .
ineffective for another couple, either because it is not 31 inert to the second couple or because it reacts with itself 32 under the conditions present during cycling. Furthermore, t , A ~ 2 - ~
1 an organic electrolyte might be perfectly suited for use in 2 a pr~mary cell and not useable for secondary cells.
3 Industrial use of any high energy density cell i8 4 dependent upon a number of factors including initial cost and service life. Wide industrial use of any electrochemi-6 cal cell is dependent upon extending the service life of 7 àll components of the cell9 including the electrolyte.
9 Generally speaking, the present invention contem-plates an ~mproved electrochemical cell that includes an 11 snode of an alkali metal or alloys thereof, a cathode of a 12 lamellar transition metal dichalcogenide and an electrolyte 13 consisting essentially of at least one ionlc salt of the 14 alkali metal contained in the anode dissolved in dioxolane solutions.
16 DETAIL~D DESCRIPTION
17 The present invention relates to an improved, re-18 chargeable, high energy density electrochemical cell. The 19 cell comprises anode cathode couples of highly electronega-2D tive alkali metals or alloys thereof and a lamellar transi-21 tion metal dichalcogenide. Alkali metals as used herein 22 include lithium, sodium and potassium, and transition metals 23 include at least one member selected from the group consist-24 ing of titanium, niobium an~ tantalum. The anode is advan-tageously made of lithium or lithium alloys because l~thium 26 has the lowest equivalent weight of the alkali metals and is D the most electronegative, thereby providing the most energy 28 per weight unit. Of the lamellar transition metal dichalco-29 genides the most preferred is titanium disulfide because it 3~ has a low equivalent weight, is electrically conductive and 31 its constituents are readily available. The electrolyte con-32 sists essentially of an ionizable salt of the anode-active 1 material dissolved in dioxolane solutions. Such cells have 2 high energy densities and can be repeatedly cycled without 3 significant fading of cell capacity.
4 The improved cell in accordance with the present S invention employs as an electrolyte an ionizable salt of 6 the anode-active material dissolved in dioxolane solutions.
7 The sale of the anode-active material should not react with 8 or promote a reaction of the dioxolane solution. When li-9 thium is employed as the anode-active material, ionic lithi-um salts, such as lithium perchlorate, lithium hexafluoro-11 phosphate, lithium hexafluoroarsenate, lithium tetrafluoro-12 borate, and the like, can be dissolved in dioxolane solu-13 ~ tions to provide electrolytes for the electrochemical cell.
14 Lithium perchlorate has been found particularly effective when used in conjunction with dioxolane or solutions of di-16 oxolane.
17 The concentration of the lithium salts in the non-18 aqueous solvent can vary from at least about 0.5 mole per ~ -19 liter (M/l) of solvent and up to the saturation point. How-ever, concentrations between about 0.1 M/l and 3 M/l have 21 been found the most effective. At concentrations of less 22 than about 0.5 M/l, the flow current through the cell is 23 significantly lowered due to the decrease in ionic mass 24 transport. At concentrations higher than about 3 M/l, the risk of precipitating lithium salts on the components of the 26 electrochemical cell is substantially increased due to in-27 creased electroiyte viscosity and decreased mass transport.
28 The ~se of dioxolane or solutions thereof as sol-29 vents for the lithium salts is an important feature of the present invention. Dioxolane dissolves substantial quanti-31 ties of the lithium salts, is substantially inert to both 32 the anode and cathode materials, and is chemically stable ~ 4 ~
1` under operating conditions.
2 The electrolyte consis~s essentially of ionlzable 3 salts of the cnode-active material and dioxolane, but other 4 additives and diluents can be employed in amounts up to
7 A recently developed rechargeable, high energy den-8 sity electrochemical cell consists of an electronegative g material as the anode-active material, a transition metal tichalcogenide as the cathode-active material, and a non-11 aqueous electrolyte. More specifically, the cell consists 12 of a lithium anode, a titanium disulfide cathode and a non-13 aqueous electrolyte consisting of lithium salts dissolved in -14 organic solvents, such as propylene carbonate, tetrahydro-15 furan, and a mixture of dimethyoxyethane and tetrahydro- `
16 furan. ~
17 An important feature of these cells is their abil-` 18 ity to be discharged and charged. Theoretically, cycling 19 by discharging and charging should be possible indefinitely~
but in practice indefinite cycling is not realized. Dendri-21 tic growth on the anode during charging and degradation of 22 the cathode material are usually the limiting factors in the 23 amount of cycling a cell can be subjected to; but the elec-24 trolyte~ particularly with nonaqueous electrolytes, can at times be the limiting factor. The effects of a particular 26 solvent on the electrochemical performance of a cell cannot 27 be determined o~ theoretical grounds, but must be ascertain-28 ed empirically. A particular organic electrolyte might be 29 highly efèctive with a given anode-cathode couple but be . .
ineffective for another couple, either because it is not 31 inert to the second couple or because it reacts with itself 32 under the conditions present during cycling. Furthermore, t , A ~ 2 - ~
1 an organic electrolyte might be perfectly suited for use in 2 a pr~mary cell and not useable for secondary cells.
3 Industrial use of any high energy density cell i8 4 dependent upon a number of factors including initial cost and service life. Wide industrial use of any electrochemi-6 cal cell is dependent upon extending the service life of 7 àll components of the cell9 including the electrolyte.
9 Generally speaking, the present invention contem-plates an ~mproved electrochemical cell that includes an 11 snode of an alkali metal or alloys thereof, a cathode of a 12 lamellar transition metal dichalcogenide and an electrolyte 13 consisting essentially of at least one ionlc salt of the 14 alkali metal contained in the anode dissolved in dioxolane solutions.
16 DETAIL~D DESCRIPTION
17 The present invention relates to an improved, re-18 chargeable, high energy density electrochemical cell. The 19 cell comprises anode cathode couples of highly electronega-2D tive alkali metals or alloys thereof and a lamellar transi-21 tion metal dichalcogenide. Alkali metals as used herein 22 include lithium, sodium and potassium, and transition metals 23 include at least one member selected from the group consist-24 ing of titanium, niobium an~ tantalum. The anode is advan-tageously made of lithium or lithium alloys because l~thium 26 has the lowest equivalent weight of the alkali metals and is D the most electronegative, thereby providing the most energy 28 per weight unit. Of the lamellar transition metal dichalco-29 genides the most preferred is titanium disulfide because it 3~ has a low equivalent weight, is electrically conductive and 31 its constituents are readily available. The electrolyte con-32 sists essentially of an ionizable salt of the anode-active 1 material dissolved in dioxolane solutions. Such cells have 2 high energy densities and can be repeatedly cycled without 3 significant fading of cell capacity.
4 The improved cell in accordance with the present S invention employs as an electrolyte an ionizable salt of 6 the anode-active material dissolved in dioxolane solutions.
7 The sale of the anode-active material should not react with 8 or promote a reaction of the dioxolane solution. When li-9 thium is employed as the anode-active material, ionic lithi-um salts, such as lithium perchlorate, lithium hexafluoro-11 phosphate, lithium hexafluoroarsenate, lithium tetrafluoro-12 borate, and the like, can be dissolved in dioxolane solu-13 ~ tions to provide electrolytes for the electrochemical cell.
14 Lithium perchlorate has been found particularly effective when used in conjunction with dioxolane or solutions of di-16 oxolane.
17 The concentration of the lithium salts in the non-18 aqueous solvent can vary from at least about 0.5 mole per ~ -19 liter (M/l) of solvent and up to the saturation point. How-ever, concentrations between about 0.1 M/l and 3 M/l have 21 been found the most effective. At concentrations of less 22 than about 0.5 M/l, the flow current through the cell is 23 significantly lowered due to the decrease in ionic mass 24 transport. At concentrations higher than about 3 M/l, the risk of precipitating lithium salts on the components of the 26 electrochemical cell is substantially increased due to in-27 creased electroiyte viscosity and decreased mass transport.
28 The ~se of dioxolane or solutions thereof as sol-29 vents for the lithium salts is an important feature of the present invention. Dioxolane dissolves substantial quanti-31 ties of the lithium salts, is substantially inert to both 32 the anode and cathode materials, and is chemically stable ~ 4 ~
1` under operating conditions.
2 The electrolyte consis~s essentially of ionlzable 3 salts of the cnode-active material and dioxolane, but other 4 additives and diluents can be employed in amounts up to
5 about 50 percent as long as the novel characteristics of
6 the electrolyte are not impaired. Straight chain ethers,
7 cyclical ethers, polyethers and organic esters are effective
8 diluents. Speciic examples of such diluents include di-
9 methyoxyethane, propylene carbonate, tetrahydrofuran and
10 furan. Solutions of dioxolane and dimethyoxyethane are
11 pRrticularly advantageous in that a greater percentage of
12 the theoretical capacity of the electrochemical cell can be
13 utilized, both initially and after recycling. The electro-
14 lyte can also contain additives for minimiæing dendritic
15 growth upon charging. Other additives can include polymeri-
16 zation inhibitors such as dimethylisoxazole, triethyl phos-
17 phite and triethyl amine.
18 In order to give those skilled in the art a better
19 appreciation of the present ~nvention, the following illus- J
20 trative examples are given:
21 EXAMPLE 1
22 A capacity limiting cathode of 0.48 gram of stoichio-
23 metric titanium disùlfide and a lithium-aluminum anode (20%
24 lithium by weight and the balance aluminum) and weighing .5
25 gram was placed in a chemically inert holder into which a
26 solution of 2.5 molar (M) lithium perchlorate in dioxolane
27 was added in amounts sufficient to comple~ely immerse the
28 anode and the cathode. One layer of porous polypropylene
29 ~abric plus an additional layer of an inorganic separator with ~ -
30 a totalthickness o~ .06 centimeters was placed between the
31 anode and the cathode to act as a separator. This cell was
32 designated Cell A. ~ ¦~
33 The initial open circult voltap,e was 2.55 volts.
- S - , , . . . ~
1()66766 1 The cell was discharged to 1.5 volts at a rate of 10 milli-2 amps per square centimeter (ma/cm2) and then charged to 2.60 3 volts at a rate of 2.5 ma/cm2. Approximately every 30th or 4 40th cycle the cell was trickle charged by reducing the charge current density to approximately 0.1 ma/cm2 and again 6 charging to 2.60 volts.
7 A similar cell (designated Cell B) except that the 8 cathode contained only 0.35 gram stoichiometric titanium 9 disulfide and the electrolyte consisted of a 2 M lithium perchlorate solution in a mixture of 70% tetrahydrofuran 11 and 307O dimethyoxyethane was tested for comparative pur-12 poses. The results o these tests are reported in Table I.
13 The theoretical capacities of the cells were cal-14 culated by applying Faraday's law to the reaction:
TiS2 + Li ~ - ) LiTiS2 16 The theoretical capacity of titanium disulfide calculated 17 in this manner was found to be 240 milliamp-hours per 18 gram of titanium disulfide. The amounts of current with-19 drawn upon discharge and utilized in charging were then re-lated to the theoretical values so that the values presented 21 in Table I are percentages of the theoretical capacities.
22 The results shown in Table I confirm the superior- -23 ity of the cell using the electrolyte of the present inven-24 tion over that of prior art elec~rolytes. The results in Table I show that cells using dioxolane can be cycled a 26 Ereater number of eimes than prior art cells.
' . .,' ' : . ~
~0667~;6 :~
.~ 00 ~d t~
,~ _, U~ U~ . . . . . . . .
U~U~U~, .......
~,~
td "
_, ~ ..:~
J~ OO~rl , ~ s~ ~, ~o ~ ~ o E~ ~ ' ~ .
D o ~ '' !: :`
~1 ~, , ~
, t, . .
.. ~, , .` ~ ~
. ~ ~o oo ~ U ~ ~ ~O $ ~ o U , ':
~ ~ ~" ~,., ~ :.
.. ~ ; 1:
_ 7
- S - , , . . . ~
1()66766 1 The cell was discharged to 1.5 volts at a rate of 10 milli-2 amps per square centimeter (ma/cm2) and then charged to 2.60 3 volts at a rate of 2.5 ma/cm2. Approximately every 30th or 4 40th cycle the cell was trickle charged by reducing the charge current density to approximately 0.1 ma/cm2 and again 6 charging to 2.60 volts.
7 A similar cell (designated Cell B) except that the 8 cathode contained only 0.35 gram stoichiometric titanium 9 disulfide and the electrolyte consisted of a 2 M lithium perchlorate solution in a mixture of 70% tetrahydrofuran 11 and 307O dimethyoxyethane was tested for comparative pur-12 poses. The results o these tests are reported in Table I.
13 The theoretical capacities of the cells were cal-14 culated by applying Faraday's law to the reaction:
TiS2 + Li ~ - ) LiTiS2 16 The theoretical capacity of titanium disulfide calculated 17 in this manner was found to be 240 milliamp-hours per 18 gram of titanium disulfide. The amounts of current with-19 drawn upon discharge and utilized in charging were then re-lated to the theoretical values so that the values presented 21 in Table I are percentages of the theoretical capacities.
22 The results shown in Table I confirm the superior- -23 ity of the cell using the electrolyte of the present inven-24 tion over that of prior art elec~rolytes. The results in Table I show that cells using dioxolane can be cycled a 26 Ereater number of eimes than prior art cells.
' . .,' ' : . ~
~0667~;6 :~
.~ 00 ~d t~
,~ _, U~ U~ . . . . . . . .
U~U~U~, .......
~,~
td "
_, ~ ..:~
J~ OO~rl , ~ s~ ~, ~o ~ ~ o E~ ~ ' ~ .
D o ~ '' !: :`
~1 ~, , ~
, t, . .
.. ~, , .` ~ ~
. ~ ~o oo ~ U ~ ~ ~O $ ~ o U , ':
~ ~ ~" ~,., ~ :.
.. ~ ; 1:
_ 7
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a reversible electrochemical cell that includes an anode having at least one alkali metal as its active mater-ial, a cathode having a lamellar transition metal dichalco-genide as the cathode-active material and an electrolyte containing ions of at least the anode-active material, the improvement which comprises an electrolyte consisting essen-tially of at least ionic salts of the anode-active material dissolved in dioxolane.
2. The electrochemical cell described in claim 1 wherein the anode-active material is lithium or alloys thereof and the cathode-active material is titanium disul-fide.
3. The electrochemical cell as described in claim 2 wherein the lithium salt is lithium perchlorate.
4. The electrochemical cell as described in claim 2 wherein the lithium salt is lithium hexafluorophosphate.
5. The electrochemical cell as described in claim 2 wherein the lithium salt is lithium hexafluoroarsenate.
6. The electrochemical cell as described in claim 2 wherein the lithium salt is lithium tetrafluoroborate.
7. The electrochemical cell as described in claim 3 wherein the concentration of the lithium perchlorate in the dioxolane is between about 0.5 and 3 M/l.
8. The electrochemical cell as described in claim 5 wherein the electrolyte contains a polymerization inhibitor.
9. The electrochemical cell as described in claim 2 wherein the electrolyte contains at least one diluent se-lected from the group consisting of straight chain ethers, polyethers, cyclical ethers and organic esters.
10. The electrochemical cell as described in claim 9 wherein the diluent is present in amounts of up to about 50%, by volume.
11. The electrochemical cell as described in claim 2 wherein the electrolyte consists essentially of an ionic lithium salt dissolved in a mixture of dioxolane and dimeth-yoxyethane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57623775A | 1975-05-09 | 1975-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066766A true CA1066766A (en) | 1979-11-20 |
Family
ID=24303530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA250,060A Expired CA1066766A (en) | 1975-05-09 | 1976-04-12 | Reversible lithium battery using a dioxolane based solvent system |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS51137839A (en) |
| BE (1) | BE841595A (en) |
| CA (1) | CA1066766A (en) |
| DE (1) | DE2619806A1 (en) |
| FR (1) | FR2312124A1 (en) |
| GB (1) | GB1522218A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125687A (en) * | 1977-06-27 | 1978-11-14 | Bell Telephone Laboratories, Incorporated | Rechargeable nonaqueous cell with chalcogenide electrode |
| US4357398A (en) * | 1981-03-05 | 1982-11-02 | The United States Of America As Represented By The United States Department Of Energy | Electrochemical cell having cylindrical electrode elements |
| US4456520A (en) * | 1982-03-01 | 1984-06-26 | Medtronic, Inc. | Porous rigid titanium disulfide electrodes for electrochemical cells and method for preparing same |
| JPS5931572A (en) * | 1982-08-16 | 1984-02-20 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium secondary battery |
| JPS59167971A (en) * | 1983-03-14 | 1984-09-21 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium secondary cell |
| JPS6079676A (en) * | 1983-10-06 | 1985-05-07 | Hitachi Maxell Ltd | Lithium secondary battery |
| EP0614239A3 (en) * | 1993-03-01 | 1996-10-16 | Tadiran Ltd | Non-aqueous safe secondary cell. |
| WO2000036683A2 (en) * | 1998-12-17 | 2000-06-22 | Moltech Corporation | Non-aqueous electrolytes for electrochemical cells |
| US7510808B2 (en) | 2004-08-27 | 2009-03-31 | Eveready Battery Company, Inc. | Low temperature Li/FeS2 battery |
| US7722988B2 (en) | 2005-08-16 | 2010-05-25 | Eveready Battery Company, Inc. | All-temperature LiFeS2 battery with ether and low concentration LiI electrolyte |
| CN113839059A (en) * | 2021-09-16 | 2021-12-24 | 湖州昆仑亿恩科电池材料有限公司 | Primary lithium battery and electrolyte thereof |
-
1976
- 1976-04-12 CA CA250,060A patent/CA1066766A/en not_active Expired
- 1976-04-22 GB GB16352/76A patent/GB1522218A/en not_active Expired
- 1976-04-28 JP JP51049323A patent/JPS51137839A/en active Pending
- 1976-04-30 FR FR7612949A patent/FR2312124A1/en active Granted
- 1976-05-05 DE DE19762619806 patent/DE2619806A1/en not_active Withdrawn
- 1976-05-07 BE BE166851A patent/BE841595A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2312124A1 (en) | 1976-12-17 |
| GB1522218A (en) | 1978-08-23 |
| DE2619806A1 (en) | 1976-11-18 |
| FR2312124B1 (en) | 1980-03-14 |
| JPS51137839A (en) | 1976-11-29 |
| BE841595A (en) | 1976-11-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |
Effective date: 19961120 |