USH496H - Electrolyte for use in an all inorganic rechargeable cell and lithium inorganic cell containing the improved electrolyte - Google Patents
Electrolyte for use in an all inorganic rechargeable cell and lithium inorganic cell containing the improved electrolyte Download PDFInfo
- Publication number
- USH496H USH496H US07/084,278 US8427887A USH496H US H496 H USH496 H US H496H US 8427887 A US8427887 A US 8427887A US H496 H USH496 H US H496H
- Authority
- US
- United States
- Prior art keywords
- electrolyte
- lialcl
- lithium
- cosolvent
- percent
- 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.)
- Abandoned
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
Definitions
- This invention relates in general to an improved electrolyte for use in all inorganic rechargeable cell and to an all inorganic rechargeable cell including the improved electrolyte and in particular to an improved electrolyte for use in a lithium/SO 2 rechargeable cell and to a lithium/SO 2 rechargeable cell including the improved electrolyte.
- An all inorganic Li/SO 2 rechargeable cell generally includes a lithium anode, a porous carbon cathode and a stable highly conductive liquid electrolyte complex LiAlCl 4 --xSO 2 .
- This complex is rapidly formed when the commonly used LiAlCl 4 electrolyte salt reacts with SO 2 gas or SO 2 liquid.
- the initially formed liquid complex has the formula LiAlCl 4 --3SO 2
- additional lowered LiAlCl 4 salt concentration can be achieved at will by diluting the above electrolyte with additional SO 2 .
- electrolyte with formulas LiAlCl--xSO 2 where x is at least 3 can be prepared.
- the starting electrolyte LiAlCl 4 --3SO 2 has a very high specific conductivity of 0.1 S/cm. The fact that this is the highest known conductivity for any ambient temperature non aqueous electrolyte makes this general class of electrolytes extremely valuable.
- the general object of this invention is to provide an improved lithium inorganic rechargeable cell system.
- a more particular object is to minimize or even eliminate LiAlCl 4 coprecipitation and thus improve cell capacity.
- the cosolvent should be capable of rapidly dissolving the LiAlCl 4 salt and, in order to minimize IR losses, must in the process form a reasonably conducting electrolyte solution.
- a particularly effective cosolvent has been found to be sulfuryl chloride, SO 2 Cl 2 .
- SO 2 Cl 2 sulfuryl chloride
- the cells include a lithium anode, a porous carbon cathode made from high surface area carbon black and a LiAlCl 4 electrolyte salt.
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- Chemical & Material Sciences (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)
Abstract
An improved electrolyte is provided in a lithium/sulfur dioxide rechargea cell, the electrolyte comprising a solution of a stable, highly conductive liquid electrolyte complex LiAlCl4 --3SO2 and up to about 50 percent by weight of sulfuryl chloride as a cosolvent.
Description
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalty thereon.
This invention relates in general to an improved electrolyte for use in all inorganic rechargeable cell and to an all inorganic rechargeable cell including the improved electrolyte and in particular to an improved electrolyte for use in a lithium/SO2 rechargeable cell and to a lithium/SO2 rechargeable cell including the improved electrolyte.
An all inorganic Li/SO2 rechargeable cell generally includes a lithium anode, a porous carbon cathode and a stable highly conductive liquid electrolyte complex LiAlCl4 --xSO2. This complex is rapidly formed when the commonly used LiAlCl4 electrolyte salt reacts with SO2 gas or SO2 liquid. Although the initially formed liquid complex has the formula LiAlCl4 --3SO2, additional lowered LiAlCl4 salt concentration can be achieved at will by diluting the above electrolyte with additional SO2. Thus, electrolyte with formulas LiAlCl--xSO2 where x is at least 3 can be prepared. The starting electrolyte LiAlCl4 --3SO2 has a very high specific conductivity of 0.1 S/cm. The fact that this is the highest known conductivity for any ambient temperature non aqueous electrolyte makes this general class of electrolytes extremely valuable.
One difficulty with the use of this electrolyte is however, that during cell discharge, the insoluble reduction product is deposited in the porous carbon cathode. Simultaneously, some of the LiAlCl4 electrolyte salt is also precipitated in the porous carbon cathode. The coprecipitation of electrolyte salt is partially responsible for the severely reduced capacity currently plaguing this system.
The general object of this invention is to provide an improved lithium inorganic rechargeable cell system. A more particular object is to minimize or even eliminate LiAlCl4 coprecipitation and thus improve cell capacity.
It has been found that the aforementioned objects can be attained by adding a suitable cosolvent to the electrolyte to allow excess LiAlCl4 that would normally precipitate to dissolve. The requirements of an effective cosolvent are:
(A) The cosolvent should be capable of rapidly dissolving the LiAlCl4 salt and, in order to minimize IR losses, must in the process form a reasonably conducting electrolyte solution.
(B) The cosolvent should be extremely miscible with liquid SO2.
(C) The cosolvent must not become easily oxidized during cell charging which typically takes place at 4.0 volts relative to lithium.
(D) The cosolvent should not become chemically degraded in the presence of AlCl3 or chlorine, both of which are formed during cell charging.
A particularly effective cosolvent has been found to be sulfuryl chloride, SO2 Cl2. One would not expect that the addition of SO2 Cl2 as a cosolvent would be able to improve cell capacity in Li/SO2 rechargeable cells since the specific conductivity of pure SO2 Cl2 is very poor. That is, pure SO2 Cl2 is one million times less conductive than is the LiAlCl4 --3SO2 electrolyte.
Experimental results were obtained in small laboratory cells. The cells include a lithium anode, a porous carbon cathode made from high surface area carbon black and a LiAlCl4 electrolyte salt.
The following electrolytes were tested: (1) LiAlCl--3SO2 ; (2) LiAlCl4 --3SO2 +10% SO2 Cl2 ; (3) LiAlCl4 --3SO2 +20% SO2 Cl2 ; and (4) LiAlCl4 --SO2 Cl2
The results of these experiments are shown in the following Table:
______________________________________ FIRST CYCLE TENTH CYCLE CAPACITY CAPACITY ELECTROLYTE mAH mAH ______________________________________ LiAlCl.sub.4 --3SO.sub.2 9 14 LiAlCl.sub.4 --3SO.sub.2 + 10% SO.sub.2 Cl.sub.2 32 20 LiAlCl.sub.4 --3SO.sub.2 + 20% SO.sub.2 Cl.sub.2 52 18 LiAlCl.sub.4 --SO.sub.2 Cl.sub.2 20 0 ______________________________________
The results clearly show that Li/LiAlCl4 --3SO2 cells constructed with 10% and 20% added SO2 Cl2 had longer capacities than either Li/LiAlCl4 --3SO2 cells or even Li/LiAlCl4 --SO2 Cl2 cells. It is clear that on the TENTH CYCLE, the advantage of the addition of low percentages of SO2 Cl2 is evident. Cells containing more than 50% added SO2 Cl2 could not be cycled ten times.
We wish it to be understood that we do not desire to be limited to the exact details as described for obvious modifications will occur to a person skilled in the art.
Claims (10)
1. An improved electrolyte for use in an all inorganic rechargeable cell, said electrolyte comprising a solution of a stable, highly conductive liquid electrolyte complex LiAlCl--XSO2 where x is at least 3, and up to about 50 percent by weight of a cosolvent that is: (a) capable of rapidly dissolving a LiAlCl4 salt and in the process forming a reasonably conducting electrolyte solution; (b) extremely miscible with liquid SO2 ; (c) not easily oxidized during cell charging; and (d) not chemically degraded in the presence of reaction products formed during cell charging.
2. An improved electrolyte according to claim 1 wherein the cosolvent is sulfuryl chloride.
3. An improved electrolyte for use in a lithium/sulfur dioxide rechargeable cell, said electrolyte comprising a solution of a stable, highly conductive liquid electrolyte complex LiAlCl--xSO2, where x is at least 3, and up to about 50 percent by weight of a cosolvent that is:
(a) capable of rapidly dissolving LiAlCl4 salt and in the process forming a reasonably conducting electrolyte solution;
(b) extremly miscible with liquid SO2 ; (c) not easily oxidized during cell charging which takes place at about 4.0 volts relative to lithium; and (d) not chemically degraded in the presence of AlCl3 or Cl2, both of which are formed during cell charging.
4. An improved electrolyte according to claim 3 wherein the liquid complex has the formula LiAlCl4 --3SO2.
5. An improved electrolyte according to claim 4 wherein the cosolvent is from about 10 percent to about 20 percent by weight of the electrolyte of sulfuryl chloride.
6. An improved electrolyte according to claim 3 wherein the cosolvent is sulfuryl chloride.
7. A lithium inorganic rechargeable electrochemical cell comprising lithium as the anode, a porous carbon as the cathode, and a solution of a stable, highly conductive liquid electrolyte complex LiAlCl4 --xSO2 awhere x is at least 3, and up to about 50 percent by weight of a cosolvent that is: (A) capable of readily dissolving LiAlCl4 salt and in the process forming a reasonably conducting electrolyte solution; (B) extremely miscible with liquid SO2 ; (C) not easily oxidized during cell charging which takes place at about 4.0 volts relative to lithium; and (D) not chemically degraded in the presence of AlCl3 or Cl2, both of which are formed during cell charging; as the electrolyte.
8. A lithium inorganic rechargeable electrochemical cell according to claim 7 wherein the liquid complex has the formula LiAlCl--3SO2.
9. A lithium inorganic rechargeable electrochemical cell according to claim 8 wherein the cosolvent is from about 10 percent to about 20 percent by weight of the electrolyte of sulfuryl chloride.
10. A lithium inorganic rechargeable electrochemical cell according to claim 7 wherein the cosolvent is sulfuryl chloride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/084,278 USH496H (en) | 1987-08-10 | 1987-08-10 | Electrolyte for use in an all inorganic rechargeable cell and lithium inorganic cell containing the improved electrolyte |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/084,278 USH496H (en) | 1987-08-10 | 1987-08-10 | Electrolyte for use in an all inorganic rechargeable cell and lithium inorganic cell containing the improved electrolyte |
Publications (1)
Publication Number | Publication Date |
---|---|
USH496H true USH496H (en) | 1988-07-05 |
Family
ID=22183931
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/084,278 Abandoned USH496H (en) | 1987-08-10 | 1987-08-10 | Electrolyte for use in an all inorganic rechargeable cell and lithium inorganic cell containing the improved electrolyte |
Country Status (1)
Country | Link |
---|---|
US (1) | USH496H (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2663467A1 (en) * | 1990-06-14 | 1991-12-20 | Commissariat Energie Atomique | CELL OF WHICH THE ANODE IS AN ALKALINE OR ALKALINE-EARTH METAL AND OF WHICH THE POSITIVE ACTIVE MATERIAL IS LIQUID. |
US20120121972A1 (en) * | 2003-09-23 | 2012-05-17 | Guenther Hambitzer | Electrochemical battery cell |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2140146C3 (en) | 1971-08-11 | 1975-11-06 | Kuehnl, H., Prof. Dr., 3000 Hannover | Galvanic element which can be used as a storage battery and has a negative electrode made of an alkali metal or aluminum and an electrolyte containing SO deep 2 |
USRE30661E (en) | 1977-03-23 | 1981-06-30 | Electrochimica Corporation | Electric current producing galvanic cell |
US4375502A (en) | 1980-05-07 | 1983-03-01 | Societe Anonyme Dite: Gipelec | Electrolyte for a lithium/thionyl chloride electric cell, a method of preparing said electrolyte and an electric cell which includes said electrolyte |
US4547441A (en) | 1984-12-03 | 1985-10-15 | Saft | Electrochemical cell with negative active material based on an alkali or alkaline earth metal |
-
1987
- 1987-08-10 US US07/084,278 patent/USH496H/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2140146C3 (en) | 1971-08-11 | 1975-11-06 | Kuehnl, H., Prof. Dr., 3000 Hannover | Galvanic element which can be used as a storage battery and has a negative electrode made of an alkali metal or aluminum and an electrolyte containing SO deep 2 |
USRE30661E (en) | 1977-03-23 | 1981-06-30 | Electrochimica Corporation | Electric current producing galvanic cell |
US4375502A (en) | 1980-05-07 | 1983-03-01 | Societe Anonyme Dite: Gipelec | Electrolyte for a lithium/thionyl chloride electric cell, a method of preparing said electrolyte and an electric cell which includes said electrolyte |
US4547441A (en) | 1984-12-03 | 1985-10-15 | Saft | Electrochemical cell with negative active material based on an alkali or alkaline earth metal |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2663467A1 (en) * | 1990-06-14 | 1991-12-20 | Commissariat Energie Atomique | CELL OF WHICH THE ANODE IS AN ALKALINE OR ALKALINE-EARTH METAL AND OF WHICH THE POSITIVE ACTIVE MATERIAL IS LIQUID. |
WO1991020103A1 (en) * | 1990-06-14 | 1991-12-26 | Commissariat A L'energie Atomique | Triggerable cell for delivering high current densities in a wide range of temperatures |
US20120121972A1 (en) * | 2003-09-23 | 2012-05-17 | Guenther Hambitzer | Electrochemical battery cell |
US8858655B2 (en) * | 2003-09-23 | 2014-10-14 | Hambitzer Gmbh | Electrochemical battery cell |
US10637096B2 (en) | 2003-09-23 | 2020-04-28 | Hambitzer Gmbh | Electrochemical battery cell |
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Legal Events
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STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
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AS | Assignment |
Owner name: UNITED STATES OF AMERICA, THE, AS REPRESENTED BY T Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MAMMONE, ROBERT J.;BINDER, MICHAEL;REEL/FRAME:005031/0576;SIGNING DATES FROM 19870722 TO 19870803 |