CA1307024C - Separator for lithium batteries and lithium batteries including the separator - Google Patents
Separator for lithium batteries and lithium batteries including the separatorInfo
- Publication number
- CA1307024C CA1307024C CA000599185A CA599185A CA1307024C CA 1307024 C CA1307024 C CA 1307024C CA 000599185 A CA000599185 A CA 000599185A CA 599185 A CA599185 A CA 599185A CA 1307024 C CA1307024 C CA 1307024C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- lithium
- separator
- anode
- porous membrane
- 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
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
ABSTRACT
A multilayer separator is provided for insertion between the cathode and anode in lithium secondary or primary batteries, the multilayer separator comprising an electrically insulating porous membrane layer and an electroactive polymeric material layer, wherein the polymer is one that will react with any lithium dendrite formed during cycling of the battery that could otherwise penetrate the separator, thus preventing an internal short circuit of the cell.
A multilayer separator is provided for insertion between the cathode and anode in lithium secondary or primary batteries, the multilayer separator comprising an electrically insulating porous membrane layer and an electroactive polymeric material layer, wherein the polymer is one that will react with any lithium dendrite formed during cycling of the battery that could otherwise penetrate the separator, thus preventing an internal short circuit of the cell.
Description
~3~702~
This invention relates in general to separators for lithium batteries and in particular to a novel finely porous or solvent swellable membrane that acts as a separator between the cathode and anode in lithium secondary or primary batteries.
One of the primary problems that has limited development of rechargeable batteries has been the formation of dendrite lithium on the negative electrode. This has led to two difficulties:
(a) Low cycling efficiency has resulted from lithium dendrite becoming electrically isolated and high corrosion rate due to high surface area of the lithium dendrites.
(b) Lithium dendrites have grown through the separator causing an internal short circuit. The resulting high currents have heated the battery to the point that the highly reactive lithium reacts explosively with the electrolyte and cathode materials. This safety hazard has been a serious drawback of rechargeable lithium batteries and even some primary lithium systems where lithium dendrites form on overcharge.
I'he development of rechargeable lithium batteries such a~ Li/LiAlC14-3SO2/C or rechargeable cells such as Li/TiS2 containing organic solvents and salts such as LiBr or LiI has at least in principle minimized the lithium cycling efficiency problem. Soluble overcharge products formed at the positive electrode have reacted with the dendrites to reform the electrolyte salt which has gone back into solution. Therefore, by sufficiently overcharging the cell, it should be possible to retrieve isolated lithium dendrites and in some cases lithium corrosion products such that no anode material is l.ost during -;`` 1307024 repeated cycling. Unfortunately, reaction of overcharge products with lithium dendrites has usually not been rapid enough to prevent cell shorting~ Furthermore, even the development of finely porous, microporous and solvent swellable membranes for lithium secondary cells has not been able to completely eliminate the internal shorting problem.
The general object of this invention is to provide a separator between the cathode and anode in lithium secondary or primary batteries that will eliminate internal shorting. A more specific object is to provide a separator material that will react with any lithium dendrite that could otherwise penetrate the separator thus preventing an internal short circuit of the battery.
It has now been found that the aforementioned objects can be attained by providing a multilayer separator including an electrically insulating porous membrane and an electroactive polymeric material contained within the separator layers wherein the polymer is one that will react with any lithium dendrite that tries to penetrate the separator thus preventing an internal short circuit of the cell. Such a polymer could be polyvinylpyridine, poly-3-methylthiophene, polythiophene, polypyrrole or polyaniline.
The invention includes a composite separator including an electrically insulating finely porous separator, microporous separator, or solvent swellable membrane. Examples of such materials include polypropylene, polyethylene, Tefzel*, Kynar* and polyvinylidine fluoride. In a lithium battery, the inner layer of separator or the inside face, i.e. the side facing the lithium * denotes trade mark ~'' ~. .
j, - ~30702~
anode, of a two layer composite separator contains a very thin layer of electroactive polymer.
Thin coatings of polyvinylpyridine can be made by dissolving the polymer in a suitable volatile organic solvent such as toluene and dipcoating the membrane with polymer and drying.
If the polymer is soluble in the electrolyte chosen for the cell, the polymer can be crosslinked, for example, by treating the thinly coated me~brane before drying, with dichlorobenzene, dibromobenzene or diiodobenzene.
Polymers that can be electrodeposited, such as poly-3-methylthiophene can be used by first sputtering a thin layer of a suitable metal on the separator surface.
Alternatively, metallized separators may be purchased commercially. Then, a very thin layer of polymer can be electrodeposited on the metallized surface.
An electrochemical cell is made by electrodepositing a 2.0 micron layer of poly-3-methylthiophene on the end of a thin platinum rod. The electrode is then placed in a flask containing LiAlC14-3S02 electrolyte and lithium reference and counter electrodes. Cyclic voltammetry experiments are carried out over the 3.7V-2.0V potential range. The results show that SO2 is effectively reduced on the polymer and that the discharge product on the polymer is essentially the same as on the bare carbon cathode. This embodiment shows that thin layers of polymer on a porous separator as described, are reduced when shorted by a lithium dendrite. Further since the discharge product is the same as that formed in a standard cell with carbon cathodes, the -~ ~307024 polymer electrode is reoxidized by cell overcharge products, as is found to occur at cathodes of Li/LiAlC14-3SO2/C cells.
I wish it to be understood that I do not desire to be limited to the exact details as described for obvious modifications will occur to a person skilled in the art.
, . .. ~
,,,, ' ~ ~ .
This invention relates in general to separators for lithium batteries and in particular to a novel finely porous or solvent swellable membrane that acts as a separator between the cathode and anode in lithium secondary or primary batteries.
One of the primary problems that has limited development of rechargeable batteries has been the formation of dendrite lithium on the negative electrode. This has led to two difficulties:
(a) Low cycling efficiency has resulted from lithium dendrite becoming electrically isolated and high corrosion rate due to high surface area of the lithium dendrites.
(b) Lithium dendrites have grown through the separator causing an internal short circuit. The resulting high currents have heated the battery to the point that the highly reactive lithium reacts explosively with the electrolyte and cathode materials. This safety hazard has been a serious drawback of rechargeable lithium batteries and even some primary lithium systems where lithium dendrites form on overcharge.
I'he development of rechargeable lithium batteries such a~ Li/LiAlC14-3SO2/C or rechargeable cells such as Li/TiS2 containing organic solvents and salts such as LiBr or LiI has at least in principle minimized the lithium cycling efficiency problem. Soluble overcharge products formed at the positive electrode have reacted with the dendrites to reform the electrolyte salt which has gone back into solution. Therefore, by sufficiently overcharging the cell, it should be possible to retrieve isolated lithium dendrites and in some cases lithium corrosion products such that no anode material is l.ost during -;`` 1307024 repeated cycling. Unfortunately, reaction of overcharge products with lithium dendrites has usually not been rapid enough to prevent cell shorting~ Furthermore, even the development of finely porous, microporous and solvent swellable membranes for lithium secondary cells has not been able to completely eliminate the internal shorting problem.
The general object of this invention is to provide a separator between the cathode and anode in lithium secondary or primary batteries that will eliminate internal shorting. A more specific object is to provide a separator material that will react with any lithium dendrite that could otherwise penetrate the separator thus preventing an internal short circuit of the battery.
It has now been found that the aforementioned objects can be attained by providing a multilayer separator including an electrically insulating porous membrane and an electroactive polymeric material contained within the separator layers wherein the polymer is one that will react with any lithium dendrite that tries to penetrate the separator thus preventing an internal short circuit of the cell. Such a polymer could be polyvinylpyridine, poly-3-methylthiophene, polythiophene, polypyrrole or polyaniline.
The invention includes a composite separator including an electrically insulating finely porous separator, microporous separator, or solvent swellable membrane. Examples of such materials include polypropylene, polyethylene, Tefzel*, Kynar* and polyvinylidine fluoride. In a lithium battery, the inner layer of separator or the inside face, i.e. the side facing the lithium * denotes trade mark ~'' ~. .
j, - ~30702~
anode, of a two layer composite separator contains a very thin layer of electroactive polymer.
Thin coatings of polyvinylpyridine can be made by dissolving the polymer in a suitable volatile organic solvent such as toluene and dipcoating the membrane with polymer and drying.
If the polymer is soluble in the electrolyte chosen for the cell, the polymer can be crosslinked, for example, by treating the thinly coated me~brane before drying, with dichlorobenzene, dibromobenzene or diiodobenzene.
Polymers that can be electrodeposited, such as poly-3-methylthiophene can be used by first sputtering a thin layer of a suitable metal on the separator surface.
Alternatively, metallized separators may be purchased commercially. Then, a very thin layer of polymer can be electrodeposited on the metallized surface.
An electrochemical cell is made by electrodepositing a 2.0 micron layer of poly-3-methylthiophene on the end of a thin platinum rod. The electrode is then placed in a flask containing LiAlC14-3S02 electrolyte and lithium reference and counter electrodes. Cyclic voltammetry experiments are carried out over the 3.7V-2.0V potential range. The results show that SO2 is effectively reduced on the polymer and that the discharge product on the polymer is essentially the same as on the bare carbon cathode. This embodiment shows that thin layers of polymer on a porous separator as described, are reduced when shorted by a lithium dendrite. Further since the discharge product is the same as that formed in a standard cell with carbon cathodes, the -~ ~307024 polymer electrode is reoxidized by cell overcharge products, as is found to occur at cathodes of Li/LiAlC14-3SO2/C cells.
I wish it to be understood that I 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 (29)
1. A multilayer separator for preventing the internal shorting of a lithium battery, said battery including a lithium anode, a cathode and said separator therebetween, said multilayer separator comprising an electrically insulating membrane layer and an electroactive polymeric material layer, such that in use, the electroactive polymer layer is adjacent the lithium anode, wherein the polymer is one that will react with any lithium dendrites formed during cycling of the battery that could otherwise penetrate the separator, thus preventing an internal short circuit of the cell.
2. A separator according to Claim 1, wherein the electroactive polymer is selected from the group consisting of polyvinylpyridine, poly-3-methylthiophene, polythiophene, polypyrrole and polyaniline.
3. A separator according to Claim 2, wherein the polymer is polyvinylpyridine.
4. A separator according to Claim 2, wherein the polymer is poly-3-methylthiophene.
5. A separator according to Claim 2, wherein the polymer is polythiophene.
6. A separator according to Claim 2, wherein the polymer is polypyrrole.
7. A separator according to Claim 2, wherein the polymer is polyaniline.
8. A separator according to Claim 2, wherein the porous membrane is metallized.
9. A separator according to Claim 2, wherein the electrically insulating porous membrane material is selected from the group consisting of polypropylene, polyethylene, tefzel, kynar and polyvinylidine fluoride.
10. A lithium battery including lithium as the anode, a cathode spaced from said anode, said anode and cathode being immersed in an electrolyte that circulates through said anode and cathode, and a multilayer separator between the anode and cathode, said multilayer separator comprising an electrically insulating porous membrane layer and an electroactive polymeric material layer adjacent the lithium anode, wherein the polymer is one that will react with any lithium dendrite formed during cycling of the battery that could otherwise penetrate the separator, thus preventing an internal short circuit of the battery.
11. A lithium battery according to Claim 10, wherein the polymer is selected from the group consisting of polyvinyl-pyridine, poly-3-methylthiophene, polythiophene, polypyrrole and polyaniline.
12. A lithium battery according to Claim 11, wherein the electrically insulating porous membrane material is selected from the group consisting of polypropylene, polyethylene, tefzel, kynar and polyvinylidine fluoride.
13. A lithium battery according to Claim 12, wherein the polymer is polyvinylpyridine.
14. A lithium battery according to Claim 12, wherein the polymer is poly-3-methylthiophene.
15. A lithium battery according to Claim 12, wherein the polymer is polythiophene.
16. A lithium battery according to Claim 12, wherein the polymer is polypyrrole.
17. A lithium battery according to Claim 12, wherein the polymer is polyaniline.
18. A lithium battery including lithium as the anode, a carbon cathode spaced from the anode, said anode and cathode being immersed in an electrolyte of lithium tetrachloroaluminate in liquid sulfur dioxide that circulates through said anode and cathode, and a multilayer separator between the anode and cathode, said multilayer separator comprising a metallized electrically insulating porous membrane layer and a 2.0 micron layer of poly-3-methylthiophene adjacent the lithium anode.
19. A lithium battery according to Claim 18, wherein the electrically insulating porous membrane material is selected from the group consisting of polypropylene, polyethylene, tefzel, kynar and polyvinylidine fluoride.
20. A method for making a multilayer separator for preventing the internal shorting of lithium batteries, said lithium batteries including a lithium anode, said multilayer separator comprising an electrically insulating porous membrane layer and an electroactive polymer material layer for location adjacent the lithium anode, said method comprising (a) dissolving the electroactive polymer material in a suitable volatile organic solvent;
(b) dipcoating the electrically insulating porous membrane layer with the dissolved electroactive polymer material;
and (c) drying.
(b) dipcoating the electrically insulating porous membrane layer with the dissolved electroactive polymer material;
and (c) drying.
21. A method according to Claim 20, wherein the electro-active polymer material is crosslinked with a member of the group consisting of dichlorobenzene, dibromobenzene and diiodobenzene.
22. A method for making a multilayer separator for preventing the internal shorting of lithium batteries, said lithium batteries including a lithium anode, said multilayer separator comprising an electrically insulating porous membrane layer and an electroactive polymeric material layer for location adjacent the lithium anode, said method comprising (a) sputtering a thin layer of a suitable metal on the porous membrane layer; and (b) electrodepositing a very thin layer of the electroactive polymer layer on the metallized surface.
23. A method according to Claim 22, wherein the electroactive polymer is selected from the group consisting of polyvinylpyridine, poly-3-methylthiophene, polythiophene, polypyrrole and polyaniline.
24. A method according to Claim 23, wherein the polymer is polyvinylpyridine.
25. A method according to Claim 23, wherein the polymer is poly-3-methylthiophene.
26. A method according to Claim 23, wherein the polymer is polythiophene.
27. A method according to Claim 23, wherein the polymer is polypyrrole.
28. A method according to Claim 23, wherein the polymer is polyaniline.
29. A method according to Claim 23, wherein the electrically insulating porous membrane material is selected from the group consisting of polypropylene, polyethylene, tefzel, kynar and polyvinylidine fluoride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/213,031 US4812375A (en) | 1988-06-27 | 1988-06-27 | Separator for lithium batteries and lithium batteries including the separator |
| US213,031 | 1988-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1307024C true CA1307024C (en) | 1992-09-01 |
Family
ID=22793459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000599185A Expired - Lifetime CA1307024C (en) | 1988-06-27 | 1989-04-19 | Separator for lithium batteries and lithium batteries including the separator |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4812375A (en) |
| CA (1) | CA1307024C (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0153002B1 (en) * | 1989-06-16 | 1998-11-16 | 와따나베 히로시 | Inorganic nonaqueous electrolytic solution type cell |
| US5006428A (en) * | 1989-11-28 | 1991-04-09 | Yardney Technical Products, Inc. | Getter electrode and improved electrochemical cell containing the same |
| FR2674685B1 (en) * | 1991-03-29 | 1996-12-13 | Alsthom Cge Alcatel | SECONDARY LITHIUM ELECTROCHEMICAL GENERATOR WITH LIQUID ORGANIC ELECTROLYTE. |
| CA2085380C (en) * | 1991-12-27 | 2005-11-29 | Celgard Inc. | Porous membrane having single layer structure, battery separator made thereof, preparations thereof and battery equipped with same battery separator |
| CA2110097C (en) * | 1992-11-30 | 2002-07-09 | Soichiro Kawakami | Secondary battery |
| US5350645A (en) * | 1993-06-21 | 1994-09-27 | Micron Semiconductor, Inc. | Polymer-lithium batteries and improved methods for manufacturing batteries |
| US5648187A (en) * | 1994-02-16 | 1997-07-15 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
| JPH07302597A (en) * | 1994-04-29 | 1995-11-14 | Mine Safety Appliances Co | Lithium battery |
| US5434021A (en) * | 1994-08-12 | 1995-07-18 | Arthur D. Little, Inc. | Secondary electrolytic cell and electrolytic process |
| US5980723A (en) * | 1997-08-27 | 1999-11-09 | Jude Runge-Marchese | Electrochemical deposition of a composite polymer metal oxide |
| KR100308690B1 (en) * | 1998-12-22 | 2001-11-30 | 이 병 길 | Microporous polymer electrolyte containing absorbent and its manufacturing method |
| US6153328A (en) * | 1999-11-24 | 2000-11-28 | Metallic Power, Inc. | System and method for preventing the formation of dendrites in a metal/air fuel cell, battery or metal recovery apparatus |
| JP4248119B2 (en) * | 2000-03-01 | 2009-04-02 | 三洋電機株式会社 | Alkaline storage battery |
| WO2001091222A1 (en) * | 2000-05-22 | 2001-11-29 | Korea Institute Of Science And Technology | A lithium secondary battery comprising a polymer electrolyte fabricated by a spray method and its fabrication method |
| WO2001091220A1 (en) * | 2000-05-22 | 2001-11-29 | Korea Institute Of Science And Technology | A hybrid polymer electrolyte fabricated by a spray method, a lithium secondary battery comprising the hybrid polymer electrolyte and their fabrication methods |
| WO2001091219A1 (en) * | 2000-05-22 | 2001-11-29 | Korea Institute Of Science And Technology | A lithium secondary battery comprising a porous polymer separator film fabricated by a spray method and its fabrication method |
| WO2001091221A1 (en) * | 2000-05-22 | 2001-11-29 | Korea Institute Of Science And Technology | A composite polymer electrolyte fabricated by a spray method, a lithium secondary battery comprising the composite polymer electrolyte and their fabrication methods |
| EP1290749A4 (en) * | 2000-05-24 | 2004-09-22 | Finecell Co Ltd | MICROPOROUS MINERAL SOLID ELECTROLYTES AND METHODS OF PREPARATION |
| US8945753B2 (en) * | 2005-01-26 | 2015-02-03 | Medtronic, Inc. | Implantable battery having thermal shutdown separator |
| US20070178385A1 (en) * | 2006-01-31 | 2007-08-02 | Kaimin Chen | Electrochemical cells having an electrolyte with swelling reducing additives |
| US20070201186A1 (en) * | 2006-02-28 | 2007-08-30 | Norton John D | Separator systems for electrochemical cells |
| US9722275B2 (en) * | 2007-12-14 | 2017-08-01 | Nanotek Instruments, Inc. | Anode protective layer compositions for lithium metal batteries |
| US20110033755A1 (en) * | 2008-04-21 | 2011-02-10 | Seeo, Inc | Protected lithium metal electrodes for rechargeable batteries |
| WO2010054270A1 (en) | 2008-11-07 | 2010-05-14 | Seeo, Inc | Electrodes with solid polymer electrolytes and reduced porosity |
| US8999008B2 (en) | 2008-11-07 | 2015-04-07 | Seeo, Inc. | Method of forming an electrode assembly |
| US8236452B2 (en) * | 2009-11-02 | 2012-08-07 | Nanotek Instruments, Inc. | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| US8962188B2 (en) | 2010-01-07 | 2015-02-24 | Nanotek Instruments, Inc. | Anode compositions for lithium secondary batteries |
| US9985292B2 (en) | 2012-11-27 | 2018-05-29 | Seeo, Inc. | Oxyphosphorus-containing polymers as binders for battery cathodes |
| WO2014179725A1 (en) | 2013-05-03 | 2014-11-06 | The Board Of Trustees Of The Leland Stanford Junior University | Improving rechargeable battery safety by multifunctional separators and electrodes |
| EP3096373A1 (en) * | 2015-05-20 | 2016-11-23 | Jaroslav Polivka | Liquid electrolyte lithium accumulator and a method of making the same |
| CN105576178A (en) * | 2016-02-29 | 2016-05-11 | 黄博然 | A kind of wet-laid non-woven ceramic diaphragm of lithium-ion power battery and preparation method thereof |
| US10559826B2 (en) | 2017-03-20 | 2020-02-11 | Global Graphene Group, Inc. | Multivalent metal ion battery having a cathode of recompressed graphite worms and manufacturing method |
| US10411291B2 (en) * | 2017-03-22 | 2019-09-10 | Nanotek Instruments, Inc. | Multivalent metal ion battery having a cathode layer of protected graphitic carbon and manufacturing method |
| CN109860474B (en) * | 2018-12-07 | 2022-04-05 | 上海空间电源研究所 | Active diaphragm and preparation method thereof |
| CN109659539B (en) * | 2018-12-20 | 2022-07-15 | 电子科技大学 | Method for preparing lithium battery cathode material based on in-situ compounding and recombination |
| WO2020252600A1 (en) * | 2019-06-21 | 2020-12-24 | The University Of British Columbia | Stretchable electrochemical cell |
| CN111969162A (en) * | 2020-08-25 | 2020-11-20 | 西安交通大学 | High-specific-energy lithium metal battery based on alloy element modified diaphragm |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1472136A (en) * | 1965-12-28 | 1967-03-10 | Accumulateurs Fixes | negative zinc electrode for accumulators |
| US3980497A (en) * | 1970-08-03 | 1976-09-14 | The Gates Rubber Company | Separators for alkaline batteries |
| US4124743A (en) * | 1977-10-13 | 1978-11-07 | Yardngy Electric Corporation | Mercury-free secondary alkaline battery and improved negative interseparator therefor |
| JPS55105971A (en) * | 1979-02-05 | 1980-08-14 | Japan Atom Energy Res Inst | Improved cell separator and its manufacturing method |
| US4762758A (en) * | 1985-12-12 | 1988-08-09 | Gould Inc. | Interelectrode separator system for electrochemical cells |
-
1988
- 1988-06-27 US US07/213,031 patent/US4812375A/en not_active Expired - Fee Related
-
1989
- 1989-04-19 CA CA000599185A patent/CA1307024C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4812375A (en) | 1989-03-14 |
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Legal Events
| Date | Code | Title | Description |
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| MKLA | Lapsed |