CA2093763C - Battery incorporating hydraulic activation of disconnect safety device on overcharge - Google Patents
Battery incorporating hydraulic activation of disconnect safety device on overchargeInfo
- Publication number
- CA2093763C CA2093763C CA002093763A CA2093763A CA2093763C CA 2093763 C CA2093763 C CA 2093763C CA 002093763 A CA002093763 A CA 002093763A CA 2093763 A CA2093763 A CA 2093763A CA 2093763 C CA2093763 C CA 2093763C
- Authority
- CA
- Canada
- Prior art keywords
- cathode
- battery
- electrolyte
- diaphragm
- anode
- 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
- 230000004913 activation Effects 0.000 title description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 6
- 239000011800 void material Substances 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 231100001261 hazardous Toxicity 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims 5
- 150000002739 metals Chemical class 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 13
- 210000004027 cell Anatomy 0.000 description 90
- 238000001994 activation Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000006870 function Effects 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- 235000015110 jellies Nutrition 0.000 description 4
- 239000008274 jelly Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910011259 LiCoOz Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000002931 mesocarbon microbead Substances 0.000 description 3
- 238000009783 overcharge test Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910018688 LixC6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004836 empirical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/578—Devices or arrangements for the interruption of current in response to pressure
-
- 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
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A novel battery construction which incorporates a disconnect safety device which is hydraulically activated by an increase in solid volume upon abusive overcharge of the battery to disconnect the cathode or anode. A
rechargeable battery which comprises: (a) a Li x MO2 cathode wherein x, is equal to or less than 1.1,and M is Ni, Co, Mn or combinations thereof; (b) a carbonaceous anode; (c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal disconnect device which activates by hydraulic means on overcharge.
rechargeable battery which comprises: (a) a Li x MO2 cathode wherein x, is equal to or less than 1.1,and M is Ni, Co, Mn or combinations thereof; (b) a carbonaceous anode; (c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal disconnect device which activates by hydraulic means on overcharge.
Description
v BATTERY INCORPORATING HYDRAULIC ACTIVATION OF
' DISCONNECT SAFETY DEVICE ON OVERCHARGE
FIELD OF THE INVENTION
This invention relates to a novel battery con-struction that incorporates a disconnect safety device which activates o.n overcharge. More particularly, this invention pertains to a novel battery construction which incorporates a disconnect safety device which is hydraul-ically activated by an increase in solid volume upon overcharge of the battery.
BACKGROUND OF THE INVENTION
A new class of rechargeable batteries based on lithium ion or rocking chair technologies is entering the marketplace in such consumer applications as power sources for camcorders, cellular telephones, portable computers, and the like. Cells making up these batteries offer advantages over competing systems in terms of high opera-ting voltages (>3 V), energy density, and cycle life.
However, as with all stored energy devices, there are risks associated with abuse. In such lithium ion cells, a problem of ignition exists if the cell is overcharged to too great an extent beyond the recommended charging voltage. Under such circumstances, the cell can heat up, vent, and ignite unless certain safety devices are incorporated. Lithium rechargeable cells are unsafe under certain recharge conditions. Charger control is effective at providing protection, but cells can contain internal pressure activated disconnect devices as additional protection. A reliable means of activating the disconnect at a specified point during overcharge is in demand. Gener-ated gases can be used and have been described elsewhere.
U.S. patent No. 4,943,497, Oishi et al., Sony Corporation, describes the problem associated with over-charging in such cells and presents a method of protection.
.. 2~93'~~63 Incorporation of an internal switch or disconnect device is used to open circuit the cell at an appropriate point during overcharge abuse. An increase in internal cell pressure is used to activate the device. Gases generated as a result of electrolyte decomposition at the cathode at elevated voltages is used as the means of pressure gener-ation.
Oishi et al. disclose a cell having an explosion proof valve which is deformable upon increase of inner pressure of the cell to cut a connection lead which con-nects the valve with a generator unit contained in the cell. The supply of charging current is cut off when the inner pressure of the cell has abnormally increased. The gradual increase of the inner pressure can be effected by selecting suitable cathode active material.
The cell design disclosed in U.S. patent No.
4,943,497 works reasonably well in that a useful commer-cial product can be made that is adequately protected internally on overcharge. Gas generation mechanisms that are relied upon to activate the disconnect device are func-tions of cell voltage, temperature, and time. The rate of gas generation is not constant, but increases with cell voltage and temperature. Quite importantly to actual cell applications, gas generation continues with time at a given voltage and temperature. Thus, while gas generation is required to ensure safe shutdown of the cell during over-charge, prolonged gas generation must be avoided during normal operation. Otherwise the disconnect device can become triggered during normal usage as gaseous decomposi-tion products accumulate with time, and gas pressure rises.
In practice, both requirements can be met with judicious choice of electrolytes and cathode materials.
However, these restrictions prevent certain other combinations from being chosen that are advantageous for other reasons (such as cost, complexity,'energy density, etc.) Also, a maximum lifetime to the disconnect function-ing is imposed if gas generation is continuous in an other-wise perfectly sealed cell.
Oishi et al. disclose a cell that achieves safe shutdown on overcharge by using a combination of cathode active materials to ensure sufficient gassing occurs on overcharge. In the embodiment described, cells made with 100% LiCoOz cathode only experienced 90o failure on over-charge. Thus, under the conditions described, a satisfac-tory cell could not be made using 100% LiCoOZ cathode.
Canadian Patent Appl. No. 2,099,657, A. Rivers-Bowerman et al. (Moll), discloses an improved cell discon-nect device. The electrochemical cell has a current cutoff means for preventing current flow. The current cutoff means has a burstable vent for preventing a dangerous explosion from occurring within the cell. The current cutoff means operates upon the exertion of a pressure in excess of a first predetermined pressure. The burstable vent operates upon the application of pressure exerted directly on the diaphragm in excess of a second predeter-mined pressure exceeding the first predetermined pressure.
Japanese Laid Open Pat. App. No. 294373/89 (Sony Corporation) discloses void requirements for a cell with a disconnect device. The battery is constructed of a con-tainer which accommodates (a) a negative electrode consist-ing of a calcinated organic body, (b) a positive electrode containing LiXM02 (where M represents at least one kind of either Co or Ni, and x is equal to or greater than 0.05 and equal to or less than 1.10), and (c) an electrolytic solution. The battery provides a cavity with a volume of 0.3 cc or greater per capacity of 1 AH.
._. 2~93'~63 SUMMARY OF THE INVENTION
This invention relates to a rechargeable safety battery construction which utilizes inherent net increase in solids volume, which occurs on overcharge, to activate a current disconnect safety device.
In one aspect, the invention pertains to a rechargeable battery which comprises: (a) a LixM02 cathode (x <1.1,M=Ni, Co, Mn or combinations thereof), (b) a carbonaceous anode, (c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal disconnect device which activates by hydraulic means on overcharge.
In the battery as described, electrode balance, void volume, and charging level can be selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or storage at high temperature.
In the battery as described, the volume of plated lithium following exhaustion of anode capacity during overcharge can be used for hydraulic activation.
In the battery as described, the cathode can be LiCoOz, the anode can be a coke-like carbon, and the electrolyte can be LiPF6 dissolved in equal volumes of propylene carbonate (PC) and diethyl carbonate (DEC).
The internal disconnect device can be constructed of a cathode compatible diaphragm, which bursts under a prescribed force, a cover with a vent hole positioned over the diaphragm, and a cathode compatible plate connected to the diaphragm and adapted to separate from the diaphragm under said prescribed force and disconnect the external connection to the cathode.
2p9 The invention is also directed to a method of preventing hazardous overcharge of a rechargeable battery having. a cathode, an anode, and an electrolyte which comprises incorporating within the battery an electrical disconnect means which activates by hydraulic net solids expansion when overcharge beyond a predetermined point occurs, thereby electrically disconnecting the cathode or the anode.
In the method as described electrode balance, void volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or high temperature use. The volume of plated lithium following the exhaustion of anode capacity during overcharge can be used for hydraulic activation.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings illustrate specific embodiments of the invention but should not be construed as restricting or limiting the scope of the claims or protection in any way:
Figure 1 illustrates a side elevation section view of the rechargeable battery with cell disconnect safety device which activates on increase in solids volume.
Figure lb illustrates a side section view of a header assembly.
Figure lc illustrates a horizontal cross-section view of the battery.
2~~3~ s~
' DISCONNECT SAFETY DEVICE ON OVERCHARGE
FIELD OF THE INVENTION
This invention relates to a novel battery con-struction that incorporates a disconnect safety device which activates o.n overcharge. More particularly, this invention pertains to a novel battery construction which incorporates a disconnect safety device which is hydraul-ically activated by an increase in solid volume upon overcharge of the battery.
BACKGROUND OF THE INVENTION
A new class of rechargeable batteries based on lithium ion or rocking chair technologies is entering the marketplace in such consumer applications as power sources for camcorders, cellular telephones, portable computers, and the like. Cells making up these batteries offer advantages over competing systems in terms of high opera-ting voltages (>3 V), energy density, and cycle life.
However, as with all stored energy devices, there are risks associated with abuse. In such lithium ion cells, a problem of ignition exists if the cell is overcharged to too great an extent beyond the recommended charging voltage. Under such circumstances, the cell can heat up, vent, and ignite unless certain safety devices are incorporated. Lithium rechargeable cells are unsafe under certain recharge conditions. Charger control is effective at providing protection, but cells can contain internal pressure activated disconnect devices as additional protection. A reliable means of activating the disconnect at a specified point during overcharge is in demand. Gener-ated gases can be used and have been described elsewhere.
U.S. patent No. 4,943,497, Oishi et al., Sony Corporation, describes the problem associated with over-charging in such cells and presents a method of protection.
.. 2~93'~~63 Incorporation of an internal switch or disconnect device is used to open circuit the cell at an appropriate point during overcharge abuse. An increase in internal cell pressure is used to activate the device. Gases generated as a result of electrolyte decomposition at the cathode at elevated voltages is used as the means of pressure gener-ation.
Oishi et al. disclose a cell having an explosion proof valve which is deformable upon increase of inner pressure of the cell to cut a connection lead which con-nects the valve with a generator unit contained in the cell. The supply of charging current is cut off when the inner pressure of the cell has abnormally increased. The gradual increase of the inner pressure can be effected by selecting suitable cathode active material.
The cell design disclosed in U.S. patent No.
4,943,497 works reasonably well in that a useful commer-cial product can be made that is adequately protected internally on overcharge. Gas generation mechanisms that are relied upon to activate the disconnect device are func-tions of cell voltage, temperature, and time. The rate of gas generation is not constant, but increases with cell voltage and temperature. Quite importantly to actual cell applications, gas generation continues with time at a given voltage and temperature. Thus, while gas generation is required to ensure safe shutdown of the cell during over-charge, prolonged gas generation must be avoided during normal operation. Otherwise the disconnect device can become triggered during normal usage as gaseous decomposi-tion products accumulate with time, and gas pressure rises.
In practice, both requirements can be met with judicious choice of electrolytes and cathode materials.
However, these restrictions prevent certain other combinations from being chosen that are advantageous for other reasons (such as cost, complexity,'energy density, etc.) Also, a maximum lifetime to the disconnect function-ing is imposed if gas generation is continuous in an other-wise perfectly sealed cell.
Oishi et al. disclose a cell that achieves safe shutdown on overcharge by using a combination of cathode active materials to ensure sufficient gassing occurs on overcharge. In the embodiment described, cells made with 100% LiCoOz cathode only experienced 90o failure on over-charge. Thus, under the conditions described, a satisfac-tory cell could not be made using 100% LiCoOZ cathode.
Canadian Patent Appl. No. 2,099,657, A. Rivers-Bowerman et al. (Moll), discloses an improved cell discon-nect device. The electrochemical cell has a current cutoff means for preventing current flow. The current cutoff means has a burstable vent for preventing a dangerous explosion from occurring within the cell. The current cutoff means operates upon the exertion of a pressure in excess of a first predetermined pressure. The burstable vent operates upon the application of pressure exerted directly on the diaphragm in excess of a second predeter-mined pressure exceeding the first predetermined pressure.
Japanese Laid Open Pat. App. No. 294373/89 (Sony Corporation) discloses void requirements for a cell with a disconnect device. The battery is constructed of a con-tainer which accommodates (a) a negative electrode consist-ing of a calcinated organic body, (b) a positive electrode containing LiXM02 (where M represents at least one kind of either Co or Ni, and x is equal to or greater than 0.05 and equal to or less than 1.10), and (c) an electrolytic solution. The battery provides a cavity with a volume of 0.3 cc or greater per capacity of 1 AH.
._. 2~93'~63 SUMMARY OF THE INVENTION
This invention relates to a rechargeable safety battery construction which utilizes inherent net increase in solids volume, which occurs on overcharge, to activate a current disconnect safety device.
In one aspect, the invention pertains to a rechargeable battery which comprises: (a) a LixM02 cathode (x <1.1,M=Ni, Co, Mn or combinations thereof), (b) a carbonaceous anode, (c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal disconnect device which activates by hydraulic means on overcharge.
In the battery as described, electrode balance, void volume, and charging level can be selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or storage at high temperature.
In the battery as described, the volume of plated lithium following exhaustion of anode capacity during overcharge can be used for hydraulic activation.
In the battery as described, the cathode can be LiCoOz, the anode can be a coke-like carbon, and the electrolyte can be LiPF6 dissolved in equal volumes of propylene carbonate (PC) and diethyl carbonate (DEC).
The internal disconnect device can be constructed of a cathode compatible diaphragm, which bursts under a prescribed force, a cover with a vent hole positioned over the diaphragm, and a cathode compatible plate connected to the diaphragm and adapted to separate from the diaphragm under said prescribed force and disconnect the external connection to the cathode.
2p9 The invention is also directed to a method of preventing hazardous overcharge of a rechargeable battery having. a cathode, an anode, and an electrolyte which comprises incorporating within the battery an electrical disconnect means which activates by hydraulic net solids expansion when overcharge beyond a predetermined point occurs, thereby electrically disconnecting the cathode or the anode.
In the method as described electrode balance, void volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or high temperature use. The volume of plated lithium following the exhaustion of anode capacity during overcharge can be used for hydraulic activation.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings illustrate specific embodiments of the invention but should not be construed as restricting or limiting the scope of the claims or protection in any way:
Figure 1 illustrates a side elevation section view of the rechargeable battery with cell disconnect safety device which activates on increase in solids volume.
Figure lb illustrates a side section view of a header assembly.
Figure lc illustrates a horizontal cross-section view of the battery.
2~~3~ s~
Figure 2a illustrates a graphical depiction of cell voltage and internal pressure versus time for a battery assembled according to the invention.
Figure 2b illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery cell which has been overcharged.
Figure 3 illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery as cycled according to a first procedure.
Figure 4 illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery assembled and cycled as according to a second procedure.
Figure 5a illustrates a graphical depiction of voltage and pressure versus time, for a rechargeable battery which has been subjected to eleven cycles.
Figure 5b illustrates a graphical depiction of pressure and float current versus time for a rechargeable battery assembled and cycled according a fourth procedure.
Figure 6 illustrates a graphical depiction of voltage and external cell temperature versus time for a re-chargeable battery constructed according to the invention, demonstrating reliable overcharge protection.
~o93~s3 DETAILED DESCRIPTION OF SPECIFIC
EMBODIMENTS OF THE INVENTION
Li ion rechargeable cells (such as those commer-cially available from Sony Corporation) can vent violently with ensuing flame if overcharged too fast for too long (for example 2C rate for one hour). Activation of the disconnect partway through this period (approximately 1/2 hour in Figure 6) will safely shut the cell down. Depend-ing on the cell balance (defined as the mole ratio of active cathode to anode material), the ability of the anode to contain Li on charge may eventually be exhausted. On further charge, low density Li metal begins to plate out.
So while there is typically a net increase in solids volume during charge and overcharge (anode volume increase is typically greater than the cathode volume decrease), a more marked increase in volume occurs as Li is plated out.
Proper choice of cell balance, absolute electrode amounts and void space in the assembled cell results in a cell whose disconnect can be activated at the desired point in overcharge and is not activated over normal operating temperature ranges or prolonged storage.
The invention disclosed and claimed herein is directed to a rechargeable safety battery which utilizes a net increase in solids volume for activation of a discon-nect device. This is an important improvement over prior systems which are activated by gaseous decomposition.
Reliability is gained because decomposition occurs to some extent during normal cell operation and the rate is great-est during float charging at high temperatures. Thus, time and cell history affect the gas background. Conversely, the solids volume is mainly a function of the state of charge and is not significantly affected by time or cell history. Thus, the reliability in normal and abuse situ-ations together can be improved. In addition, even for a given cell history, it is difficult to engineer the decom-_. 2p9~'~~3 _8_ position such that adequate gassing occurs for protection, yet not too much occurs for normal use.
Since gaseous decomposition products are not required for the activation function, a larger range of electrochemical systems can be chosen. The invention has immediate application to Li ion rechargeable cells, but is not fundamentally limited to this type of cell.
The subject invention relies on the material prop-erties of the components, in particular the volume occupied as a function of temperature and state of lithiation (or charge) to activate a disconnect device in a lithium ion type cell. As a result, the generation of gas is not required. The life of the cell can be maximized by reduc-ing the electrolyte decomposition to a minimum. Also, time is not an important factor in the activation mechanism of the disconnect, allowing a wider range of options in the choice of electrolyte and cathode.
Description of Battery Construction The batteries according to the invention are constructed using intercalation compounds for both the active electrode materials. Compounds with the formula LiXMOZ, where x<1.1 and M is one or more transition metals, are used as the cathode while a carbonaceous material such as coke, graphite, pitch and the like, are used as the anode. These materials are used in powder form with particle sizes mainly in the range of 1-50 ~,m and are mounted on current collecting substrate foils using a suitable binder material. For purposes of making electri cal contacts, a conductive dilutant, either graphite or carbon black, is generally mixed in with the active elec trode material and binder.
._ 2~9~~~~
_ g -In the cells constructed for demonstration in the Examples which follow, cathode foils were prepared using LiCoOz powder obtained from Nihon Kagaku, KS15 graphite obtained from Lonza as the conductive dilutant, and poly-vinylidene fluoride (PVDF) powder from Kureha as the binder. A slurry of these components was prepared using a suitable amount of N-methyl-pyrrolidone (NMP) as the solvent in a ratio 91:6:3 parts by weight of LiCo02:graphite:PVDF. The slurry was then coated onto both sides of an aluminium foil substrate (-20 ~. thick), dried and then compressed such that a loading of 25 1/2 mg/cmZ of solids was applied to each side with a total resulting electrode thickness of 180 Similarly, anode foils were prepared using meso-carbon microbeads (MCMB) carbon as the primary anode material obtained from Osaka Gas, Super S (Trade-mark) carbon black from Ensagri as an additional conductive dilutant, and PVDF powder from Kureha as the binder. A
slurry was prepared from these materials in the ratio 88:2:10 parts by weight of MCMB:Super S: PVDF again by dissolving in a suitable amount of NMP solvent. This slurry was then coated on both sides of a copper foil substrate (-10 ~. thick) , dried and then compressed such that a loading of 12 mg/cm2 of solids was applied to each side with a total electrode thickness of 200 Dry cell assemblies were then prepared by spiral-ly winding an anode and cathode segment together into a "jelly roll" with two microporous Celgard 2400 (Trade-mark) film sheets present as separators. Typically, anode and cathode segments were 41 cm long by 57 1/2 mm wide and 37 cm long by 54 1/2 mm wide respectively. The jelly roll was then inserted into a conventional "4/3A" size battery container. (66.4 mm high, 16.6 mm OD). Appropriate ~p93~63 insulating pieces were included and appropriate tab connec-tions were made to the cell case and header.
The header used was of special construction that incorporated a pressure relief vent and a pressure operat-ed disconnect device. This header is the subject of a copending patent application (U.S. Patent Application No.
07/927,824). The disconnect pressure was set at --150 psi, while the pressure relief vent was set to open at -350 psi.
Electrolyte was added in several increments to activate the battery. In the following examples, a 1M
solution of LiPF6 dissolved in equal volumes of PC and DEC
was used as an electrolyte. Typically 5.9 g of solution was added. The header was then crimp sealed in place using conventional means.
Description of Invention in Relation to Drawinas Figure 1a shows a side section view of a specific cell construction according to the invention. As illus-trated in Figure la, in section view, a battery can 3, typically constructed of nickel plated steel, has a header assembly 1 at the top thereof. The header 1 and can 3 are sealed by seal 10. An insulating disk 2 is located immedi-ately below the neck portion 11 immediately under seal 10 and header assembly 1. A second insulating disk 7 is positioned above the base of the can 3. A jelly roll assembly 4, constructed as described below in relation to Figure lc, takes up most of the interior volume of the can 3. A cathode tab 5 is shown extending vertically in the central region of the can 3. An anode tab 6 is illus-trated extending vertically in the exterior region of the can 3. The upper horizontal broken line 12 indicates the upper edge of the anode. The upper horizontal broken line 13 illustrates the upper edge of the cathode.
2a93~63 The lower broken horizontal line 14 illustrates the lower edge of the cathode. The lower horizontal broken line 15 illustrates the lower edge of the anode. The electrolyte 8 is indicated generally within the interior of the can 3. The vertically extending spacer 9 is indicated in the central area of the can by broken lines.
Figure lb shows a detailed side section view of the header assembly 1 used in the cell construction of the invention. As illustrated in Figure lb, an external metal cover 16 is crimped at the periphery by an electrically conductive diaphragm 17.
The diaphragm 17 must be constructed of a cathode compatible material, such as aluminum, in this case. A
thin-walled grooved area is included in the diaphragm 17 design to burst upon application of sufficient physical force thereto. The diaphragm 17 thus acts as the pressure relief vent.
The cover 16 is typically constructed of stain-less steel and incorporates a vent hole 25 of some kind to allow the escape of gas and/or liquid in the event that the pressure relief vent is activated.
The diaphragm 17 is further electrically con-nected to an aluminum plate 18 by a critical weld 19. An electrically insulating gasket 20 positions the plate 18 with respect to the diaphragm. The gasket 20 electrically separates the positive header assembly 2 from the negative can 3. Additionally, the gasket 20 is used to provide a seal between the cell contents and the outside environment.
The cathode tab 5 (see Figures la and lc) is attached to the plate 18 at a site other than that of the critical weld 19. The plate 18 includes in it holes 26 to allow the flow of liquid and/or gas through it for purposes ~p93'~G3 of applying physical force to the diaphragm 17. The plate 18 is effectively fixed in position with reference to the gasket 20. Upon application of sufficient internal force-to the diaphragm 17, via holes 26, the critical weld 19 is broken. The diaphragm 17 is then free to move away upward-ly from the plate 18. When this occurs, the electrical path between the outside positive cover 16 and the plate 18 is broken thereby providing a pressure disconnect function.
Figure lc shows a detailed horizontal cross-section view of the cell. The helical jelly roll structure consisting of the cathode 21, anode 22 and separator 23 is illustrated. Also indicated are the can 3, spacer 9, cathode tab 5 and anode tab 6.
Cells such as these are capable of delivering large capacities for many cycles. This specific design is rated to deliver 800 mAh capacity (100% DOD) at 400 mA
(C/2) discharge rates over the cell lifetime following a fast -2 hour charge period to a 4 V cut-off. The maximum charge current of a charger for such a cell was taken to be 1.6 A (2C) rate. Thus, for purposes of testing these experimental batteries, overcharge testing was performed at a constant 2C rate until safe shutdown or cell failure was accomplished.
For purposes of effecting the desired result of hydraulic activation of the disconnect device, many factors must be considered. In the preceding description, and in the examples which follow, the choice of materials, elec-trode construction and operating conditions were made initially without consideration for disconnect activation.
It was then possible to accomplish both performance and activation objectives simply by varying the void volume in the cell. However, it will be obvious to those skilled in the art that other choices of materials, electrode con-struction and/or operating conditions may require the 2093'763 adjustment of other parameters. Thus, not all these parameters can be varied independently and still be compen-sated for simply by void adjustment. It is the intended scope of this disclosure, and the following claims to cover all possible battery constructions whereby the volume of plated lithium following the exhaustion of the anode capacity during overcharge is used for hydraulic activation of the disconnect.
As fabricated, at a given temperature, cells according to the invention generally are in a state with maximum internal void. Upon charging, lithium atoms are moved from the cathode host to the anode. Generally, the net electrode solids volume increases during this process.
While the volume occupied by the cathode is often (but not always) reduced as lithium is extracted, the volume oc-cupied by the anode increases as lithium is inserted. The net change in volume is usually positive on charge. Close to a reversible situation exists on subsequent discharge-charge cycles. In principle, a battery construction can be envisaged that uses this net volume increase to hydrauli-cally activate a disconnect at any desired point during normal charge, or preferably during an overcharge situ-ation.
It is, however, important to recognize that the battery must be capable of operation over wide temperature ranges, typically 0°C and up to 60°C. The net volume of the contents generally increases more rapidly than the internal volume of the container as temperature is in-creased. Thus, it is important to engineer the battery such that hydraulic activation does not occur as a result of using the battery at normal elevated temperatures. In practice, the net volume increase as the temperature is raised over this normal operating range is similar to the net volume increase seen in the electrode components during .w. 2~93~63 charge. Thus, it is difficult to achieve both performance and hydraulic activation goals in this way.
The situation changes, however, if the anode capacity is exhausted at an appropriate time during overcharge. At this point, the anode is no longer capable of intercalating lithium and lithium metal deposition must occur on the anode instead. The rate of net volume change increases markedly at this point since lithium metal is significantly less dense than the corresponding Li-carbon intercalation compound per unit lithium. Compare the rate of lithium intercalated graphite expansion which goes roughly as 3.3 cc increase in volume per mole Li interca-lated (derived from LixC6 lattice parameter data presented in Phase diactrams of LiXC6 Phys.Rev.B 1991 Vol. 44, No. 17, J. Dahn (page 9170)) versus a 13 cc increase in volume per mole of Li plated. If the battery is engineered such that lithium plating occurs in overcharge situations prior to cell failure with ignition, it becomes possible in practice to use the associated net volume increase to activate the safety disconnect.
A necessary condition, then, is that the lithium capacity of the cathode must exceed that of the anode. The ratio moles of cathode is called the balance.
moles of anode The batteries described in this disclosure have a preferred balance of approximately 1.5. Generally, the upper capacity limit on carbonaceous anodes is taken as 1 mole of Li per C6. However, this limit is less for coke like carbons and can be greater for modified carbons such as certain boron substituted carbon materials. Thus, the preferred balance will depend greatly on the materials used for the electrodes. Another necessary condition is that the lithium available for plating must exceed the void W_ 2093~G3 volume in the cell plus whatever additional volume is necessary to activate the disconnect.
It will be recognized that the net volume of the contents of the battery will be a function of all factors that influence the relative volume of any component includ-ing material choice, temperature, state of lithiation, and relative amounts of the components. Those skilled in the art are familiar with a variety of factors that make it difficult to predict the exact preferred construction.
These include irreversible losses of lithium that occur on the initial charge of the battery, the presence of some gaseous decomposition products even if minimized, and other factors. Normally then, fine tuning would be required using empirical methods.
Examples Example I
A battery was assembled as described in the preceding disclosure. The disconnect was bypassed such that the activation pressure was only slightly reduced, but would not disconnect internally. The battery was also equipped with a low volume pressure transducer attached via a small welded tube. This apparatus increased the internal cell volume by approximately 0.8 ml. The void for the entire assembly was adjusted to be 0.4 ml. The cell was charged and cycled once at 21°C to the normal 4 V upper limit. Figure 2a shows the cell voltage and internal pressure versus time for this cell. The cell delivered .87 Ah on discharge at 800 mA. The cell was then overcharged at 2C rate at ambient temperature as described earlier.
Figure 2b shows cell voltage, charge current, external cell temperature and internal pressure versus time for the cell.
The activation point of the disconnect is indicated by the dip in the pressure curve at approximately 0.45 hours.
This is a result of diaphragm movement which slightly .... 2093'~6~
increases internal void. The pressure relief activated just before 0.7 hours. Finally, the cell ignited just before 0.9 hours into the test. Thus, had the disconnect been active, this cell would have been disabled safely.
The onset of lithium plating, based solely on the total primary electrode materials available and one mole of lithium per C6 as the maximum anode capacity, would be approximately 0.3 hours into the test (i.e. Initial condi-tions have cathode of Li.55CoOZ and anode of Li.~C6. The conditions at anode exhaustion would be approximately Li,34Co02 and Li~C6) . There would theoretically be a maximum of .34 moles of Li per mole of initial cathode available for plating, corresponding to an additional volume of about 0.4 cc for activating a disconnect.
Example 2 A battery was assembled and cycled as in Example 1, except the void was adjusted to 0.2m1. A similar overcharge test was performed. Figure 3 shows an earlier time to activation (0.15 hours) and venting (0.35 hours) compared to Example 1. Again, ignition occurred at about 0.9 hours into the test. Had the disconnect been active, this cell would have been disabled safely.
Example 3 A battery was assembled and cycled as in Example 1, except the void was 0.6 ml. A similar overcharge test was performed. Figure 4 shows a later time than Example 1 to activation and venting at over 0.8 hours. Again, ignition occurred just after 0.9 hours into the test.
This test shows that had the disconnect device been active, there would be insufficient margin of safety .~. 2093'~~3 for overcharge protection. Thus, voids <0.6 ml are re-quired in this embodiment.
Example 4 A battery was assembled and cycled as in Example 1. The cell was subjected to 11 additional cycles at 21°C
as shown in Figure 5a. After this, the cell was installed in an incubator at 60°C with the voltage held at a constant 4 V (float charged). Figure 5b shows pressure and float current versus time. Noise on the pressure curve is a result of temperature fluctuations as the incubator door was opened many times a day.
The resulting pressure is well below the activa-tion pressure and decreases with time. This decrease is believed to be partly a result of equilibration processes and permeation of gas through the plastic seal. The seal was most permeable to the H2 generated mainly on the first charge in fresh cells. This occurs at the cathode and the source is water confined inside on assembly. While some gaseous decomposition products are probably produced, a significant pressure build-up does not occur.
Example 5 A cell was assembled and cycled as in Example 4 except that the void was set at 0.2m1. This cell was also installed in an incubator at 60°C on open circuit. The relief vent activated and electrolyte leaked out within 0.2 hours of installation before float testing could even begin. The pressure could be seen to increase rapidly as a result of cell component thermal expansion. This cell therefore is unacceptable for use over the normal tempera ture range.
.._ 2~93'~~3 These examples illustrate that batteries can be constructed with acceptable performance and use plated Li to hydraulically activate a disconnect on overcharge.
Example 6 Seventy-one cells were constructed as described in the specification with 0.4 ml voids and active discon-nects. All cells were cycled initially as in Example 1.
All cells were subjected to overcharge abuse as in Example 1. The disconnects in all cells activated well before 0.9 hours into the test. No subsequent ignition occurred.
Figure 6 shows voltage and external temperature for one of these cells. Activation of the disconnect occurred at about 0.65 hours. This example shows that reliable overcharge protection can be obtained using the invention batteries. These batteries incorporated LiCoOZ
only for the cathode.
As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the spirit or scope thereof. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
Figure 2b illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery cell which has been overcharged.
Figure 3 illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery as cycled according to a first procedure.
Figure 4 illustrates a graphical depiction of cell voltage, charged current, external cell temperature and internal pressure versus time for a rechargeable battery assembled and cycled as according to a second procedure.
Figure 5a illustrates a graphical depiction of voltage and pressure versus time, for a rechargeable battery which has been subjected to eleven cycles.
Figure 5b illustrates a graphical depiction of pressure and float current versus time for a rechargeable battery assembled and cycled according a fourth procedure.
Figure 6 illustrates a graphical depiction of voltage and external cell temperature versus time for a re-chargeable battery constructed according to the invention, demonstrating reliable overcharge protection.
~o93~s3 DETAILED DESCRIPTION OF SPECIFIC
EMBODIMENTS OF THE INVENTION
Li ion rechargeable cells (such as those commer-cially available from Sony Corporation) can vent violently with ensuing flame if overcharged too fast for too long (for example 2C rate for one hour). Activation of the disconnect partway through this period (approximately 1/2 hour in Figure 6) will safely shut the cell down. Depend-ing on the cell balance (defined as the mole ratio of active cathode to anode material), the ability of the anode to contain Li on charge may eventually be exhausted. On further charge, low density Li metal begins to plate out.
So while there is typically a net increase in solids volume during charge and overcharge (anode volume increase is typically greater than the cathode volume decrease), a more marked increase in volume occurs as Li is plated out.
Proper choice of cell balance, absolute electrode amounts and void space in the assembled cell results in a cell whose disconnect can be activated at the desired point in overcharge and is not activated over normal operating temperature ranges or prolonged storage.
The invention disclosed and claimed herein is directed to a rechargeable safety battery which utilizes a net increase in solids volume for activation of a discon-nect device. This is an important improvement over prior systems which are activated by gaseous decomposition.
Reliability is gained because decomposition occurs to some extent during normal cell operation and the rate is great-est during float charging at high temperatures. Thus, time and cell history affect the gas background. Conversely, the solids volume is mainly a function of the state of charge and is not significantly affected by time or cell history. Thus, the reliability in normal and abuse situ-ations together can be improved. In addition, even for a given cell history, it is difficult to engineer the decom-_. 2p9~'~~3 _8_ position such that adequate gassing occurs for protection, yet not too much occurs for normal use.
Since gaseous decomposition products are not required for the activation function, a larger range of electrochemical systems can be chosen. The invention has immediate application to Li ion rechargeable cells, but is not fundamentally limited to this type of cell.
The subject invention relies on the material prop-erties of the components, in particular the volume occupied as a function of temperature and state of lithiation (or charge) to activate a disconnect device in a lithium ion type cell. As a result, the generation of gas is not required. The life of the cell can be maximized by reduc-ing the electrolyte decomposition to a minimum. Also, time is not an important factor in the activation mechanism of the disconnect, allowing a wider range of options in the choice of electrolyte and cathode.
Description of Battery Construction The batteries according to the invention are constructed using intercalation compounds for both the active electrode materials. Compounds with the formula LiXMOZ, where x<1.1 and M is one or more transition metals, are used as the cathode while a carbonaceous material such as coke, graphite, pitch and the like, are used as the anode. These materials are used in powder form with particle sizes mainly in the range of 1-50 ~,m and are mounted on current collecting substrate foils using a suitable binder material. For purposes of making electri cal contacts, a conductive dilutant, either graphite or carbon black, is generally mixed in with the active elec trode material and binder.
._ 2~9~~~~
_ g -In the cells constructed for demonstration in the Examples which follow, cathode foils were prepared using LiCoOz powder obtained from Nihon Kagaku, KS15 graphite obtained from Lonza as the conductive dilutant, and poly-vinylidene fluoride (PVDF) powder from Kureha as the binder. A slurry of these components was prepared using a suitable amount of N-methyl-pyrrolidone (NMP) as the solvent in a ratio 91:6:3 parts by weight of LiCo02:graphite:PVDF. The slurry was then coated onto both sides of an aluminium foil substrate (-20 ~. thick), dried and then compressed such that a loading of 25 1/2 mg/cmZ of solids was applied to each side with a total resulting electrode thickness of 180 Similarly, anode foils were prepared using meso-carbon microbeads (MCMB) carbon as the primary anode material obtained from Osaka Gas, Super S (Trade-mark) carbon black from Ensagri as an additional conductive dilutant, and PVDF powder from Kureha as the binder. A
slurry was prepared from these materials in the ratio 88:2:10 parts by weight of MCMB:Super S: PVDF again by dissolving in a suitable amount of NMP solvent. This slurry was then coated on both sides of a copper foil substrate (-10 ~. thick) , dried and then compressed such that a loading of 12 mg/cm2 of solids was applied to each side with a total electrode thickness of 200 Dry cell assemblies were then prepared by spiral-ly winding an anode and cathode segment together into a "jelly roll" with two microporous Celgard 2400 (Trade-mark) film sheets present as separators. Typically, anode and cathode segments were 41 cm long by 57 1/2 mm wide and 37 cm long by 54 1/2 mm wide respectively. The jelly roll was then inserted into a conventional "4/3A" size battery container. (66.4 mm high, 16.6 mm OD). Appropriate ~p93~63 insulating pieces were included and appropriate tab connec-tions were made to the cell case and header.
The header used was of special construction that incorporated a pressure relief vent and a pressure operat-ed disconnect device. This header is the subject of a copending patent application (U.S. Patent Application No.
07/927,824). The disconnect pressure was set at --150 psi, while the pressure relief vent was set to open at -350 psi.
Electrolyte was added in several increments to activate the battery. In the following examples, a 1M
solution of LiPF6 dissolved in equal volumes of PC and DEC
was used as an electrolyte. Typically 5.9 g of solution was added. The header was then crimp sealed in place using conventional means.
Description of Invention in Relation to Drawinas Figure 1a shows a side section view of a specific cell construction according to the invention. As illus-trated in Figure la, in section view, a battery can 3, typically constructed of nickel plated steel, has a header assembly 1 at the top thereof. The header 1 and can 3 are sealed by seal 10. An insulating disk 2 is located immedi-ately below the neck portion 11 immediately under seal 10 and header assembly 1. A second insulating disk 7 is positioned above the base of the can 3. A jelly roll assembly 4, constructed as described below in relation to Figure lc, takes up most of the interior volume of the can 3. A cathode tab 5 is shown extending vertically in the central region of the can 3. An anode tab 6 is illus-trated extending vertically in the exterior region of the can 3. The upper horizontal broken line 12 indicates the upper edge of the anode. The upper horizontal broken line 13 illustrates the upper edge of the cathode.
2a93~63 The lower broken horizontal line 14 illustrates the lower edge of the cathode. The lower horizontal broken line 15 illustrates the lower edge of the anode. The electrolyte 8 is indicated generally within the interior of the can 3. The vertically extending spacer 9 is indicated in the central area of the can by broken lines.
Figure lb shows a detailed side section view of the header assembly 1 used in the cell construction of the invention. As illustrated in Figure lb, an external metal cover 16 is crimped at the periphery by an electrically conductive diaphragm 17.
The diaphragm 17 must be constructed of a cathode compatible material, such as aluminum, in this case. A
thin-walled grooved area is included in the diaphragm 17 design to burst upon application of sufficient physical force thereto. The diaphragm 17 thus acts as the pressure relief vent.
The cover 16 is typically constructed of stain-less steel and incorporates a vent hole 25 of some kind to allow the escape of gas and/or liquid in the event that the pressure relief vent is activated.
The diaphragm 17 is further electrically con-nected to an aluminum plate 18 by a critical weld 19. An electrically insulating gasket 20 positions the plate 18 with respect to the diaphragm. The gasket 20 electrically separates the positive header assembly 2 from the negative can 3. Additionally, the gasket 20 is used to provide a seal between the cell contents and the outside environment.
The cathode tab 5 (see Figures la and lc) is attached to the plate 18 at a site other than that of the critical weld 19. The plate 18 includes in it holes 26 to allow the flow of liquid and/or gas through it for purposes ~p93'~G3 of applying physical force to the diaphragm 17. The plate 18 is effectively fixed in position with reference to the gasket 20. Upon application of sufficient internal force-to the diaphragm 17, via holes 26, the critical weld 19 is broken. The diaphragm 17 is then free to move away upward-ly from the plate 18. When this occurs, the electrical path between the outside positive cover 16 and the plate 18 is broken thereby providing a pressure disconnect function.
Figure lc shows a detailed horizontal cross-section view of the cell. The helical jelly roll structure consisting of the cathode 21, anode 22 and separator 23 is illustrated. Also indicated are the can 3, spacer 9, cathode tab 5 and anode tab 6.
Cells such as these are capable of delivering large capacities for many cycles. This specific design is rated to deliver 800 mAh capacity (100% DOD) at 400 mA
(C/2) discharge rates over the cell lifetime following a fast -2 hour charge period to a 4 V cut-off. The maximum charge current of a charger for such a cell was taken to be 1.6 A (2C) rate. Thus, for purposes of testing these experimental batteries, overcharge testing was performed at a constant 2C rate until safe shutdown or cell failure was accomplished.
For purposes of effecting the desired result of hydraulic activation of the disconnect device, many factors must be considered. In the preceding description, and in the examples which follow, the choice of materials, elec-trode construction and operating conditions were made initially without consideration for disconnect activation.
It was then possible to accomplish both performance and activation objectives simply by varying the void volume in the cell. However, it will be obvious to those skilled in the art that other choices of materials, electrode con-struction and/or operating conditions may require the 2093'763 adjustment of other parameters. Thus, not all these parameters can be varied independently and still be compen-sated for simply by void adjustment. It is the intended scope of this disclosure, and the following claims to cover all possible battery constructions whereby the volume of plated lithium following the exhaustion of the anode capacity during overcharge is used for hydraulic activation of the disconnect.
As fabricated, at a given temperature, cells according to the invention generally are in a state with maximum internal void. Upon charging, lithium atoms are moved from the cathode host to the anode. Generally, the net electrode solids volume increases during this process.
While the volume occupied by the cathode is often (but not always) reduced as lithium is extracted, the volume oc-cupied by the anode increases as lithium is inserted. The net change in volume is usually positive on charge. Close to a reversible situation exists on subsequent discharge-charge cycles. In principle, a battery construction can be envisaged that uses this net volume increase to hydrauli-cally activate a disconnect at any desired point during normal charge, or preferably during an overcharge situ-ation.
It is, however, important to recognize that the battery must be capable of operation over wide temperature ranges, typically 0°C and up to 60°C. The net volume of the contents generally increases more rapidly than the internal volume of the container as temperature is in-creased. Thus, it is important to engineer the battery such that hydraulic activation does not occur as a result of using the battery at normal elevated temperatures. In practice, the net volume increase as the temperature is raised over this normal operating range is similar to the net volume increase seen in the electrode components during .w. 2~93~63 charge. Thus, it is difficult to achieve both performance and hydraulic activation goals in this way.
The situation changes, however, if the anode capacity is exhausted at an appropriate time during overcharge. At this point, the anode is no longer capable of intercalating lithium and lithium metal deposition must occur on the anode instead. The rate of net volume change increases markedly at this point since lithium metal is significantly less dense than the corresponding Li-carbon intercalation compound per unit lithium. Compare the rate of lithium intercalated graphite expansion which goes roughly as 3.3 cc increase in volume per mole Li interca-lated (derived from LixC6 lattice parameter data presented in Phase diactrams of LiXC6 Phys.Rev.B 1991 Vol. 44, No. 17, J. Dahn (page 9170)) versus a 13 cc increase in volume per mole of Li plated. If the battery is engineered such that lithium plating occurs in overcharge situations prior to cell failure with ignition, it becomes possible in practice to use the associated net volume increase to activate the safety disconnect.
A necessary condition, then, is that the lithium capacity of the cathode must exceed that of the anode. The ratio moles of cathode is called the balance.
moles of anode The batteries described in this disclosure have a preferred balance of approximately 1.5. Generally, the upper capacity limit on carbonaceous anodes is taken as 1 mole of Li per C6. However, this limit is less for coke like carbons and can be greater for modified carbons such as certain boron substituted carbon materials. Thus, the preferred balance will depend greatly on the materials used for the electrodes. Another necessary condition is that the lithium available for plating must exceed the void W_ 2093~G3 volume in the cell plus whatever additional volume is necessary to activate the disconnect.
It will be recognized that the net volume of the contents of the battery will be a function of all factors that influence the relative volume of any component includ-ing material choice, temperature, state of lithiation, and relative amounts of the components. Those skilled in the art are familiar with a variety of factors that make it difficult to predict the exact preferred construction.
These include irreversible losses of lithium that occur on the initial charge of the battery, the presence of some gaseous decomposition products even if minimized, and other factors. Normally then, fine tuning would be required using empirical methods.
Examples Example I
A battery was assembled as described in the preceding disclosure. The disconnect was bypassed such that the activation pressure was only slightly reduced, but would not disconnect internally. The battery was also equipped with a low volume pressure transducer attached via a small welded tube. This apparatus increased the internal cell volume by approximately 0.8 ml. The void for the entire assembly was adjusted to be 0.4 ml. The cell was charged and cycled once at 21°C to the normal 4 V upper limit. Figure 2a shows the cell voltage and internal pressure versus time for this cell. The cell delivered .87 Ah on discharge at 800 mA. The cell was then overcharged at 2C rate at ambient temperature as described earlier.
Figure 2b shows cell voltage, charge current, external cell temperature and internal pressure versus time for the cell.
The activation point of the disconnect is indicated by the dip in the pressure curve at approximately 0.45 hours.
This is a result of diaphragm movement which slightly .... 2093'~6~
increases internal void. The pressure relief activated just before 0.7 hours. Finally, the cell ignited just before 0.9 hours into the test. Thus, had the disconnect been active, this cell would have been disabled safely.
The onset of lithium plating, based solely on the total primary electrode materials available and one mole of lithium per C6 as the maximum anode capacity, would be approximately 0.3 hours into the test (i.e. Initial condi-tions have cathode of Li.55CoOZ and anode of Li.~C6. The conditions at anode exhaustion would be approximately Li,34Co02 and Li~C6) . There would theoretically be a maximum of .34 moles of Li per mole of initial cathode available for plating, corresponding to an additional volume of about 0.4 cc for activating a disconnect.
Example 2 A battery was assembled and cycled as in Example 1, except the void was adjusted to 0.2m1. A similar overcharge test was performed. Figure 3 shows an earlier time to activation (0.15 hours) and venting (0.35 hours) compared to Example 1. Again, ignition occurred at about 0.9 hours into the test. Had the disconnect been active, this cell would have been disabled safely.
Example 3 A battery was assembled and cycled as in Example 1, except the void was 0.6 ml. A similar overcharge test was performed. Figure 4 shows a later time than Example 1 to activation and venting at over 0.8 hours. Again, ignition occurred just after 0.9 hours into the test.
This test shows that had the disconnect device been active, there would be insufficient margin of safety .~. 2093'~~3 for overcharge protection. Thus, voids <0.6 ml are re-quired in this embodiment.
Example 4 A battery was assembled and cycled as in Example 1. The cell was subjected to 11 additional cycles at 21°C
as shown in Figure 5a. After this, the cell was installed in an incubator at 60°C with the voltage held at a constant 4 V (float charged). Figure 5b shows pressure and float current versus time. Noise on the pressure curve is a result of temperature fluctuations as the incubator door was opened many times a day.
The resulting pressure is well below the activa-tion pressure and decreases with time. This decrease is believed to be partly a result of equilibration processes and permeation of gas through the plastic seal. The seal was most permeable to the H2 generated mainly on the first charge in fresh cells. This occurs at the cathode and the source is water confined inside on assembly. While some gaseous decomposition products are probably produced, a significant pressure build-up does not occur.
Example 5 A cell was assembled and cycled as in Example 4 except that the void was set at 0.2m1. This cell was also installed in an incubator at 60°C on open circuit. The relief vent activated and electrolyte leaked out within 0.2 hours of installation before float testing could even begin. The pressure could be seen to increase rapidly as a result of cell component thermal expansion. This cell therefore is unacceptable for use over the normal tempera ture range.
.._ 2~93'~~3 These examples illustrate that batteries can be constructed with acceptable performance and use plated Li to hydraulically activate a disconnect on overcharge.
Example 6 Seventy-one cells were constructed as described in the specification with 0.4 ml voids and active discon-nects. All cells were cycled initially as in Example 1.
All cells were subjected to overcharge abuse as in Example 1. The disconnects in all cells activated well before 0.9 hours into the test. No subsequent ignition occurred.
Figure 6 shows voltage and external temperature for one of these cells. Activation of the disconnect occurred at about 0.65 hours. This example shows that reliable overcharge protection can be obtained using the invention batteries. These batteries incorporated LiCoOZ
only for the cathode.
As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the spirit or scope thereof. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
Claims (22)
1. A rechargeable battery cell which comprises:
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1, and M is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal electrical disconnect device which activates by the displacement of said electrolyte resulting from the net increase in solids volume which occurs on overcharge of the battery that exceeds the liquid and solid void volume in the battery cell;
wherein electrode balance, void, volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or storage at high temperature.
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1, and M is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal electrical disconnect device which activates by the displacement of said electrolyte resulting from the net increase in solids volume which occurs on overcharge of the battery that exceeds the liquid and solid void volume in the battery cell;
wherein electrode balance, void, volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not during normal float charging or storage at high temperature.
2. A battery as claimed in claim 1 wherein the volume of plated lithium following exhaustion of anode capacity during overcharge contributes to displacing the electrolyte.
3. A battery as claimed in claim 1 wherein the cathode (a) is LiCoO2, the anode (b) is a coke-like carbon, and the electrolyte (c) is 1M of LiPF6 dissolved in equal volumes of propylene carbonate and diethyl carbonate.
4. A battery as claimed in claim 1 wherein the internal disconnect device is constructed of a cathode compatible diaphragm, a cover with a vent hole positioned over the diaphragm, and a cathode compatible plate connected to the diaphragm and adapted to separate from the diaphragm under a hydraulic force exerted by the electrolyte against the diaphragm and disconnect an external electrical connection to the cathode, prior to battery cell failure.
5. A battery as claimed in claim 4 wherein the cathode compatible plate has therein at least one hole which enables electrolyte to pass from the interior of the battery to a plate-adjacent side of the cathode compatible diaphragm.
6. A battery as claimed in claim 4 wherein the cathode compatible diaphragm is connected to the cathode compatible plate by a critical weld.
7. A method of preventing hazardous overcharge of a rechargeable battery having a cathode, an anode, and an electrolyte which comprises incorporating within the battery an electrical disconnect means which activates by the displacement of said electrolyte resulting from the net increase in solids volume when overcharge beyond a point where liquid and solids void in the battery is exceeded, thereby electrically disconnecting the cathode or the anode; wherein electrode balance, void volume and charging level are selected so that the disconnect device operates during overcharge of use prior to cell failure, but not during normal float charging or storage at high temperature.
8. A method as claimed in claim 7 wherein the cathode is Li x MO2 wherein x is equal to or less than 1.1 and M is selected from the group of metals consisting of Ni, Co, Mn or combination thereof, the anode is a carbonaceous material, and the electrolyte is one or more lithium salts dissolved in one or more non-aqueous organic solvents.
9. A method as claimed in claim 7 or 8 wherein the volume of plated lithium following the exhaustion of anode capacity during overcharge contributes to displacing the electrolyte to disconnect the cathode or the anode.
10. A method as claimed in claim 7 or 8 wherein the cathode (a) is LiCoO2, the anode (b) is a coke-like carbon, and the electrolyte is 1M of LiPF6 dissolved in equal volumes of propylene carbonate and diethyl carbonate.
11. A rechargeable battery which comprises:
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1 and M
is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic salts; and (d) an internal electrical disconnect device which is constructed of a cathode compatible diaphragm, a cover with a vent hole positioned over the diaphragm, and a cathode compatible plate connected to the diaphragm, said cathode compatible plate having therein means for enabling electrolyte in the battery to impinge against the plate-adjacent side of the diaphragm when net increase in solids volume and volume of plated lithium following exhaustion of anode capacity during overcharge of the battery exceeds liquid and solid void volume in the battery and displaces the electrolyte to cause the diaphragm to separate from the plate and thereby disconnect an electrical connection to the cathode, prior to battery cell failure, wherein electrode balance, void volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not normal float charging or high temperature use.
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1 and M
is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic salts; and (d) an internal electrical disconnect device which is constructed of a cathode compatible diaphragm, a cover with a vent hole positioned over the diaphragm, and a cathode compatible plate connected to the diaphragm, said cathode compatible plate having therein means for enabling electrolyte in the battery to impinge against the plate-adjacent side of the diaphragm when net increase in solids volume and volume of plated lithium following exhaustion of anode capacity during overcharge of the battery exceeds liquid and solid void volume in the battery and displaces the electrolyte to cause the diaphragm to separate from the plate and thereby disconnect an electrical connection to the cathode, prior to battery cell failure, wherein electrode balance, void volume and charging level are selected so that the disconnect device operates during overcharge abuse prior to cell failure, but not normal float charging or high temperature use.
12. A battery as claimed in claim 11 wherein the cathode compatible plate has therein at least one hole which enables electrolyte to pass from the interior of the battery to the plate-adjacent side of the cathode compatible diaphragm.
13. A battery as claimed in claim 11 wherein the diaphragm is connected to the plate by a critical weld.
14. A method of preventing hazardous overcharge of a rechargeable battery having a cathode of Li x MO2 wherein x is equal to or less than 1.1 and M is selected from the group of metals consisting of Ni, Co, Mn or combinations thereof; an anode of carbonaceous material, and an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents, which comprises incorporating within the battery an electrical disconnect means which operates during overcharge abuse prior to cell failure, but not during normal float charging or high temperature use, by selection of electrode balance, void volume and charging level, which disconnect means activates by the displacement of electrolyte resulting from the net increase in solids volume which occurs on overcharge beyond a point where the liquid and solids void volume in the battery is exceeded, wherein said net increase in solids volume includes the volume of plated lithium following exhaustion of anode capacity during overcharge.
15. A method as claimed in claim 14 wherein the cathode is LiCoO2, the anode is a coke-like carbon, and the electrolyte is 1M of LiPF6 dissolved in equal volumes of propylene carbonate and diethyl carbonate.
16. A method for preventing the hazardous overcharge of a rechargeable battery cell comprising an anode, a cathode and an electrolyte comprising the step of disconnecting the anode or cathode of said battery in response to the electrolyte displacement resulting from the net increase in the solid volume of said battery cell on overcharging in excess of the void volume of said battery cell; wherein electrode balance, void volume and charging level are selected so that said disconnecting step occurs in response to overcharge abuse prior to cell failure, but not in response to normal float charging or high temperature use.
17. The method of claim 16 wherein said rechargeable battery cell comprises:
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1 and M
is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal electrical disconnect device which activates by said electrolyte displacement resulting from said net increase in solid volume occurring on overcharge of said battery in excess of said void battery cell void volume.
(a) a Li x MO2 cathode wherein x is equal to or less than 1.1 and M
is Ni, Co, Mn or combinations thereof;
(b) a carbonaceous anode;
(c) an electrolyte of one or more lithium salts dissolved in one or more non-aqueous organic solvents; and (d) an internal electrical disconnect device which activates by said electrolyte displacement resulting from said net increase in solid volume occurring on overcharge of said battery in excess of said void battery cell void volume.
18. The method of claim 17 wherein the volume of plated lithium following exhaustion of anode capacity during overcharge contributes to displacing said electrolyte.
19. The method of claim 17 wherein said cathode is LiCoO2 said anode is a coke-like carbon, and said electrolyte is 1M LiPF6 dissolved in equal volumes of propylene carbonate and diethyl carbonate.
20. The method of claim 17 wherein said internal disconnect device is constructed of a cathode compatible diaphragm, a cover with a vent hole positioned over said diaphragm, and a cathode compatible plate connected to said diaphragm and adapted to separate from said diaphragm under a hydraulic force exerted by said electrolyte against said diaphragm and disconnect an external electrical connection to said cathode, prior to battery cell failure.
21. The method of claim 20 wherein said cathode compatible plate has therein at least one hole which enables electrolyte to pass from the interior of said battery to the plate-adjacent side of said cathode compatible diaphragm.
22. The method of claim 20 wherein said cathode compatible diaphragm is connected to said cathode compatible plate by a critical weld.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002093763A CA2093763C (en) | 1993-04-08 | 1993-04-08 | Battery incorporating hydraulic activation of disconnect safety device on overcharge |
| US08/201,349 US5464705A (en) | 1993-04-08 | 1994-02-24 | Battery incorporating hydraulic activation of disconnect safety device on overcharge |
| JP6068719A JPH06325796A (en) | 1993-04-08 | 1994-04-06 | Battery with a breaker that activates when overcharged |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002093763A CA2093763C (en) | 1993-04-08 | 1993-04-08 | Battery incorporating hydraulic activation of disconnect safety device on overcharge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2093763A1 CA2093763A1 (en) | 1994-10-09 |
| CA2093763C true CA2093763C (en) | 1999-12-07 |
Family
ID=4151444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093763A Expired - Lifetime CA2093763C (en) | 1993-04-08 | 1993-04-08 | Battery incorporating hydraulic activation of disconnect safety device on overcharge |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5464705A (en) |
| JP (1) | JPH06325796A (en) |
| CA (1) | CA2093763C (en) |
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|---|---|---|---|---|
| CA2129558C (en) * | 1994-08-05 | 2001-04-24 | Ulrich Von Sacken | Battery with improved safety during mechanical abuse |
| JP3555240B2 (en) * | 1995-05-12 | 2004-08-18 | ソニー株式会社 | Sealed battery |
| US5741606A (en) * | 1995-07-31 | 1998-04-21 | Polystor Corporation | Overcharge protection battery vent |
| CA2240415C (en) | 1995-10-31 | 2002-12-24 | Matsushita Electric Industrial Co., Ltd. | Explosion-proof seal plate for sealed type cell and production method thereof |
| CA2163187C (en) * | 1995-11-17 | 2003-04-15 | Huanyu Mao | Aromatic monomer gassing agents for protecting non-aqueous lithium batteries against overcharge |
| KR100386394B1 (en) * | 1996-02-16 | 2003-08-14 | 후지 덴키 가가쿠 가부시키가이샤 | Battery with explosion-proof function |
| US5609972A (en) * | 1996-03-04 | 1997-03-11 | Polystor Corporation | Cell cap assembly having frangible tab disconnect mechanism |
| US5853912A (en) * | 1996-07-10 | 1998-12-29 | Saft America, Inc. | Lithium ion electrochemical cell with safety valve electrical disconnect |
| US6812985B1 (en) | 1996-09-23 | 2004-11-02 | Lg.Philips Lcd Co., Ltd. | Liquid crystal display device |
| JPH10241736A (en) * | 1997-02-26 | 1998-09-11 | Rohm Co Ltd | Battery structure |
| KR100251512B1 (en) | 1997-07-12 | 2000-04-15 | 구본준 | Transverse electric field liquid crystal display device |
| US6248473B1 (en) * | 1997-07-25 | 2001-06-19 | Eveready Battery Company, Inc. | Composite cover for a battery |
| JPH11144705A (en) * | 1997-11-11 | 1999-05-28 | Matsushita Electric Ind Co Ltd | Explosion-proof non-aqueous electrolyte secondary battery and method for setting its rupture pressure |
| US6210824B1 (en) | 1998-01-15 | 2001-04-03 | Texas Instruments Incorporated | Current interrupt apparatus for electrochemical cells |
| US6045950A (en) * | 1998-06-26 | 2000-04-04 | Duracell Inc. | Solvent for electrolytic solutions |
| US6346343B1 (en) * | 1999-11-11 | 2002-02-12 | U.S. Philips Corporation | Secondary lithium battery comprising lithium deposited on negative electrode material |
| JP3368877B2 (en) | 1999-11-17 | 2003-01-20 | 新神戸電機株式会社 | Cylindrical lithium-ion battery |
| CA2373904C (en) * | 2000-03-07 | 2010-01-26 | Teijin Limited | Lithium ion secondary battery, separator, battery pack and charging method |
| US20030113613A1 (en) * | 2001-12-17 | 2003-06-19 | Takeuchi Esther S. | High energy density rechargeable cell for medical device applications |
| JP4109184B2 (en) * | 2003-11-20 | 2008-07-02 | Ｔｄｋ株式会社 | Lithium ion secondary battery |
| BRPI0511211B8 (en) * | 2004-05-28 | 2023-01-10 | Lg Chemical Ltd | LITHIUM SECONDARY BATTERY |
| US20060024584A1 (en) * | 2004-05-28 | 2006-02-02 | Kim Dong M | Additives for lithium secondary battery |
| CN101305481B (en) * | 2005-09-02 | 2011-01-12 | A123系统公司 | Battery cell design and method of its construction |
| US8084158B2 (en) * | 2005-09-02 | 2011-12-27 | A123 Systems, Inc. | Battery tab location design and method of construction |
| KR100882914B1 (en) * | 2007-05-21 | 2009-02-10 | 삼성에스디아이 주식회사 | Battery Pack |
| US8236441B2 (en) | 2007-07-24 | 2012-08-07 | A123 Systems, Inc. | Battery cell design and methods of its construction |
| EP2215674B1 (en) * | 2007-11-30 | 2017-06-07 | A123 Systems LLC | Battery cell design with asymmetrical terminals |
| JP5285337B2 (en) * | 2008-06-13 | 2013-09-11 | 株式会社エヌ・ティ・ティ・ドコモ | Battery test apparatus and battery test method |
| JP5152098B2 (en) * | 2009-05-15 | 2013-02-27 | トヨタ自動車株式会社 | Sealed secondary battery |
| JP5081932B2 (en) * | 2010-01-25 | 2012-11-28 | 日立ビークルエナジー株式会社 | Sealed battery and manufacturing method thereof |
| US10128486B2 (en) | 2015-03-13 | 2018-11-13 | Purdue Research Foundation | Current interrupt devices, methods thereof, and battery assemblies manufactured therewith |
| WO2017214247A1 (en) | 2016-06-07 | 2017-12-14 | Navitas Systems, Llc | High loading electrodes |
| US11978919B2 (en) * | 2018-07-13 | 2024-05-07 | HYDRO-QUéBEC | Battery safety vent assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788112A (en) * | 1987-08-17 | 1988-11-29 | Kung Chin Chung | Rechargeable storage battery |
| JP2646657B2 (en) * | 1988-05-23 | 1997-08-27 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| CA2000873C (en) * | 1988-10-21 | 1999-12-14 | Shigeru Oishi | Cell having current cutoff valve |
| CA2055305C (en) * | 1990-11-17 | 2002-02-19 | Naoyuki Sugeno | Nonaqueous electrolyte secondary battery |
-
1993
- 1993-04-08 CA CA002093763A patent/CA2093763C/en not_active Expired - Lifetime
-
1994
- 1994-02-24 US US08/201,349 patent/US5464705A/en not_active Expired - Lifetime
- 1994-04-06 JP JP6068719A patent/JPH06325796A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06325796A (en) | 1994-11-25 |
| CA2093763A1 (en) | 1994-10-09 |
| US5464705A (en) | 1995-11-07 |
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