JPS63245858A - Nonaqueous secondary battery and process for the manufacture - Google Patents
Nonaqueous secondary battery and process for the manufactureInfo
- Publication number
- JPS63245858A JPS63245858A JP62079249A JP7924987A JPS63245858A JP S63245858 A JPS63245858 A JP S63245858A JP 62079249 A JP62079249 A JP 62079249A JP 7924987 A JP7924987 A JP 7924987A JP S63245858 A JPS63245858 A JP S63245858A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- electrode
- capacity
- positive electrode
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000008569 process Effects 0.000 title description 3
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 230000002441 reversible effect Effects 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 trinickel tetraoxide Chemical compound 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 238000001947 vapour-phase growth Methods 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- HQASLXJEKYYFNY-UHFFFAOYSA-N selenium(2-);titanium(4+) Chemical compound [Ti+4].[Se-2].[Se-2] HQASLXJEKYYFNY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical group Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 description 1
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- LNMGXZOOXVAITI-UHFFFAOYSA-N bis(selanylidene)hafnium Chemical compound [Se]=[Hf]=[Se] LNMGXZOOXVAITI-UHFFFAOYSA-N 0.000 description 1
- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 description 1
- IYJABVNLJXJBTP-UHFFFAOYSA-N bis(selanylidene)tantalum Chemical compound [Se]=[Ta]=[Se] IYJABVNLJXJBTP-UHFFFAOYSA-N 0.000 description 1
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 description 1
- WVMYSOZCZHQCSG-UHFFFAOYSA-N bis(sulfanylidene)zirconium Chemical compound S=[Zr]=S WVMYSOZCZHQCSG-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- NRJVMVHUISHHQB-UHFFFAOYSA-N hafnium(4+);disulfide Chemical compound [S-2].[S-2].[Hf+4] NRJVMVHUISHHQB-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HVEIXSLGUCQTMP-UHFFFAOYSA-N selenium(2-);zirconium(4+) Chemical compound [Se-2].[Se-2].[Zr+4] HVEIXSLGUCQTMP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- FAWYJKSBSAKOFP-UHFFFAOYSA-N tantalum(iv) sulfide Chemical compound S=[Ta]=S FAWYJKSBSAKOFP-UHFFFAOYSA-N 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
く技術分野〉
本発明は負極による容量支配型の非水二次電池に関し、
負極にリチウム、カリウム等のアルカリ金属、アルカリ
土類金属、希土類金属又は遷移金属を可逆的にインター
カレート及びディンターカレート可能な炭素質材料を用
いる非水二次電池及びその製造方法に関するものである
。[Detailed Description of the Invention] Technical Field> The present invention relates to a capacity-dominated non-aqueous secondary battery using a negative electrode.
This invention relates to a nonaqueous secondary battery using a carbonaceous material capable of reversibly intercalating and dintercalating alkali metals, alkaline earth metals, rare earth metals, or transition metals such as lithium and potassium as a negative electrode, and a method for manufacturing the same. be.
〈従来技術〉
電子機器等の小型化、軽量化に伴ない、リチウム、カリ
ウム等の軽金属を利用したエネルギー密度の高い二次電
池が注目を集めている。これらの二次電池の負極には、
リチウムやカリウム等の軽金属の単体、リチウム−アル
ミニウム合金やウソド合金等の低融点合金を利用した軽
金属合金又は導電性高分子若しくは熱焼成炭素体等の炭
素を主成分とした材料が用いられ、また他方の正極には
、五酸化バナジウムや二酸化マンガン等の金属酸化物、
二硫化チタンやセレン化チタン等のカルコゲン化合物又
は有機ポリマーが使用されている。ここに示したような
従来の非水二次電池系においては、負極の容量が少なか
ったり放電深度に制限があり、そのために正極に用いら
れる材料に大幅な制約があった。<Prior Art> As electronic devices and the like become smaller and lighter, secondary batteries with high energy density using light metals such as lithium and potassium are attracting attention. The negative electrode of these secondary batteries is
Single light metals such as lithium and potassium, light metal alloys using low-melting point alloys such as lithium-aluminum alloys and oxodo alloys, or materials mainly composed of carbon such as conductive polymers or heat-sintered carbon bodies are used. The other positive electrode contains metal oxides such as vanadium pentoxide and manganese dioxide,
Chalcogen compounds or organic polymers such as titanium disulfide and titanium selenide are used. In conventional non-aqueous secondary battery systems such as those shown here, the capacity of the negative electrode is small and the depth of discharge is limited, which places significant restrictions on the materials used for the positive electrode.
その理由としては、リチウム、カリウム等の軽金属の単
体を電極とした場合、頻繁な充電・放電の繰り返しによ
る金属の溶解・析出過程の結果、電池の内部短絡の原因
となる金属デンドライトが生成すること、リチウム−ア
ルミニウム合金を電極とした場合、放電によって合金中
のリチウム濃度が低下し、容量減少の原因となる合金電
極の脆化を起こすこと、ウッド合金などの低融点合金を
利用した場合では、電位を著しく貴にする過放電状態に
おいて特性劣化の原因となる合金成分の溶解が起こるこ
と、などが挙げられる。すなわち、これらの負極を完全
放電等のように深い放電深度の状態にまで放電すると電
極に何らかの支障をきたし、電池性能に悪影響を与える
ことになるために、正極に深い放電深度まで放電しても
特性に何ら影響の現われない活物質を用い、放電容量が
正極支配となるようにして負極の負担を軽減しなければ
ならなかった。The reason for this is that when a single light metal such as lithium or potassium is used as an electrode, metal dendrites are formed as a result of the metal dissolution and precipitation process due to frequent charging and discharging, which can cause internal short circuits in the battery. When a lithium-aluminum alloy is used as an electrode, the lithium concentration in the alloy decreases due to discharge, causing embrittlement of the alloy electrode which causes a decrease in capacity.When using a low melting point alloy such as Wood's alloy, For example, in an over-discharge state where the potential becomes extremely noble, alloy components may dissolve, causing property deterioration. In other words, if these negative electrodes are discharged to a deep discharge depth such as a complete discharge, it will cause some kind of trouble to the electrodes and have a negative impact on battery performance, so even if the positive electrode is discharged to a deep discharge depth, It was necessary to use an active material that does not affect the characteristics in any way so that the discharge capacity is dominated by the positive electrode, thereby reducing the burden on the negative electrode.
また、深い放電深度の状態にしても比較的劣化しにくい
導電性高分子などの炭素を主成分とした従来の材料を用
いること及び放電の終了条件を制御することにより、負
極支配型の電池を可能とすることができるが、これらの
構造では放電容量が少なくなり、電池を高エネルギー密
度化することができない。In addition, by using conventional carbon-based materials such as conductive polymers that are relatively resistant to deterioration even at deep discharge depths, and by controlling the discharge termination conditions, negative electrode-dominated batteries can be developed. However, with these structures, the discharge capacity is reduced and the battery cannot be made to have a high energy density.
〈発明の目的〉
本発明は負極の深い放電深度まで放電しても特性に何ら
影響の現われない電極構造を用いることで放電容量が負
極支配となり得る高容量の二次電池の実現を可能とし、
従来では非水二次電池用の正極として使用の困難であっ
た材料を使用可能とし、非水二次電池系として幅のある
電池及びその製造方法を提供することを目的とする。<Objective of the Invention> The present invention makes it possible to realize a high-capacity secondary battery in which the discharge capacity is dominated by the negative electrode by using an electrode structure in which the characteristics are not affected in any way even when the negative electrode is discharged to a deep discharge depth.
It is an object of the present invention to enable the use of materials that have conventionally been difficult to use as positive electrodes for non-aqueous secondary batteries, and to provide a battery that has a wide range of uses as a non-aqueous secondary battery system, and a method for manufacturing the same.
〈発明の概要〉
従来の技術により発生する種々の問題を鑑み、鋭意研究
を重ねた結果、炭化水素又は炭化水素化合物を出発原料
とし熱分解による気相堆積法で得られる炭素質材料を、
触媒作用を有する導電性基板上へ堆積した電極が、電池
用電極材料として高い容量を保有しかつ深い放電深度ま
で放電しても特性に何ら影響が現われないことを見い出
した。<Summary of the Invention> In view of various problems caused by conventional techniques, as a result of extensive research, we have developed a carbonaceous material obtained by a vapor phase deposition method using thermal decomposition using hydrocarbons or hydrocarbon compounds as starting materials.
It has been found that an electrode deposited on a conductive substrate with catalytic action has a high capacity as a battery electrode material, and its characteristics are not affected at all even when discharged to a deep discharge depth.
炭素質材料は、ベンゼン、ナフタリン、アントラセン、
ヘキサメチレンベンゼン、１，２−ジブロモエチレン、
２−ブチン、アセチレン、ビフェニル、ジフェニルアセ
チレン等の炭化水素あるいは他の特性基を付加乃至置換
した炭化水素化合物を水素及び／又はアルゴンガスをキ
ャリアガスとするバブラ法、蒸発法、昇華法等の各種搬
送方法により気化して反応系へ供給し、反応系内で１５
００℃以下の低温熱分解による気相堆積法でニッケル等
の触媒作用を有する金属基体に直接形成することにより
得られる。ここで、低温熱分解する濃度と温度は、出発
原料にする炭化水素あるいは炭化水素化合物材料により
異なるが、通常数ミリモルパーセントの濃度及び１００
０℃程度の温度で制御される。Carbonaceous materials include benzene, naphthalene, anthracene,
hexamethylenebenzene, 1,2-dibromoethylene,
Hydrocarbons such as 2-butyne, acetylene, biphenyl, diphenylacetylene, etc. or hydrocarbon compounds to which other characteristic groups have been added or substituted can be processed using bubbler methods, evaporation methods, sublimation methods, etc., in which hydrogen and/or argon gas is used as a carrier gas. It is vaporized by the transportation method and supplied to the reaction system, and 15
It can be obtained by directly forming it on a metal substrate having a catalytic effect, such as nickel, by a vapor deposition method using low-temperature pyrolysis at 00° C. or lower. Here, the concentration and temperature for low-temperature pyrolysis vary depending on the hydrocarbon or hydrocarbon compound material used as the starting material, but usually the concentration is several mmol percent and 100
The temperature is controlled at about 0°C.
本発明の電池は、前述の低温熱分解による気相堆積法で
得られる炭素材料を触媒性を有する導電性基板上へ堆積
したものを負極とし、他に正極及びイオン導電性物質と
から構成される。The battery of the present invention is composed of a carbon material obtained by the above-mentioned low-temperature pyrolysis vapor deposition method deposited on a conductive substrate having catalytic properties as a negative electrode, and a positive electrode and an ion conductive material. Ru.
正極には、バナジウム酸化物、五酸化ニオブ。Vanadium oxide and niobium pentoxide are used for the positive electrode.
三二酸化ビスマス、三二酸化アンチモン、クロム酸化物
、三酸化モリブデン、三酸化タングステン。Bismuth sesquioxide, antimony sesquioxide, chromium oxide, molybdenum trioxide, tungsten trioxide.
二酸化セレン、二酸化テルル 三二酸化鉄，四三酸化ニッケル、酸化ニッケル。Selenium dioxide, tellurium dioxide Iron sesquioxide, trinickel tetraoxide, nickel oxide.
三酸化コバルト、酸化コバルト等の酸化物又は硫化チタ
ン、硫化ジルコニウム、硫化ハフニウム。Oxides such as cobalt trioxide and cobalt oxide, or titanium sulfide, zirconium sulfide, and hafnium sulfide.
硫化タンタル、硫化モリブデン、硫化タングステン、セ
レン化チタン、セレン化ジルコニウム、セレン化ハフニ
ウム、セレン化バナジウム、セレン化ニオブ、セレン化
タンタル、セレン化モリブデン、セレン化タングステン
等のカルコゲン化合物などの単一化合物あるいは２種類
以上の複合物若しくは混合物が用いられる。又、これら
化合物に少量のドーパントを添加してもかまわない。正
極活物質の結晶状態は単結晶、微結晶、非晶質のいずれ
の状態でもよくこれらが共存していてもよい。Single compounds such as chalcogen compounds such as tantalum sulfide, molybdenum sulfide, tungsten sulfide, titanium selenide, zirconium selenide, hafnium selenide, vanadium selenide, niobium selenide, tantalum selenide, molybdenum selenide, tungsten selenide, etc. Compounds or mixtures of two or more types are used. Further, a small amount of dopant may be added to these compounds. The crystalline state of the positive electrode active material may be single crystal, microcrystalline, or amorphous, and these may coexist.
正極の形態は、フィルム状、薄膜状、焼結体、ペースト
状９粒状、高多孔体、ゲル状、インゴット等のいずれで
あってもよくまたこれらの混合物であってもかまわない
。The positive electrode may be in the form of a film, a thin film, a sintered body, a paste-like particle, a highly porous body, a gel, an ingot, or a mixture thereof.
イオン導電性物質とは負極炭素質材料に対し電気化学的
かつ可逆的にインターカレート、ディンターカレート可
能なイオン又はそのイオンにより構成される塩類及びそ
れらを安定に存在させ得る物質のことであり、例えば非
プロトン性有機溶媒溶液等の電解質溶液、固体電解質、
溶融塩などが挙げられる。尚、正極と負極の接触を妨げ
るためのセパレータを正極と負極の間に配置してもかま
わない。An ion conductive substance is an ion that can electrochemically and reversibly intercalate or dintercalate into a negative electrode carbonaceous material, or a salt composed of such an ion, and a substance that can stably cause these to exist. , electrolyte solutions such as aprotic organic solvent solutions, solid electrolytes,
Examples include molten salt. Note that a separator may be placed between the positive electrode and the negative electrode to prevent contact between the positive electrode and the negative electrode.
〈発明の効果〉
ニッケル等の触媒作用を有する導電性の電極基体上に炭
化水素あるいは炭化水素化合物の低温熱分解による気相
堆積法で形成して得られる炭素質材料からなる電極は、
充電・放電の繰り返し及び過放電することになる可逆的
に充電・放電の可能な容量が減少することなく、また、
炭素質材料が導電性の電極基体上に直接形成されて電気
的、機械的に連結され、新たな導電材の添加や結着剤の
添加を必要としないために電極材料の充填密度が高くな
り、その結果高エネルギー密度の電極が得られる。また
、工程が簡単化され、二次電池用の電極として非常に有
効なものである。<Effects of the Invention> An electrode made of a carbonaceous material obtained by forming it on a conductive electrode substrate having a catalytic action such as nickel by a vapor phase deposition method using low-temperature thermal decomposition of a hydrocarbon or a hydrocarbon compound is
without reducing the capacity that can be reversibly charged and discharged due to repeated charging and discharging and over-discharging, and
The carbonaceous material is formed directly on the conductive electrode substrate and is electrically and mechanically connected, and the packing density of the electrode material is increased because there is no need to add a new conductive material or binder. , resulting in a high energy density electrode. Moreover, the process is simplified and it is very effective as an electrode for secondary batteries.
上記触媒作用を有する導電性基板上へ堆積された炭素質
材料を負極とし、可逆的に充電・放電可能な容量を負極
に比べ大とした正極と組み合わせて得られる二次電池は
、充電・放電の繰り返し回数及び過放電することによる
可逆的に充電・放電の可能な容量の減少がなく、また、
高エネルギー密度となることから二次電池として優れた
特性を得ることが可能となるため、その工業的価値は極
めて大である。A secondary battery obtained by using the carbonaceous material deposited on the above-mentioned catalytic conductive substrate as a negative electrode and combining it with a positive electrode that has a larger reversible charging and discharging capacity than the negative electrode can be used for charging and discharging. There is no reduction in the capacity that can be reversibly charged and discharged due to the number of repetitions and over-discharge, and
Because it has a high energy density, it is possible to obtain excellent characteristics as a secondary battery, so its industrial value is extremely large.
〈実施例〉 第１図は本発明の１実施例を示す電池の構成図である。<Example> FIG. 1 is a block diagram of a battery showing one embodiment of the present invention.
負極にベンゼンを出発原料とし低温熱分解法で発泡性ニ
ッケル基体に直接気相堆積して得られた炭素質材料を用
い、正極２にＣｒＢＯＢを、また両電極間にＩＭの過塩
素酸リチウムを溶解したプロピレンカーボネートを電解
液として含有したポリエチレン製の不繊布よりなるセパ
レータ６を用い、第１図に示す形状の電池を作製した。A carbonaceous material obtained by direct vapor phase deposition on a foamable nickel substrate using benzene as a starting material by low-temperature pyrolysis is used for the negative electrode, CrBOB is used for the positive electrode 2, and IM lithium perchlorate is placed between both electrodes. A battery having the shape shown in FIG. 1 was fabricated using a separator 6 made of a nonwoven polyethylene fabric containing dissolved propylene carbonate as an electrolyte.
ここで、負極１である炭素質材料は、第２図に示す反応
装置を用いて作製した。即ち、一旦脱水処理を施しさら
に真空移送による蒸留精製操作を行なったベンゼンを収
納した容器１１内にアルゴンガス供給器１２よりアルゴ
ンガスを供給し、ベンゼンのバブルを行なった後パイレ
ックス製ガラス管１３を介して石英製反応管１４ヘベン
ゼンを給送する。この際、容器１１をベンゼンの蒸発に
よる吸熱量の分だけ加熱することにより温度を一定に保
持し、またニードル弁１５．１６を操作することにより
ベンゼン量を最適化した。反応管１４には発泡状ニッケ
ルから成る直径１５闘φ、厚さ１．５胃肩の電極基体の
載置されたホルダー１７が設置されており、反応管１４
の外周囲には加熱炉１８が設けられている加熱炉１８に
よりホルダー１７及び電極基体を約１０００℃に約３０
分間維持し、パイレックス製ガラス管１３より供給され
るベンゼンを熱分解し、電極基体に３９．８〜の炭素質
材料を堆積させた。Here, the carbonaceous material that is the negative electrode 1 was produced using a reaction apparatus shown in FIG. That is, argon gas is supplied from an argon gas supply device 12 into a container 11 containing benzene that has been subjected to a dehydration treatment and further subjected to a distillation purification operation by vacuum transfer, and after bubbling the benzene, a Pyrex glass tube 13 is inserted. Hebenzene is fed through the quartz reaction tube 14. At this time, the temperature was kept constant by heating the container 11 by the amount of heat absorbed by the evaporation of benzene, and the amount of benzene was optimized by operating the needle valves 15 and 16. The reaction tube 14 is equipped with a holder 17 on which an electrode base made of foamed nickel and having a diameter of 15 mm and a thickness of 1.5 mm is placed.
A heating furnace 18 is provided around the outer periphery of the holder 17 and the electrode base at a temperature of about 1000°C for about 30 minutes.
The temperature was maintained for 1 minute, and the benzene supplied from the Pyrex glass tube 13 was thermally decomposed, and a carbonaceous material of 39.8~ was deposited on the electrode substrate.
熱分解反応後の反応管１４内に残留するガスは排気設備
１９．２０を通して除去する。この様にして炭素体を堆
積させた電極基体をプレス機で成形し本実施例の電池の
負極１とした。尚、この電極の容量を調べたところ、可
逆的充電・放電可能な容量が１２．５ ｍＡｈ であ
った。正極２のＣｒ３Ｏ８なる組成の酸化物は、三酸化
クロムを耐圧容器内で２３０℃の温度で熱処理すること
により得た。The gas remaining in the reaction tube 14 after the pyrolysis reaction is removed through exhaust equipment 19,20. The electrode substrate on which the carbon body was deposited in this manner was molded using a press to form the negative electrode 1 of the battery of this example. When the capacity of this electrode was examined, it was found that the reversible charging/discharging capacity was 12.5 mAh. The oxide having a composition of Cr3O8 of the positive electrode 2 was obtained by heat-treating chromium trioxide at a temperature of 230° C. in a pressure vessel.
この酸化物１００重量部に対し、アセチレンブラツク１
０重量部、ポリ四フッ化エチレン樹脂粉末５重量部を加
えて混練し、正極活物質の混合物を得た。この混合物１
００”１２を２１０℃の温度でかつ３０ＱＫｇｃＩｎ−
２の加圧力で成型し本実施例の電池の正極２とした。ま
た、この電極の容量を調べたところ可逆的充電・放電可
能な容量が１９．７ ｍＡｈであった。正極２及び負極
１の容量は２００℃で８時間減圧乾燥し脱水処理を施し
た後、グローブボックス内で１Ｍ過塩素酸リチウムを溶
解したプロピレンカーボネート中で調べたものである。For 100 parts by weight of this oxide, 1 part by weight of acetylene black
0 parts by weight and 5 parts by weight of polytetrafluoroethylene resin powder were added and kneaded to obtain a mixture of positive electrode active materials. This mixture 1
00”12 at a temperature of 210°C and 30QKgcIn-
It was molded with a pressure of 2 to form the positive electrode 2 of the battery of this example. Further, when the capacity of this electrode was investigated, the reversible charging/discharging capacity was 19.7 mAh. The capacities of the positive electrode 2 and the negative electrode 1 were examined in a glove box in propylene carbonate in which 1M lithium perchlorate was dissolved after drying under reduced pressure at 200° C. for 8 hours and dehydration treatment.
第１図の電池は、予め正極容器４にスポット溶接しであ
る金属性ネット５に正極２を圧着し、１Ｍ過塩素酸リチ
ウムを溶解したプロピレンカーボネートを含有したポリ
プロピレン製セパレータ６をのせた後、予め負極ｌをス
ポット溶接しである負極蓋３を冠せ、絞め金型を用いて
鮫め、ポリプロピレン製パツキン７によりシールし、コ
イン型状の電池Ａとしたものである。In the battery shown in FIG. 1, the positive electrode 2 is pressure-bonded to a metal net 5 that has been spot-welded to the positive electrode container 4 in advance, and a polypropylene separator 6 containing propylene carbonate in which 1M lithium perchlorate is dissolved is placed. The negative electrode 1 was spot-welded in advance, a negative electrode cover 3 was placed on top, the lid 3 was sealed using a squeeze mold, and the battery was sealed with a polypropylene gasket 7 to form a coin-shaped battery A.
電池Ａを１ｍＡの電流で充電・放電を繰り返し、繰り返
しのサイクル数に対する放電容量の変化を第３図に実線
で示した。Battery A was repeatedly charged and discharged with a current of 1 mA, and the change in discharge capacity with respect to the number of repeated cycles is shown in FIG. 3 by a solid line.
〈比較例１〉
負極にリチウム金属を用い、正極に上記実施例と同様の
正極を用い、負極蓋に集電用金属ネットを設け、その他
は上記実施例と同様の条件としてコイン型状の電池Ｂを
作製した。電池Ｂの正極の可逆的充電・放電可能な容量
は１．５ｍＡｈ であり、負極の理論放電容量は３０
０ｍＡｈ であった。電池Ｂを１ｍＡの電流で充電・
放電を繰り返し、繰り返しのサイクル数に対する放電容
量の変化を第３図に破線で示した。<Comparative Example 1> A coin-shaped battery was manufactured using lithium metal for the negative electrode, the same positive electrode as in the above example for the positive electrode, a metal net for current collection on the negative electrode lid, and the other conditions being the same as in the above example. B was produced. The reversible charge/discharge capacity of the positive electrode of battery B is 1.5 mAh, and the theoretical discharge capacity of the negative electrode is 30 mAh.
It was 0mAh. Charge battery B with a current of 1 mA.
Discharge was repeated, and the change in discharge capacity with respect to the number of repeated cycles is shown in FIG. 3 by a broken line.
〈比較例２〉
負極にリチウム金属を用い、正極に上記実施例と同様の
材料を用い、正極と負極の可逆的充電・放電可能な容量
に比が異なること以外は比較例１と同様の電池Ｃを作製
した。電池Ｃの正極の充電・放電可能な容量は１５．０
ｍＡｈ であり、負極の理論放電容量は１２．０
ｍＡｈ であった。電池Ｃを１ｍＡの電流で充電・放
電を繰り返したところ初め９．５ ｍＡｈ の放電容
量が得られたが３サイクルめの放電容量はＯｍＡｈ
であった。<Comparative Example 2> A battery similar to Comparative Example 1 except that lithium metal was used for the negative electrode, the same material as in the above example was used for the positive electrode, and the ratio of the reversible charge/discharge capacity of the positive electrode and negative electrode was different. C was produced. The charging/discharging capacity of the positive electrode of battery C is 15.0
mAh, and the theoretical discharge capacity of the negative electrode is 12.0
It was mAh. When battery C was repeatedly charged and discharged with a current of 1 mA, a discharge capacity of 9.5 mAh was initially obtained, but the discharge capacity in the third cycle was OmAh.
Met.
第１図は本発明のｌ実施例を示す二次電池の模式断面図
である。第２図は、第１図に示す実施例の説明に係る炭
素質材料生成装置のブロック構成図である。第３図は、
電池Ａ及び電池Ｂの充電・放電可能な容量とサイクル数
の関係を示す特性図である。
１・・・負極、２・・・正極、３・・・負極蓋、４・・
・正極容器、５・・・金属製ネット、６・・・セパレー
タ、７・・・パツキン、１１・・・バフル容器、１２・
・・アルゴンガス供給系、１３・・・パイレックス反応
管、１４・・・反応管、１５．１６・・・ニードル弁、
１７・・・試料ホルダー、１８・・・加熱炉、１９．２
０・・・排気設備。
代理人 弁理士 杉 山 毅 至（他１名）ＬＩＶｕＪ
／りFIG. 1 is a schematic cross-sectional view of a secondary battery showing an embodiment of the present invention. FIG. 2 is a block diagram of the carbonaceous material production apparatus according to the embodiment shown in FIG. 1. FIG. Figure 3 shows
FIG. 3 is a characteristic diagram showing the relationship between the chargeable/dischargeable capacity and the number of cycles of batteries A and B. 1... Negative electrode, 2... Positive electrode, 3... Negative electrode lid, 4...
- Positive electrode container, 5... Metal net, 6... Separator, 7... Packing, 11... Baffle container, 12.
... Argon gas supply system, 13... Pyrex reaction tube, 14... Reaction tube, 15.16... Needle valve,
17... Sample holder, 18... Heating furnace, 19.2
0...Exhaust equipment. Agent Patent Attorney Takeshi Sugiyama (and 1 other person) LIVuJ
/the law of nature
Claims (1)
電可能な容量に比べて大である非水二次電池において、
前記負極が触媒作用を呈する導電性基体に直接堆積され
かつアルカリ金属、アルカリ土類金属、希土類金属又は
遷移金属を可逆的にインターカレート及びデインターカ
レートする熱分解炭素質材料で形成されていることを特
徴とする非水二次電池。 ２、導電性基体がニッケルである特許請求の範囲第１項
記載の非水二次電池。 ３、正極の可逆的充放電可能な容量が負極の可逆的充放
電可能な容量に比べて大である非水二次電池の製造方法
において、前記負極が炭化水素または炭化水素化合物を
出発原料とし、熱分解による気相堆積法で、触媒作用を
有する導電性基体に、アルカリ金属、アルカリ土類金属
、希土類金属又は遷移金属を可逆的にインターカレート
及びデインターカレートする炭素質材料を直接堆積する
ことにより形成されることを特徴とする非水二次電池の
製造方法。 ４、導電性基体としてニッケルを用いる特許請求の範囲
第３項記載の非水二次電池の製造方法。[Claims] 1. In a nonaqueous secondary battery in which the reversible chargeable and dischargeable capacity of the positive electrode is larger than that of the negative electrode,
the negative electrode is deposited directly on a catalytic conductive substrate and is formed of a pyrolytic carbonaceous material that reversibly intercalates and deintercalates alkali metals, alkaline earth metals, rare earth metals or transition metals; A non-aqueous secondary battery characterized by: 2. The non-aqueous secondary battery according to claim 1, wherein the conductive substrate is nickel. 3. A method for producing a non-aqueous secondary battery in which the reversible chargeable and dischargeable capacity of the positive electrode is larger than that of the negative electrode, wherein the negative electrode uses a hydrocarbon or a hydrocarbon compound as a starting material. , a carbonaceous material that reversibly intercalates and deintercalates alkali metals, alkaline earth metals, rare earth metals, or transition metals is directly applied to a catalytic conductive substrate using a pyrolytic vapor deposition method. A method for manufacturing a non-aqueous secondary battery, characterized in that it is formed by deposition. 4. The method for manufacturing a non-aqueous secondary battery according to claim 3, wherein nickel is used as the conductive substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62079249A JPH0828238B2 (en) | 1987-03-31 | 1987-03-31 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62079249A JPH0828238B2 (en) | 1987-03-31 | 1987-03-31 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63245858A true JPS63245858A (en) | 1988-10-12 |
| JPH0828238B2 JPH0828238B2 (en) | 1996-03-21 |
Family
ID=13684583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62079249A Expired - Fee Related JPH0828238B2 (en) | 1987-03-31 | 1987-03-31 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0828238B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994221A (en) * | 1988-06-03 | 1991-02-19 | Sharp Kabushiki Kaisha | Method for the production of a carbon electrode |
| JPH03266358A (en) * | 1990-03-15 | 1991-11-27 | Sharp Corp | Manufacture of carbon electrode and nonaqueous secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57103274A (en) * | 1980-12-17 | 1982-06-26 | Yuasa Battery Co Ltd | Secondary battery with nonaqueous electrolyte |
| JPS5918578A (en) * | 1982-07-21 | 1984-01-30 | Nippon Denso Co Ltd | Organic battery |
| JPS6036315A (en) * | 1983-08-10 | 1985-02-25 | Toray Ind Inc | Carbon fiber structure and secondary battery using it |
-
1987
- 1987-03-31 JP JP62079249A patent/JPH0828238B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57103274A (en) * | 1980-12-17 | 1982-06-26 | Yuasa Battery Co Ltd | Secondary battery with nonaqueous electrolyte |
| JPS5918578A (en) * | 1982-07-21 | 1984-01-30 | Nippon Denso Co Ltd | Organic battery |
| JPS6036315A (en) * | 1983-08-10 | 1985-02-25 | Toray Ind Inc | Carbon fiber structure and secondary battery using it |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994221A (en) * | 1988-06-03 | 1991-02-19 | Sharp Kabushiki Kaisha | Method for the production of a carbon electrode |
| JPH03266358A (en) * | 1990-03-15 | 1991-11-27 | Sharp Corp | Manufacture of carbon electrode and nonaqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0828238B2 (en) | 1996-03-21 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |