CN109863633A - 电化学装置 - Google Patents
电化学装置 Download PDFInfo
- Publication number
- CN109863633A CN109863633A CN201780065310.3A CN201780065310A CN109863633A CN 109863633 A CN109863633 A CN 109863633A CN 201780065310 A CN201780065310 A CN 201780065310A CN 109863633 A CN109863633 A CN 109863633A
- Authority
- CN
- China
- Prior art keywords
- anion
- electrochemical appliance
- electroconductive polymer
- electrolyte
- 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.)
- Granted
Links
- 150000001450 anions Chemical class 0.000 claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 27
- 239000007773 negative electrode material Substances 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 230000014509 gene expression Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229910005143 FSO2 Inorganic materials 0.000 claims description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000006850 spacer group Chemical group 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 thiofuran ethylene derivative Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 230000006866 deterioration Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
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- 229920001971 elastomer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910013350 LiBCl4 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910010940 LiFSO3 Inorganic materials 0.000 description 1
- 229910013164 LiN(FSO2)2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- CYGKLLHTPPFPHH-UHFFFAOYSA-N aniline;hydrate Chemical compound O.NC1=CC=CC=C1 CYGKLLHTPPFPHH-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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Abstract
本发明在将包含能够掺杂和脱掺杂阴离子的导电性高分子的正极、和包含能够吸储和放出锂离子的负极材料的负极组合而成的电化学装置中,维持浮动特性。电化学装置具备:正极,包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质;负极,包含能够吸储和放出锂离子的负极活性物质;和电解液,包含阴离子和锂离子。构成正极所含的导电性高分子的单体单元的总量A(mol)、与电化学装置所含的阴离子的总量B(mol)满足关系式:0<B/A<0.7。
Description
技术领域
本发明涉及将包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质的正极、和包含能够吸储和放出锂离子的负极活性物质的负极组合而成的电化学装置。
背景技术
近年来,具有锂离子二次电池与双电层电容器的中间性能的电化学装置引起关注,例如正在研究将导电性高分子作为正极活性物质使用。这样的包含导电性高分子作为正极活性物质的电子化学装置通过阴离子的吸附(掺杂)和脱离(脱掺杂)进行充放电,因此反应电阻小,与普通的锂离子二次电池的正极相比具有高的输出。作为导电性高分子,已知聚苯胺、聚吡咯等(参照专利文献1和2)。
现有技术文献
专利文献
专利文献1:日本特开平1-146255号公报
专利文献2:日本特开2014-35836号公报
发明内容
电化学装置例如用作在因停电等向PC、服务器等设备的电力供给被阻断的情况下用于向设备供给电力的备用电源。通常维持向电化学装置施加规定的电压的状态(进行浮动充电),在停电等异常时,由电化学装置向设备供给电力(电化学装置放电)。然而,若长时间进行浮动充电,则有正极活性物质(导电性高分子)劣化而容量降低的倾向。因此,抑制电化学装置的浮动充电后的容量降低(维持浮动特性)是重要的。
关于构成正极中的导电性高分子的单体单元的量和电化学装置所含的阴离子的量的平衡、与浮动特性的关系的研究依然没有充分进行。
鉴于上述情况,本发明的一个方面涉及电化学装置,其具备:正极,包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质;负极,包含能够吸储和放出锂离子的负极活性物质;和电解液,包含上述阴离子和上述锂离子,构成上述正极所含的上述导电性高分子的单体单元的总量A(mol)、与上述电化学装置所含的上述阴离子的总量B(mol)满足下述关系式:
0<B/A<0.7。
根据本发明,在将包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质的正极、和包含能够吸储和放出锂离子的负极活性物质的负极组合而成的电化学装置中,能够抑制浮动充电后的容量降低(维持浮动特性)。
附图说明
图1是本发明的实施方式涉及的电化学装置的截面示意图。
图2是用于说明该实施方式涉及的电化学装置的构成的示意图。
图3是表示本发明的实施方式涉及的电化学装置中的B/A与容量维持率的关系的图表。
具体实施方式
本发明涉及一种电化学装置,其具备:正极,作为正极材料包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质;负极,包含能够吸储和放出锂离子的负极活性物质;和电解液,包含阴离子和锂离子。充电时,电解液中的阴离子被掺杂于导电性高分子,电解液中的锂离子被吸储于负极材料。放电时,阴离子从导电性高分子脱掺杂,向电解液中移动,锂离子从负极材料放出,向电解液中移动。本发明中,导电性高分子包括在脱掺杂状态下几乎没有导电性或没有导电性的情况。
构成正极所含的导电性高分子的单体单元的总量A(mol)、与电化学装置所含的阴离子的总量B(mol)满足下述关系式:
0<B/A<0.7。
构成正极所含的导电性高分子的单体单元的总量A与电化学装置所含的阴离子的总量B相比越大,则B/A越成为接近0的值。电化学装置所含的阴离子的总量B至少包含为了得到规定的放电容量所必需的量即可。
B/A为上述范围内的情况下,能够维持浮动特性。B/A为0.7以上的情况下,电解液所含的阴离子的量变多,充电时在正极中掺杂阴离子的导电性高分子的比例变大。与此相伴,长时间的浮动充电时劣化的导电性高分子的比例变大,因此浮动特性降低。
B/A优选为0.2以上。在此情况下,在充电时导电性高分子能够从电解液掺杂适当量的阴离子,能够得到良好的放电容量。另外,电解液中所含的阴离子的量变多,能够得到良好的离子传导性,因此能够得到良好的放电容量。
构成正极所含的导电性高分子的单体单元的总量A(mol)、与在电化学装置的充电状态下掺杂于正极所含的导电性高分子的阴离子的量C(mol)优选满足下述关系式:
0<C/A<0.7。
在此情况下,能够减小充电时在正极中掺杂阴离子的导电性高分子的比例,从而充分降低长时间的浮动充电时劣化的导电性高分子的比例,能够进一步维持浮动特性。在电化学装置的充电状态下,电解液中的阴离子的大部分被掺杂于正极的导电性高分子,电解液几乎不含阴离子的情况下,上述C的值与上述B的值几乎相同。
被掺杂于正极所含的导电性高分子的阴离子的量C(mol)可以表示为由在电化学装置的放电状态下电解液所含的阴离子的量D(mol)减去在电化学装置的充电状态下电解液所含的阴离子的量E(mol)而得的值。
此处,上述的充电状态是指电化学装置的SOC为90%~100%的情况。上述的放电状态是指电化学装置的SOC为0%~10%的情况。SOC(state of charge,荷电状态)是指充电量相对于满充电时的容量的比例。
SOC为0%~10%的放电状态是电化学装置的电压成为放电终止电压的状态,SOC为90%~100%的充电状态是电化学装置的电压成为充电终止电压的状态。放电终止电压和充电终止电压、还包括充放电条件在内是由制造商确定的。通常根据制造商提供的充放电电路、产品信息,能够唯一地确定。
作为导电性高分子使用π共轭系高分子,作为负极活性物质使用碳材料的情况下,充电终止电压例如被设定为3.4~4.2V,放电终止电压通常被设定为2.5~2.6V。作为导电性高分子使用π共轭系高分子,作为负极活性物质使用钛酸锂的情况下,充电终止电压通常被设定为2.4~2.5V,放电终止电压通常被设定为1.1~1.2V。
为了提高放电特性,导电性高分子优选构成该导电性高分子的每一个单体单元具有至少1个阴离子的接收位点。此处,阴离子的接收位点表示在充电时导电性高分子从该导电性高分子的分子结构的观点出发理论上能够接收(掺杂)阴离子的位点。例如,将苯胺作为重复单体单元的聚苯胺在理论上,每1个苯胺的单体单元具有1个阴离子的接收位点。
导电性高分子优选为具有包含杂原子的重复单元的π共轭系高分子。π共轭系高分子的杂原子(氮原子、硫原子等)容易与阴离子发生相互作用。可以认为在伴随充放电的导电性高分子的氧化还原之时,阴离子对杂原子进行吸附或脱离。
作为π电子共轭系高分子,例如可以使用选自苯胺、吡咯、噻吩、呋喃、噻吩乙烯、吡啶和它们的衍生物中的至少1种的聚合性化合物的均聚物和/或共聚物。即,作为π电子共轭系高分子,可以使用包含来源于上述聚合性化合物的单体单元的均聚物、包含2种以上的来源于上述聚合性化合物的单体单元的共聚物。更具体来说,可以得到聚苯胺、聚吡咯、聚噻吩、聚呋喃、聚噻吩乙烯、聚吡啶、以它们为基本骨架的高分子衍生物等。高分子衍生物是指例如苯胺衍生物、吡咯衍生物、噻吩衍生物、呋喃衍生物、噻吩乙烯衍生物、吡啶衍生物等这样的衍生物化合物的聚合物,例如可以举出以聚噻吩作为基本骨架的聚(3,4-乙烯二氧噻吩)(PEDOT)。这些之中,从能够得到稳定的电化学特性(充放电特性)出发,π电子共轭系高分子优选为聚苯胺、聚吡咯、聚噻吩和以它们为基本骨架的高分子衍生物。此外,从容量密度高的方面出发,π电子共轭系高分子更优选为聚苯胺。
导电性高分子的重均分子量没有特别限定,例如为1000~100000。
作为伴随充放电而导电性高分子能够掺杂和脱掺杂的阴离子,例如可以举出ClO4 -、BF4 -、PF6 -、AlCl4 -、SbF6 -、SCN-、CF3SO3 -、FSO3 -、CF3CO2 -、AsF6 -、B10Cl10 -、Cl-、Br-、I-、BCl4 -、N(FSO2)2 -、N(CF3SO2)2 -等。其中优选含卤原子的含氧酸阴离子、亚氨阴离子等。作为含卤原子的含氧酸阴离子,优选四氟硼酸阴离子(BF4 -)、六氟磷酸阴离子(PF6 -)、高氯酸阴离子(ClO4 -)、氟代硫酸阴离子(FSO3 -)等。这些之中,从导电性高分子容易可逆性地进行掺杂和脱掺杂出发,更优选PF6 -,可以是充电状态和放电状态下电解液所含的阴离子全部的90摩尔%以上为PF6 -。另外,作为亚氨阴离子,优选双(氟磺酰基)亚氨阴离子(N(FSO2)2 -)。这些可以单独使用,也可以组合2种以上使用。
优选以在充电状态(SOC90%~100%)下电解液几乎不含阴离子(例如,充电状态的电解液中的阴离子浓度小于0.5mol/L)的方式,减少电解液中的阴离子量而进行调整。在此情况下,可以减小在充电时在正极中掺杂阴离子的导电性高分子的比例。因此,即使在长时间的浮动充电时,也容易降低劣化的导电性高分子的比例,能够更加良好地维持浮动特性。
另外,若以电解液的阴离子浓度高的状态进行浮动充电,则有导电性高分子容易劣化的倾向。从这一点出发,也优选以充电状态时的电解液的阴离子浓度小于0.5mol/L的方式调整电解液中的阴离子量。其中,优选以充电状态时的电解液的阴离子浓度成为0.1mol/L以上的方式调整电解液中的阴离子量。由此,能够抑制电化学装置的放电容量的降低。
另一方面,优选在放电状态(SOC0%~10%)下以电解液中的阴离子的浓度成为1.0~2.5mol/L左右的方式调整电解液中的阴离子量。在此情况下,可以使充电时被掺杂于导电性高分子的阴离子在放电时效率良好地从导电性高分子脱掺杂。
以下,对于电化学装置的每个构成要素,进一步进行详细说明。
(正极)
正极例如具有包含上述的导电性高分子作为正极活性物质的正极材料层。正极材料层通常担载于正极集电体。正极集电体例如使用导电性的片材材料。作为片材材料,使用金属箔、金属多孔体、冲压金属等。作为正极集电体的材质,可以使用铝、铝合金、镍、钛等。
正极材料层除了正极活性物质以外,可以还含有导电剂和粘结剂。作为导电剂,可以举出炭黑、碳纤维等。作为粘结剂,可以举出氟树脂、丙烯酸类树脂、橡胶材料、纤维素衍生物等。
正极材料层所含的导电性高分子是通过将作为导电性高分子的原料的聚合性化合物(单体)进行聚合而合成的。导电性高分子的合成可以利用电解聚合来进行,也可以利用化学聚合来进行。例如可以准备导电性的片材材料(例如金属箔)作为正极集电体,在单体溶液中浸渍正极集电体和对向电极,将正极集电体作为阳极,在正极集电体与对向电极之间流过电流,由此,以覆盖正极集电体的表面的至少一部分的方式形成导电性高分子的膜(正极材料层)。单体溶液中,作为掺杂剂,可以包含上述例示的阴离子,也可以包含硫酸离子、硝酸离子等除上述例示的阴离子以外的阴离子。另外,可以添加促进电解聚合的氧化剂。
(负极)
负极例如具有包含负极活性物质的负极材料层。负极材料层通常担载于负极集电体。负极集电体例如使用导电性的片材材料。作为片材材料,使用金属箔、金属多孔体、冲压金属等。作为负极集电体的材质,可以使用铜、铜合金、镍、不锈钢等。
作为负极活性物质,可以举出碳材料、金属化合物、合金、陶瓷材料等。作为碳材料,优选石墨、难石墨化碳(硬碳)、易石墨化碳(软碳),特别优选石墨、硬碳。作为金属化合物,可以举出硅氧化物、锡氧化物等。作为合金,可以举出硅合金、锡合金等。作为陶瓷材料,可以举出钛酸锂、锰酸锂等。这些可以单独使用,也可以组合2种以上使用。其中,从能够降低负极的电位的方面出发,优选碳材料。
负极材料层中除了负极活性物质以外,优选包含导电剂、粘结剂等。导电剂和粘结剂可以使用正极材料层中例示的材料。
优选负极中事先预掺杂锂离子。由此,负极的电位降低,因此正极与负极的电位差(即电压)变大,电化学装置的能量密度提高。
向负极预掺杂锂离子例如按照以下进行:将作为锂离子供给源的金属锂层形成于负极材料层的表面,锂离子由金属锂层溶出至电解液中,溶出的锂离子吸储于负极活性物质。例如使用石墨、硬碳作为负极活性物质的情况下,锂离子插入至石墨的层间、硬碳的细孔。被预掺杂的锂离子的量可以通过金属锂层的质量控制。
负极具备的负极材料层例如通过如下形成:制备将负极活性物质、导电剂、粘结剂等与分散介质一起进行混合而得的负极合剂糊料,将负极合剂糊料涂布于负极集电体。
向负极预掺杂锂离子的工序可以在组装电极组之前进行,也可以将电极组与电解液一起容纳于电化学装置的壳体之后进行预掺杂。
(电解液)
电解液(非水电解液)包含溶剂(非水溶剂)和溶解于溶剂的锂盐。锂盐包含充电时被掺杂于导电性高分子的阴离子和吸储于负极活性物质的锂离子。
作为锂盐,例如可以举出LiClO4、LiBF4、LiPF6、LiAlCl4、LiSbF6、LiSCN、LiCF3SO3、LiFSO3、LiCF3CO2、LiAsF6、LiB10Cl10、LiCl、LiBr、LiI、LiBCl4、LiN(FSO2)2、LiN(CF3SO2)2等。这些可以单独使用1种,也可以组合2种以上使用。其中,优选使用选自具有含卤原子的含氧酸阴离子的锂盐和具有亚氨阴离子的锂盐中的至少1种。
充电状态(SOC90%~100%)下的电解液中的锂盐的浓度例如小于0.5mol/L。
作为溶剂,可以使用碳酸亚乙酯、碳酸亚丙酯(PC)、碳酸亚丁酯等环状碳酸酯、碳酸二甲酯(DMC)、碳酸二乙酯、碳酸甲乙酯等链状碳酸酯、甲酸甲酯、乙酸甲酯、丙酸甲酯、丙酸乙酯等脂肪族羧酸酯、γ-丁内酯、γ-戊内酯等内酯类、1,2-二甲氧基乙烷(DME)、1,2-二乙氧基乙烷(DEE)、乙氧基甲氧基乙烷(EME)等链状醚、四氢呋喃、2-甲基四氢呋喃等环状醚、二甲基亚砜、1,3-二氧戊环、甲酰胺、乙酰胺、二甲基甲酰胺、二氧戊环、乙腈、丙腈、硝基甲烷、乙二醇二乙醚、三甲氧基甲烷、环丁砜、甲基环丁砜、1,3-丙磺酸内酯等。这些可以单独使用,也可以组合2种以上使用。其中,从离子传导性的观点出发,优选包含DMC和PC的混合溶剂,优选DMC和PC占溶剂的50质量%以上,进而优选占80质量%以上。此时,DMC与PC的体积比(DMC/PC)例如为30/70~70/30即可。
根据需要,电解液中可以使溶剂中包含添加剂。例如,作为在负极表面形成锂离子传导性高的覆膜的添加剂,可以添加碳酸亚乙烯酯、碳酸乙烯基亚乙酯、碳酸二乙烯基亚乙酯等不饱和碳酸酯。
(间隔件)
优选在正极与负极之间隔着间隔件。作为间隔件,例如使用纤维素纤维制的无纺布、玻璃纤维制的无纺布、聚烯烃制的微多孔膜、织造布、无纺布等。间隔件的厚度例如为10~300μm、优选为10~40μm。
一边参照图1和图2一边对本发明的实施方式涉及的电化学装置进行说明。
电极组10为如图2所示的卷绕体,具备正极21、负极22、和介于它们之间的间隔件23。卷绕体的最外周通过卷绕固定带24固定。正极21与引线接头15A连接,负极22与引线接头15B连接。电化学装置具备电极组10、容纳电极组10的有底壳体11、将有底壳体11的开口密封的封口体12、从封口体12导出的引线14A、14B和电解液(未图示)。引线14A、14B分别与引线接头15A、15B连接。封口体12例如由包含橡胶成分的弹性材料形成。对于有底壳体11的开口端附近,向内侧拉深加工,开口端以与封口体12铆接的方式进行卷曲加工。
上述的实施方式中示出了具备卷绕型的电极组的圆筒形状的电化学装置,也可以构成具备使正极和负极在两极间隔着间隔件而层叠的电极组的方形形状的电化学装置。
[实施例]
以下,基于实施例,进一步详细地说明本发明,但本发明并非限定于实施例。
(1)正极的制作
准备厚度为30μm的铝箔作为正极集电体。另一方面,准备包含苯胺和硫酸的苯胺水溶液。
将正极集电体和对向电极浸渍于苯胺水溶液,以10mA/cm2的电流密度进行20分钟电解聚合,使掺杂有作为导电性高分子的掺杂剂的硫酸离子(SO4 2-)的导电性高分子(聚苯胺)的膜附着于正极集电体的正面和背面的整个面。
将掺杂有硫酸离子的导电性高分子进行还原,将所掺杂的硫酸离子进行脱掺杂。这样一来,形成硫酸离子被脱掺杂的多孔的导电性高分子膜(正极材料层)。导电性高分子膜的厚度在正极集电体的每单面为60μm。充分清洗导电性高分子膜,随后进行了干燥。需要说明的是,通过调整作为导电性高分子的掺杂剂的硫酸离子的脱掺杂量,可以调整伴随充放电而在导电性高分子中掺杂和脱掺杂的阴离子的量、或调整在充放电过程中在电解液中含有的阴离子的量。
(2)负极的制作
准备厚度为20μm的铜箔作为负极集电体。另一方面,制备将硬碳97质量份、羧基纤维素1质量份、苯乙烯丁二烯橡胶2质量份混合而成的混合粉末与水按照重量比为40:60的比例进行混炼而得的碳糊料。将碳糊料涂布于负极集电体的两面并干燥,得到在两面具有厚度为35μm的负极材料层的负极。接下来,在负极材料层形成以预掺杂结束后的电解液中的负极电位相对于金属锂为0.2V以下的方式计算的量的金属锂层。
(3)电极组的制作
在正极和负极分别连接引线接头之后,如图2所示,将纤维素制无纺布的间隔件(厚度35μm)与正极、负极分别交替重合而得的层叠体进行卷绕,形成电极组。
(4)电解液的制备
在碳酸亚丙酯与碳酸二甲酯的体积比1∶1的混合物中添加0.2质量%的碳酸亚乙烯酯,从而制备溶剂。在所得到的溶剂中使LiPF6作为锂盐以规定浓度溶解,制备具有六氟磷酸离子(PF6 -)作为阴离子的电解液。
(5)电化学装置的制作
在具有开口的有底壳体中容纳电极组和电解液,组装图1所示的电化学装置。随后,一边在正极和负极的端子间施加3.8V的充电电压,一边在25℃进行24小时陈化,使锂离子向负极进行预掺杂。
在上述电化学装置的制作中,使壳体内容纳的电解液的量恒定,改变壳体内容纳的电解液的锂盐的浓度,制作B/A为表1所示的值的No.1~12的试验电池单元。需要说明的是,表1中的No.1~6为实施例,No.7~12为比较例。
[表1]
[评价]
(1)容量维持率的测定(浮动特性的评价)
对于上述所得到的电化学装置,按照下述条件依次充电、休止、放电而进行充放电试验,测定初始的放电容量A(每1g正极活性物质的容量)。
环境温度25℃
充电:以恒电流1C充电至到达充电终止电压3.8V
休止:5分钟
放电:以恒电流1C放电至到达放电终止电压2.5V
1C充电表示:将相当于电化学装置的额定容量C(单位:mAh)的电量以1小时进行恒电流充电。1C放电表示:将相当于电化学装置的额定容量C的电量以1小时进行恒电流放电。
另行准备上述所得到的电化学装置,以与上述充电条件相同的条件充电后,进而以3.8V的恒电压充电1000小时(浮动充电)。随后,以与上述放电条件相同的条件进行放电,测定放电容量B。
使用上述所得到的放电容量A和B,通过下述式求出容量维持率,评价浮动特性。
容量维持率(%)=(放电容量B/放电容量A)×100
(2)A和B的测定
(i)构成正极所含的导电性高分子的单体单元的总量A(mol)
分解电化学装置并取出正极,从正极集电体剥离正极材料层后,使用ICP发光光谱分析法,求出正极材料层中所含的聚苯胺中的氮原子的总摩尔量。基于每1个单体单元(苯胺骨架)包含1个氮原子,求出构成正极材料层中的导电性高分子的单体单元的总量A(mol)。聚苯胺理论上在每1个单体单元(苯胺骨架)具有1个阴离子的接收位点。
(ii)电化学装置所含的阴离子的总量B(mol)
电化学装置所含的阴离子(PF6 -)的总量B(mol)通过将正极所含的阴离子量(mol)和电解液所含的阴离子量(mol)加和而求出。
正极所含的阴离子(PF6 -)量通过以下方法求出:将电化学装置分解并取出正极,从正极集电体剥离正极材料层,随后,使正极材料层加热溶解于混酸(盐酸、硝酸和水的混合物),放冷后,过滤不溶成分并定容,用ICP发光光谱分析法测定P浓度。
电解液所含的阴离子(PF6 -)量使用容纳于电化学装置中的电解液的量和电解液的阴离子(PF6 -)浓度求出。
容纳于电化学装置的电解液的量通过以下方法求出:分解电化学装置,取出包含电解液的电极组,测定干燥前的电极组的重量W1,随后,将电极组解体,将正极、负极、间隔件分别进行水洗后干燥,测定干燥后的正极、负极、间隔件的总重量W2,并且,将W1减去W2的值作为电解液量。
容纳于电化学装置的电解液的阴离子浓度通过以下方法求出:将电化学装置分解并采集间隔件中包含的电解液,用ICP发光光谱分析法测定P浓度。
如表1和图3所示,B/A小于0.7的实施例的试验电池单元(No.1~6)中,容量维持率高,浮动充电后的容量降低被抑制。B/A为0.7以上的比较例的试验电池单元(No.7~12)中,容量维持率降低。
产业上的可利用性
本发明涉及的电化学装置可以适宜地应用于要求比双电层电容器、锂离子电容器更高容量、且比锂离子二次电池更高输出的用途。
附图标记说明
10:电极组、11:有底壳体、12:封口体、14A、14B:引线、15A、15B:引线接头、21:正极、22:负极、23:间隔件、24:卷绕固定带。
Claims (4)
1.一种电化学装置,其具备:
正极,包含能够掺杂和脱掺杂阴离子的导电性高分子作为正极活性物质;
负极,包含能够吸储和放出锂离子的负极活性物质;和
电解液,包含所述阴离子和所述锂离子,
其中,构成所述正极所含的所述导电性高分子的单体单元的总量A、与所述电化学装置所含的所述阴离子的总量B满足下述关系式:
0<B/A<0.7,
所述A与B的单位均为mol。
2.如权利要求1所述的电化学装置,其中,
所述导电性高分子包含选自聚苯胺、聚吡咯、聚噻吩和以它们为基本骨架的高分子衍生物中的至少1种。
3.如权利要求1或2所述的电化学装置,其中,
所述阴离子包含选自BF4 -、PF6 -、ClO4 -、FSO3 -和N(FSO2)2 -中的至少1种。
4.如权利要求1~3中任一项所述的电化学装置,其中,
所述电解液包含碳酸二甲酯和碳酸亚丙酯作为溶剂。
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