JP4467926B2 - Electrochemical element - Google Patents
Electrochemical element Download PDFInfo
- Publication number
- JP4467926B2 JP4467926B2 JP2003290160A JP2003290160A JP4467926B2 JP 4467926 B2 JP4467926 B2 JP 4467926B2 JP 2003290160 A JP2003290160 A JP 2003290160A JP 2003290160 A JP2003290160 A JP 2003290160A JP 4467926 B2 JP4467926 B2 JP 4467926B2
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- Japan
- Prior art keywords
- compound
- bond
- group
- active material
- atom
- 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
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- 150000001875 compounds Chemical class 0.000 claims description 157
- 239000000126 substance Substances 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 239000011149 active material Substances 0.000 claims description 36
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000004434 sulfur atom Chemical group 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 238000006479 redox reaction Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- -1 lithium halide salts Chemical class 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910018557 Si O Inorganic materials 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920001197 polyacetylene Polymers 0.000 claims description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910003077 Ti−O Inorganic materials 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011245 gel electrolyte Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical group 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000000758 substrate Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 12
- 239000010931 gold Substances 0.000 description 12
- 238000011282 treatment Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 150000002898 organic sulfur compounds Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical group S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910011939 Li2.6 Co0.4 N Inorganic materials 0.000 description 2
- 229910012465 LiTi Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- 150000001787 chalcogens Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HGOTVGUTJPNVDR-UHFFFAOYSA-N 2-(4,5-dimethyl-1,3-dithiol-2-ylidene)-4,5-dimethyl-1,3-dithiole Chemical compound S1C(C)=C(C)SC1=C1SC(C)=C(C)S1 HGOTVGUTJPNVDR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZVPVCVWMMDMYSP-UHFFFAOYSA-N C1OC(CC(S2)=C(C3)SC2=C2SC(CC4=C(C5)OCCO4)=C5S2)=C3OC1 Chemical compound C1OC(CC(S2)=C(C3)SC2=C2SC(CC4=C(C5)OCCO4)=C5S2)=C3OC1 ZVPVCVWMMDMYSP-UHFFFAOYSA-N 0.000 description 1
- LZJCVNLYDXCIBG-UHFFFAOYSA-N C1SC(SC(S2)=C(S3)SC4=C3SCCS4)=C2SC1 Chemical compound C1SC(SC(S2)=C(S3)SC4=C3SCCS4)=C2SC1 LZJCVNLYDXCIBG-UHFFFAOYSA-N 0.000 description 1
- QQIBQMVSZILKLA-UHFFFAOYSA-N C1SC(SC(S2)=C3SC(OCCOC4)=C4S3)=C2SC1 Chemical compound C1SC(SC(S2)=C3SC(OCCOC4)=C4S3)=C2SC1 QQIBQMVSZILKLA-UHFFFAOYSA-N 0.000 description 1
- 0 CSC(S1)=C(S*)SC1=C1SC(CO)=C(CO)S1 Chemical compound CSC(S1)=C(S*)SC1=C1SC(CO)=C(CO)S1 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- OBBRJKAZINSLLI-UHFFFAOYSA-N IC(S1)=CSC1=C1SC(OC=CO2)=C2S1 Chemical compound IC(S1)=CSC1=C1SC(OC=CO2)=C2S1 OBBRJKAZINSLLI-UHFFFAOYSA-N 0.000 description 1
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 1
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GYXNAZRCWZPSMO-UHFFFAOYSA-N SCCCC(S1)=CSC1=C1SC=CS1 Chemical compound SCCCC(S1)=CSC1=C1SC=CS1 GYXNAZRCWZPSMO-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 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
Description
本発明は、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子に関する。 The present invention relates to an electrochemical device that is lightweight, has high energy density, and has excellent cycle characteristics.
近年、移動体通信機器、携帯電子機器の開発にともない、その電源の需要は非常に大きくなっている。電池、なかでも繰り返し充放電が可能なリチウム二次電池は、起電力が高く、高いエネルギー密度が得られ、繰り返し使用が可能なことから、携帯電子機器等の電源として広範囲に用いられている。 In recent years, with the development of mobile communication devices and portable electronic devices, the demand for their power sources has become very large. Batteries, particularly lithium secondary batteries that can be repeatedly charged and discharged, have a high electromotive force, a high energy density, and can be used repeatedly. Therefore, they are widely used as power sources for portable electronic devices and the like.
しかし、携帯電子機器の小型軽量化に伴い、電池の高エネルギー密度化に対する要望もますます高まってきており、さらに高いエネルギー密度を有する新規な電極材料の出現が望まれている。このような背景のもと、電池の高エネルギー密度化に直接的に結びつく電極材料の高エネルギー密度化を目指して、材料開発の取り組みが積極的に行われている。 However, with the reduction in size and weight of portable electronic devices, there is an increasing demand for higher energy density of batteries, and the emergence of new electrode materials having higher energy density is desired. Against this background, efforts for material development have been actively carried out with the aim of increasing the energy density of electrode materials that are directly linked to increasing the energy density of batteries.
近年、エネルギー密度が高く、より軽量な電池を作製するために、有機化合物を電極材料に用いる検討が行われている。有機化合物は、比重が１ｇ／ｃｍ３程度と軽く、現在リチウム二次電池の材料として用いられているコバルト酸リチウムなどの酸化物と比較して軽量である。このため、より軽量で高容量な電池を作製することが可能となる。 In recent years, studies have been made on using an organic compound as an electrode material in order to produce a lighter battery having a higher energy density. The organic compound has a specific gravity as low as about 1 g / cm 3 and is lighter than an oxide such as lithium cobaltate currently used as a material for lithium secondary batteries. For this reason, it becomes possible to produce a lighter and higher capacity battery.
例えば、ジスルフィド結合を持つ有機化合物を電極材料に用いた二次電池が提案されている（特許文献１、２参照）。この有機硫黄化合物は、最も簡単には、Ｍ+−-Ｓ−Ｒ−Ｓ-−Ｍ+と表される。ここで、Ｒは脂肪族あるいは芳香族の有機基、Ｓは硫黄、Ｍ＋はプロトンあるいは金属カチオンを示す。この化合物は、電気化学的酸化反応によりＳ−Ｓ結合を介して互いに結合し、
Ｍ+−-Ｓ−Ｒ−Ｓ−Ｓ−Ｒ−Ｓ−Ｓ−Ｒ−Ｓ-−Ｍ+
のような形で高分子化する。こうして生成した高分子は、電気化学的還元反応により、元のモノマーに戻る。二次電池では、この反応を充放電反応に用いる。
For example, a secondary battery using an organic compound having a disulfide bond as an electrode material has been proposed (see Patent Documents 1 and 2). This organic sulfur compound is most simply represented as M + − −S−R−S − −M + . Here, R represents an aliphatic or aromatic organic group, S represents sulfur, and M + represents a proton or a metal cation. This compound binds to each other via an SS bond by an electrochemical oxidation reaction,
M + − − S−R−S−S−R−S−S−R−S − −M +
It becomes a polymer in the form of The polymer thus produced returns to the original monomer by an electrochemical reduction reaction. In the secondary battery, this reaction is used for the charge / discharge reaction.
また、単体硫黄を電極材料に用いることも提案されている（特許文献３参照）。しかし、どちらの場合も高容量化は可能であるが、サイクル特性が低いという問題がある。これは、硫黄系材料の酸化還元反応におけるジスルフィド結合の解列・再結合では、再結合する頻度が低くなるためである。また、一度解列すると再結合する頻度が低いということは、たとえ理論的に高いエネルギー密度を有していたとしても、すべての反応可能な部位が反応できないことを意味する。これでは、実際には高エネルギー密度を有する材料とは言えない。
以上のように、硫黄系材料を電極材料に用いた軽量で高エネルギー密度な電気化学素子においては、酸化還元反応に伴い、硫黄系材料の構造変化が起こるため、サイクル特性が低いという問題がある。本発明は、この点を鑑みたものであり、軽量で高エネルギー密度な電気化学素子のサイクル特性の改善を目的とする。 As described above, in a lightweight and high energy density electrochemical element using a sulfur-based material as an electrode material, there is a problem that the cycle characteristics are low because the structural change of the sulfur-based material occurs due to the oxidation-reduction reaction. . The present invention has been made in view of this point, and an object of the present invention is to improve the cycle characteristics of a lightweight, high energy density electrochemical device.
本発明は、導電性を有する炭素材料と、活物質とを含む正極と、負極と、リチウムの、ハロゲン化物の塩、過塩素酸塩および含フッ素化合物の塩よりなる群から選択された少なくとも一のリチウム塩が含まれる電解質とを含み、酸化還元反応に伴う電子移動を電気エネルギーとして取り出し、充放電可能な電気化学素子であって、前記活物質が、以下の一般式（１）： The present invention provides at least one selected from the group consisting of a conductive carbon material, a positive electrode including an active material , a negative electrode, and a lithium halide salt, perchlorate salt, and fluorine-containing compound salt. And an electrolyte containing the lithium salt of the above, wherein the active material has the following general formula (1):
（式中、Ｒ1およびＲ2は、それぞれ独立に鎖状または環状の脂肪族基であり、Ｒ1とＲ2は同じであっても異なっていてもよく、Ｘ1〜Ｘ4は、それぞれ硫黄原子であり、前記脂肪族基は、酸素原子、窒素原子、硫黄原子およびケイ素原子よりなる群から選ばれる１種以上を含むことができる。）で表される構造を有する化合物を含み、前記化合物が、以下の一般式（２）： (In the formula, R 1 and R 2 are each independently a chain or cyclic aliphatic group, R 1 and R 2 may be the same or different, and X 1 to X 4 are respectively a sulfur atom, wherein the aliphatic group is seen containing an oxygen atom, a nitrogen atom, may include one or more selected from the group consisting of sulfur atom and a silicon atom.) the compound having the structure represented by, The compound is represented by the following general formula (2):
（式中、Ｒ 3 〜Ｒ 6 は、それぞれ独立に鎖状または環状の脂肪族基、水素原子またはヒドロキシル基であり、Ｒ3〜Ｒ6は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、硫黄原子およびケイ素原子よりなる群から選ばれる１種以上を含むことができる。）で表される電気化学素子に関する。
一般式（１）において、前記脂肪族基としては、特に制限はないが、炭素数１〜６の脂肪族基が好ましい。特に、一般式（１）の構造が、２つの環状π電子系グループを二重結合で繋いだ構造となるように、脂肪族基を選択することが好ましい。
Wherein R 3 to R 6 are each independently a chain or cyclic aliphatic group, a hydrogen atom or a hydroxyl group, and R 3 to R 6 may be the same or different, radicals are oxygen atom, nitrogen atom, an electrochemical device represented by can.) include one or more selected from a group consisting of sulfur atom and a silicon atom.
In the general formula (1), the aliphatic group is not particularly limited, but an aliphatic group having 1 to 6 carbon atoms is preferable. In particular, the aliphatic group is preferably selected so that the structure of the general formula (1) has a structure in which two cyclic π-electron groups are connected by a double bond.
一般式（１）で表される構造を有する化合物には、また、一般式（３）： In the compound having the structure represented by the general formula (1), the general formula ( 3 ):
（式中、ＸおよびＹは、それぞれ独立に硫黄原子、酸素原子またはメチレン基であり、ＸとＹは同じであっても異なっていてもよい。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、一般式（４）：
( Wherein, X and Y are each independently a sulfur atom, an oxygen atom or a methylene group, and X and Y may be the same or different).
In the compound having the structure represented by the general formula (1), the general formula (4):
（式中、Ｒ 9 およびＲ 10 は、それぞれ独立に鎖状または環状の脂肪族基、水素原子またはヒドロキシル基であり、Ｒ9とＲ10は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、イオウ原子およびケイ素原子よりなる群から選ばれる１種以上を含むことができ、ｎは３である。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、一般式（５）：
Wherein R 9 and R 10 are each independently a chain or cyclic aliphatic group, a hydrogen atom or a hydroxyl group, and R 9 and R 10 may be the same or different, The group group can include one or more selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, and n is 3.
In the compound having the structure represented by the general formula (1), the general formula (5):
で表される化合物を用いることができる。
一般式（２）および（４）において、前記脂肪族基としては、例えば、アルキル基、アルコキシ基、ヒドロキシアルキル基、チオアルキル基、アルデヒド基、カルボン酸基などが挙げられる。
前記化合物が、前記一般式（２）で表される構造が重合してなる高分子化合物である。
また、前記化合物が、前記一般式（２）で表される構造と、主鎖としてポリアセチレン鎖とが結合してなる高分子化合物である。 The compound represented by these can be used.
In the general formulas (2) and (4), examples of the aliphatic group include an alkyl group, an alkoxy group, a hydroxyalkyl group, a thioalkyl group, an aldehyde group, and a carboxylic acid group.
The compound is a polymer compound obtained by polymerizing the structure represented by the general formula (2).
Further, the compound is a polymer compound in which the structure represented by the general formula (2) and a polyacetylene chain as a main chain are bonded.
前記高分子化合物は膜を形成していることが好ましい。膜の厚さは１０〜３００μｍであることが好ましい。このような膜は、化学合成や一般式（２）の構造を有する低分子化合物の電解重合などによって得ることができる。 The polymer compound preferably forms a film. The thickness of the film is preferably 10 to 300 μm. Such a film can be obtained by chemical synthesis or electrolytic polymerization of a low molecular compound having the structure of the general formula (2) .
本発明の電気化学素子において、前記電解質は、溶媒および前記溶媒に拡散するアニオンとカチオンからなり、前記化合物は、酸化還元反応に伴い、前記カチオンおよび／またはアニオンと配位結合を形成する能力を有することが好ましい。前記カチオンは、リチウムイオンであることが好ましい。 In the electrochemical device of the present invention, the electrolyte is composed of a solvent and an anion and a cation diffusing into the solvent, and the compound has an ability to form a coordinate bond with the cation and / or the anion accompanying a redox reaction. It is preferable to have. The cation is preferably a lithium ion.
前記負極が、炭素材料を負極活物質として含むことが好ましい。また、前記負極が、リチウム金属、リチウム含有複合窒化物およびリチウム含有複合チタン酸化物、Ｓｎと炭素の複合物、Ｓｎと他の金属との複合物よりなる群から選ばれる少なくとも１種を負極活物質として含むことが好ましい。 The negative electrode preferably contains a carbon material as a negative electrode active material. Further, the negative electrode has at least one selected from the group consisting of lithium metal, lithium-containing composite nitride and lithium-containing composite titanium oxide, a composite of Sn and carbon, and a composite of Sn and another metal. It is preferable to include as a substance.
本発明は、さらに、酸化還元反応に伴う電子移動を電気エネルギーとして取り出す電気化学素子であって、正極と、負極と、電解質とからなり、前記正極および前記負極より選ばれる少なくとも一方が、一般式（２）〜（５）のいずれかで表される構造を有する化合物およびそれを担持する基材を含み、前記基材と一般式（２）〜（５）のいずれかで表される構造を有する化合物とが、化学結合により結合されている電気化学素子に関する。
前記正極が、さらに、前記化合物を担持する基材を含み、前記基材と前記化合物とが、化学結合により結合されている。 The present invention further relates to an electrochemical element that takes out electron transfer associated with an oxidation-reduction reaction as electric energy, comprising a positive electrode, a negative electrode, and an electrolyte, wherein at least one selected from the positive electrode and the negative electrode has a general formula A compound having a structure represented by any one of (2) to (5) and a base material supporting the compound, and a structure represented by any one of the base material and the general formulas (2) to (5) The present invention relates to an electrochemical element in which a compound having a chemical bond is bonded by a chemical bond.
The positive electrode further includes a base material supporting the compound, and the base material and the compound are bonded by a chemical bond.
前記化学結合は、共有結合および配位結合よりなる群から選択される少なくとも１種であることが好ましい。前記共有結合は、Ｓｉ−Ｏ結合、Ｔｉ−Ｏ結合およびアミド結合よりなる群から選択される少なくとも１種を含むことがこのましい。前記配位結合は、金属−硫黄結合であることが好ましい。前記基材には、金属、金属酸化物、粘土層間化合物、炭素化合物、珪素化合物、樹脂などを用いることができる。 The chemical bond is preferably at least one selected from the group consisting of a covalent bond and a coordinate bond. The covalent bond preferably includes at least one selected from the group consisting of a Si—O bond, a Ti—O bond, and an amide bond. The coordination bond is preferably a metal-sulfur bond. A metal, a metal oxide, a clay intercalation compound, a carbon compound, a silicon compound, a resin, or the like can be used for the substrate.
前記正極が、さらに、前記化合物を担持する基材を含み、前記基材と前記化合物とが、化学結合により結合されている。 The positive electrode further includes a base material supporting the compound, and the base material and the compound are bonded by a chemical bond.
本発明によれば、一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質に用いることから、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子を得ることができる。 According to the present invention, a compound having a structure represented by any one of the general formulas (2) to (5) is used as an electrode active material, so that an electrochemical element that is lightweight, has a high energy density, and is excellent in cycle characteristics. Obtainable.
本発明の電気化学素子は、酸化還元反応に伴う電子移動を電気エネルギーとして取り出す電気化学素子であって、正極と、負極と、電解質とからなり、前記正極および前記負極より選ばれる少なくとも一方が、一般式（１）： The electrochemical element of the present invention is an electrochemical element that takes out electron transfer associated with a redox reaction as electric energy, and includes a positive electrode, a negative electrode, and an electrolyte, and at least one selected from the positive electrode and the negative electrode is General formula (1):
（式中、Ｒ1およびＲ2は、それぞれ鎖状または環状の脂肪族基であり、Ｒ1とＲ2は同じであっても異なっていてもよく、Ｘ1〜Ｘ4は、それぞれ硫黄原子であり、前記脂肪族基は、酸素原子、窒素原子、硫黄原子およびケイ素原子よりなる群から選ばれる１種以上を含むことができる。）で表される構造を有する化合物（以下、活物質化合物ともいう）からなることを特徴とする。活物質化合物は、電池内において酸化還元反応を行い、電子の授受を行う。
(In the formula, R 1 and R 2 are each linear or cyclic aliphatic group, R 1 and R 2 may be different even in the same, X 1 to X 4 are, their respective a vulcanization Kihara child, before Symbol aliphatic group having an oxygen atom, a nitrogen atom, may include one or more selected from sulfur atom and a silicon atom by Li Cheng group. structure represented by) It is characterized by comprising a compound (hereinafter also referred to as an active material compound). The active material compound performs an oxidation-reduction reaction in the battery, and exchanges electrons.
活物質化合物は、その構造を大きく変化させることなく酸化還元反応を行うことができる。その機構は以下のとおりである。
活物質化合物は、構造対称性を有し、平面構造を有する。また、活物質化合物は、分子の中心に炭素−炭素二重結合を有し、かつ、硫黄、酸素などのカルコゲン元素を含む環状構造を有する。カルコゲン元素は孤立電子対を有する。そのため、分子上にπ電子共役電子雲が形成される。この分子上に広がったπ電子共役電子雲は、電子の授受が可能である。電子の授受は、活物質化合物の酸化・還元反応として進行する。
The active material compound can perform a redox reaction without greatly changing its structure. The mechanism is as follows.
The active material compound has structural symmetry and a planar structure. The active material compound has a carbon-carbon double bond at the center of the molecule and a cyclic structure containing a chalcogen element such as sulfur or oxygen. The chalcogen element has a lone pair of electrons. Therefore, a π electron conjugated electron cloud is formed on the molecule. The π-electron conjugated electron cloud spreading on the molecule can exchange electrons. Transfer of electrons proceeds as an oxidation / reduction reaction of the active material compound.
例えば、還元反応（放電反応）時には、活物質化合物が還元され、電解質中のカチオンが、還元された分子に配位する。その後の酸化反応（充電反応）時には、活物質化合物に配位していたカチオンが脱離する。この反応を電池反応として用いることができる。また、酸化反応（充電反応）時に活物質化合物が酸化される場合には、電解質のアニオンが、酸化された分子に配位する。その後の還元反応（放電反応）時には、活物質化合物に配位していたアニオンが脱離する。 For example, during the reduction reaction (discharge reaction), the active material compound is reduced, and the cation in the electrolyte is coordinated to the reduced molecule. During the subsequent oxidation reaction (charging reaction), the cations coordinated to the active material compound are eliminated. This reaction can be used as a battery reaction. When the active material compound is oxidized during the oxidation reaction (charging reaction), the anion of the electrolyte coordinates to the oxidized molecule. During the subsequent reduction reaction (discharge reaction), the anion coordinated with the active material compound is eliminated.
このような一連の酸化還元反応において、活物質化合物は、結合の解裂・再結合といった大きな構造変化を起こさないと考えられる。酸化還元反応に伴って前記化合物の分子が大きく構造変化すると、次の反応を行う際にも分子の構造変化が必要となり、このとき大きなエネルギーが必要となる。そのため反応性は低下する。従って、酸化還元反応に伴う大きな構造変化がないことは、反応を効率的に行い得ることを示している。 In such a series of oxidation-reduction reactions, it is considered that the active material compound does not cause a large structural change such as bond breakage / recombination. If the molecule of the compound undergoes a large structural change along with the oxidation-reduction reaction, the structural change of the molecule is required also during the next reaction, and at this time, a large amount of energy is required. Therefore, the reactivity decreases. Therefore, the absence of a large structural change associated with the redox reaction indicates that the reaction can be performed efficiently.
以上のように、本発明では、分子上に広がったπ電子共役部位を酸化還元反応部位とする化合物を電極活物質に用いている。上記反応機構では、酸化還元反応に伴って活物質の骨格の大きな構造変化は起こらない。従って、酸化還元反応の繰り返しによる活物質の構造的な劣化が抑制されるため、優れた充放電サイクル特性が得られる。 As described above, in the present invention, a compound having a π-electron conjugated site spread on a molecule as a redox reaction site is used as an electrode active material. In the above reaction mechanism, a large structural change of the skeleton of the active material does not occur with the redox reaction. Accordingly, structural deterioration of the active material due to repeated redox reactions is suppressed, so that excellent charge / discharge cycle characteristics can be obtained.
さらに、上記反応機構では、通常の有機硫黄系化合物が起こすような結合・解裂反応と比べて、速い反応速度を期待できる。反応速度が速くなると、電池特性としては優れたレート特性を期待できることから、急速充放電にも有利である。 Furthermore, in the above reaction mechanism, a higher reaction rate can be expected as compared with a bonding / cleavage reaction caused by a normal organic sulfur compound. When the reaction rate is increased, excellent rate characteristics can be expected as battery characteristics, which is advantageous for rapid charge / discharge.
本発明においては、一般式（２）〜（５）のいずれかで表される構造を有する化合物のなかでも、特にテトラチアフルバレン構造を有する化合物を好ましく用いることができる。また、一般式（２）〜（５）のいずれかで表される構造を有する限り、低分子化合物から高分子化合物まで用いることができる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, among compounds having a structure represented by any one of the general formulas (2) to (5), a compound having a tetrathiafulvalene structure can be preferably used. Moreover, as long as it has the structure represented by either of General formula (2)-(5), it can use from a low molecular compound to a high molecular compound. These may be used alone or in combination of two or more.
本発明において、高分子化合物とは、低分子化合物が重合してなる分子量１００００以上の化合物を言う。高分子化合物は、低分子化合物に比べて電解液などに溶解しにくい性質を有する。従って、高分子化合物を電極活物質として用いた場合には、電解液への活物質の溶出が抑えられ、サイクル特性の安定性が、さらに高められる。 In the present invention, the high molecular compound refers to a compound having a molecular weight of 10,000 or more obtained by polymerizing a low molecular compound. The high molecular compound has a property that it is difficult to dissolve in an electrolytic solution or the like as compared with the low molecular compound. Therefore, when a polymer compound is used as the electrode active material, elution of the active material into the electrolytic solution is suppressed, and the stability of the cycle characteristics is further enhanced.
高分子化合物としては、ポリアセチレン鎖を主鎖として有する化合物が好ましい。また、一分子内に一般式（２）〜（５）のいずれかで表される構造を２個以上含むことが好ましい。ポリアセチレン鎖の分子量は１００００〜２０００００であることが好ましい。
活物質化合物の好ましい具体例としては、例えば、化学式（６）：
As the polymer compound, a compound having a polyacetylene chain as a main chain is preferable. Moreover, it is preferable that two or more structures represented by any one of the general formulas (2) to (5) are included in one molecule. The molecular weight of the polyacetylene chain is preferably 10,000 to 200,000.
Preferable specific examples of the active material compound include, for example, chemical formula (6):
で表される化合物、化学式（７）： A compound represented by the formula (7):
で表される化合物、化学式（８）： A compound represented by the formula (8):
で表される化合物、化学式（９）： A compound represented by the formula (9):
で表される化合物、化学式（１０）： A compound represented by formula ( 10 ):
で表される化合物、化学式（１１）： A compound represented by the formula ( 11 ):
で表される化合物、化学式（１２）： A compound represented by formula ( 12 ):
で表される化合物、化学式（１３）： A compound represented by the formula ( 13 ):
で表される化合物、化学式（１４）： A compound represented by formula ( 14 ):
で表される化合物等を挙げることができる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。
活物質化合物は、電気化学素子のなかでも、特に二次電池の電極活物質として用いるのに適しているが、電解コンデンサの電極にも用いることができる。
The compound etc. which are represented by these can be mentioned. These may be used alone or in combination of two or more.
The active material compound is particularly suitable for use as an electrode active material for a secondary battery among electrochemical elements, but can also be used for an electrode of an electrolytic capacitor .
二次電池においては、一般式（２）〜（５）のいずれかで表される構造を有する化合物は、正極と負極の両方に用いてもよく、どちらか一方に用いてもよい。どちらか一方の電極に前記化合物を用いる場合には、他方の電極活物質には、二次電池の活物質として従来から用いられている材料を特に限定なく用いることができる。 In the secondary battery, the compound having a structure represented by any one of the general formulas (2) to (5) may be used for both the positive electrode and the negative electrode, or may be used for either one of them. When the compound is used for either one of the electrodes, a material conventionally used as an active material for the secondary battery can be used without particular limitation for the other electrode active material.
正極活物質として一般式（２）〜（５）のいずれかで表される構造を有する化合物を用いる場合には、負極活物質として、例えば、グラファイト、非晶質炭素などの炭素材料、リチウム金属、リチウム含有複合窒化物、リチウム含有チタン酸化物、Ｓｎと炭素との複合物、Ｓｎと他の金属との複合物等を用いることができる。また、負極活物質として一般式（２）〜（５）のいずれかで表される構造を有する化合物を用いる場合には、正極活物質として、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４などの金属酸化物等を用いることができる。 When the compound having a structure represented by any one of the general formulas (2) to (5) is used as the positive electrode active material, examples of the negative electrode active material include carbon materials such as graphite and amorphous carbon, and lithium metal. , Lithium-containing composite nitrides, lithium-containing titanium oxides, composites of Sn and carbon, composites of Sn and other metals, and the like can be used. In the case of using a compound having a structure represented by any one of formulas (2) to (5) as a negative electrode active material, as a cathode active material, such as LiCoO 2, LiNiO 2, LiMn 2 O 4 A metal oxide or the like can be used.
一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質に用いた場合、電極抵抗を低減する目的で、カーボンブラック、グラファイト、アセチレンブラック等の炭素材料、ポリアニリン、ポリピロール、ポリチオフェンなどの導電性高分子等を導電補助剤として電極活物質に混合させてもよい。また、イオン伝導補助剤として、ポリエチレンオキシドなどからなる固体電解質、ポリメタクリル酸メチルなどからなるゲル電解質を電極活物質に混合させてもよい。 When a compound having a structure represented by any one of the general formulas (2) to (5) is used as an electrode active material, carbon materials such as carbon black, graphite, and acetylene black, polyaniline are used for the purpose of reducing electrode resistance. In addition, a conductive polymer such as polypyrrole or polythiophene may be mixed with the electrode active material as a conductive auxiliary agent. Further, as an ion conduction auxiliary agent, a solid electrolyte made of polyethylene oxide or the like, or a gel electrolyte made of polymethyl methacrylate or the like may be mixed with the electrode active material.
電極内物質の構成材料の結着性を向上させるために、結着剤を用いてもよい。結着剤としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、ポリテトラフルオロエチレン、スチレン−ブタジエン共重合体、ポリプロピレン、ポリエチレン、ポリイミド等を用いることができる。 In order to improve the binding property of the constituent material of the substance in the electrode, a binder may be used. As the binder, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, styrene-butadiene copolymer, polypropylene, polyethylene, polyimide, etc. Can be used.
正極集電体または負極集電体には、ニッケル、アルミニウム、金、銀、銅、ステンレス鋼、アルミニウム合金等からなる金属箔、金属メッシュ等を用いることができる。集電体上にカーボンなどを塗布することにより、電極の抵抗値を減少させたり、集電体に触媒効果をもたせたり、集電体と活物質と化学的または物理的に結合させたりしてもよい。 For the positive electrode current collector or the negative electrode current collector, a metal foil, a metal mesh, or the like made of nickel, aluminum, gold, silver, copper, stainless steel, an aluminum alloy, or the like can be used. By applying carbon or the like on the current collector, the resistance value of the electrode is reduced, the current collector has a catalytic effect, or the current collector and the active material are chemically or physically bonded. Also good.
正極と負極の間にセパレータを介在させる場合には、セパレータに電解液を含浸させる。電解液は、溶媒および前記溶媒に溶解した溶質からなることが好ましい。電解液自体をゲル化させてセパレータとしての機能を持たせてもよい。この場合、ポリアクリロニトリル、アクリレート単位またはメタクリレート単位を含む重合体、エチレンとアクリロニトリルとの共重合体等のマトリックスに電解液を含浸させることが好ましい。マトリックスには架橋高分子を用いることが好ましい。 When a separator is interposed between the positive electrode and the negative electrode, the separator is impregnated with an electrolytic solution. The electrolytic solution preferably includes a solvent and a solute dissolved in the solvent. The electrolyte solution itself may be gelled to have a function as a separator. In this case, it is preferable to impregnate the electrolyte with a matrix such as polyacrylonitrile, a polymer containing an acrylate unit or a methacrylate unit, or a copolymer of ethylene and acrylonitrile. It is preferable to use a crosslinked polymer for the matrix.
電解液の溶質としては、リチウム、ナトリウム、カリウムなどのアルカリ金属またはマグネシウムなどのアルカリ土類金属のハロゲン化物、過塩素酸塩およびトリフロロメタンスルホン酸塩に代表される含フッ素化合物の塩等が好ましい。具体的には、例えば、フッ化リチウム、塩化リチウム、過塩素酸リチウム、トリフロロメタンスルホン酸リチウム、四ホウフッ化リチウム、ビストリフロロメチルスルホニルイミドリチウム、チオシアン酸リチウム、過塩素酸マグネシウム、トリフロロメタンスルホン酸マグネシウム、四ホウフッ化ナトリウムなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the solute of the electrolyte include halides of alkali metals such as lithium, sodium and potassium or alkaline earth metals such as magnesium, and salts of fluorine-containing compounds represented by perchlorate and trifluoromethanesulfonate. preferable. Specifically, for example, lithium fluoride, lithium chloride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetraborofluoride, lithium bistrifluoromethylsulfonylimide, lithium thiocyanate, magnesium perchlorate, trifluoromethane Examples thereof include magnesium sulfonate and sodium tetraborofluoride. These may be used alone or in combination of two or more.
電解液の溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、テトラヒドロフラン、ジオキソラン、スルホラン、ジメチルホルムアミド等の有機溶媒が好ましく用いられる。 As the solvent for the electrolytic solution, for example, organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide and the like are preferably used.
電解液の代わりに固体電解質を用いてもよい。固体電解質としては、Ｌｉ２Ｓ−ＳｉＳ２、Ｌｉ２Ｓ−Ｐ２Ｏ５、Ｌｉ２Ｓ−Ｂ２Ｓ５、Ｌｉ２Ｓ−Ｐ２Ｓ５−ＧｅＳ２、ナトリウム／アルミナ（Ａｌ２Ｏ３）、無定形または低相転移温度（Ｔｇ）のポリエーテル、無定形フッ化ビニリデン−６フッ化プロピレンコポリマー、異種高分子のブレンド体、ポリエチレンオキサイドなどが挙げられる。 A solid electrolyte may be used instead of the electrolytic solution. Examples of the solid electrolyte include Li 2 S—SiS 2 , Li 2 S—P 2 O 5 , Li 2 S—B 2 S 5 , Li 2 S—P 2 S 5 —GeS 2 , sodium / alumina (Al 2 O 3 ), Amorphous or low phase transition temperature (Tg) polyethers, amorphous vinylidene fluoride-6-propylene copolymer, blends of different polymers, polyethylene oxide, and the like.
活物質化合物は、化学結合を介して基材に担持させることができる。この場合、活物質化合物は、その誘導体であってもよい。化学結合は、共有結合であっても、配位結合であってもよい。活物質化合物を基材に担持することにより、電極（特に正極）活物質としての安定性が向上し、電池のサイクル特性を向上させることが可能となる。共有結合としては、Ｓｉ−Ｏ結合、Ｔｉ−Ｏ結合、アミド結合およびペプチド結合が好ましく、配位結合としては、金属−硫黄結合が好ましい。 The active material compound can be supported on the substrate through a chemical bond. In this case, the active material compound may be a derivative thereof. The chemical bond may be a covalent bond or a coordination bond. By supporting the active material compound on the base material, the stability as an electrode (particularly positive electrode) active material is improved, and the cycle characteristics of the battery can be improved. As the covalent bond, a Si—O bond, a Ti—O bond, an amide bond and a peptide bond are preferable, and as the coordination bond, a metal-sulfur bond is preferable.
基材には、金属、金属酸化物、粘土層間化合物、炭素材料、珪素化合物、樹脂類などを用いることができる。なお、金属には、アルミニウム、チタン、ニッケル、ステンレス鋼、金、銀、銅、白金、パラジウムなどを用いることが好ましく、金属酸化物には、ガラス、アルミナ、チタニアなどを用いることが好ましい。また、炭素材料には、カーボンブラック、グラファイト、アセチレンブラックなどを用いることができる。これらは表面水酸基、カルボキシル基等の官能基の量を多くする表面処理を行ってもよい。また、樹脂類には、フッ素樹脂、カーボン系樹脂、シリコーン樹脂、アミド樹脂、導電性樹脂などを用いることが好ましい。導電性樹脂としては、ポリアニリン、ポリピロール、ポリチオフェンなどが好ましい。 For the substrate, metals, metal oxides, clay intercalation compounds, carbon materials, silicon compounds, resins, and the like can be used. Note that aluminum, titanium, nickel, stainless steel, gold, silver, copper, platinum, palladium, or the like is preferably used as the metal, and glass, alumina, titania, or the like is preferably used as the metal oxide. Moreover, carbon black, graphite, acetylene black, etc. can be used for the carbon material. These may be subjected to surface treatment to increase the amount of functional groups such as surface hydroxyl groups and carboxyl groups. For the resins, it is preferable to use a fluororesin, a carbon-based resin, a silicone resin, an amide resin, a conductive resin, or the like. As the conductive resin, polyaniline, polypyrrole, polythiophene and the like are preferable.
Ｓｉ−Ｏ結合やＴｉ−Ｏ結合は、例えばＲｎＳｉＸ（４−ｎ）で表される有機珪素化合物やＲｎＴｉＸ（４−ｎ） で表される有機チタン化合物（Ｒは、それぞれ独立に有機基であり、Ｘは、それぞれ独立にハロゲン原子、アルコキシ基またはアシロキシ基であり、ｎは１〜３の整数である。）と、基材上に存在する水酸基との脱ハロゲン化水素または脱アルコール反応によって形成される。 The Si—O bond or Ti—O bond is, for example, an organosilicon compound represented by R n SiX (4-n) or an organotitanium compound represented by R n TiX (4-n). An organic group, X is each independently a halogen atom, an alkoxy group or an acyloxy group, and n is an integer of 1 to 3) and a dehydrohalogenated or dehydrated hydroxyl group present on the substrate. Formed by alcohol reaction.
例えば有機珪素化合物であるＲＳｉＣｌ３の場合、
Ｒ−ＳｉＣｌ３ ＋ ３ＲＯＨ → Ｒ−Ｓｉ（ＯＲ）３ ＋ ３ＨＣｌ
の反応により、Ｓｉ−Ｏ結合が形成される。従って、基材表面上には、多くの水酸基が存在することが好ましい。なお、上記のような脱ハロゲン化水素反応は、ガラス表面の疎水化処理に多用されており、例えば疎水化処理により樹脂との接着性を改善したガラス繊維を用いてガラス繊維強化樹脂が製造されている。
For example, in the case of RSiCl 3 which is an organosilicon compound,
R-SiCl 3 + 3ROH → R-Si (OR) 3 + 3HCl
As a result of the reaction, a Si—O bond is formed. Therefore, it is preferable that many hydroxyl groups exist on the substrate surface. The dehydrohalogenation reaction as described above is frequently used for the hydrophobic treatment of the glass surface. For example, a glass fiber reinforced resin is produced using glass fiber whose adhesion to the resin is improved by the hydrophobic treatment. ing.
ここで、ＲｎＳｉＸ（４−ｎ）で表される有機珪素化合物やＲｎＴｉＸ（４−ｎ） で表される有機チタン化合物として、Ｒが一般式（２）〜（５）のいずれかで表される構造を有する有機基である化合物を用いることにより、基体上に一般式（２）〜（５）のいずれかで表される構造を有する化合物を担持させることができる。実際には、Ｒが一般式（２）〜（５）のいずれかで表される構造を有する有機基であるＲｎＳｉＸ（４−ｎ）やＲｎＴｉＸ（４−ｎ）を溶媒に溶解させ、溶液に基材を浸漬させることにより、縮合反応が進行して、簡単に基体上に一般式（２）〜（５）のいずれかで表される構造を有する化合物を担持させることができる。 Here, as an organosilicon compound represented by R n SiX (4-n) or an organotitanium compound represented by R n TiX (4-n) , R is any one of the general formulas (2) to (5). By using a compound that is an organic group having a structure represented by formula (1) , a compound having a structure represented by any one of the general formulas (2) to (5) can be supported on the substrate. Actually, R n SiX (4-n) or R n TiX (4-n) , which is an organic group having a structure represented by any one of the general formulas (2) to (5) , is dissolved in a solvent. And the substrate is immersed in the solution, the condensation reaction proceeds, and the compound having a structure represented by any one of the general formulas (2) to (5) can be easily supported on the substrate. .
基材表面上の置換基と、一般式（２）〜（５）のいずれかで表される構造を有する化合物の置換基とを選択することにより、様々な化学結合を形成することができる。例えば、基材表面上にアミノ基を、一般式（２）〜（５）のいずれかで表される構造を有する化合物の置換基としてカルボキシル基を選択する場合には、アミノ基とカルボキシル基との間でアミド結合が形成される。アミノ基およびカルボキシル基は、基材および一般式（２）〜（５）のいずれかで表される構造を有する化合物のどちらに存在していてもよい。 Various chemical bonds can be formed by selecting a substituent on the surface of the substrate and a substituent of the compound having a structure represented by any one of the general formulas (2) to (5) . For example, when selecting a carboxyl group as a substituent of a compound having a structure represented by any one of the general formulas (2) to (5) on the substrate surface, the amino group and the carboxyl group An amide bond is formed between the two. The amino group and the carboxyl group may be present in either the base material or the compound having a structure represented by any one of the general formulas (2) to (5) .
次に、金属−硫黄結合は、金属と、チオール基との反応によって形成することができる。チオール基は、金属に配位・吸着し、金属−硫黄結合を形成することが知られている。この反応を利用して、チオールは、金属表面上に自己集合膜を形成する。活物質化合物に置換基としてチオール基を持たせ、これを金属と接触させると、配位反応が進行し、金属−硫黄結合が形成される。基材には、金属の他に、金属イオンを表面に有する樹脂、炭素材料等を用いることもできる。 A metal-sulfur bond can then be formed by reaction of the metal with a thiol group. It is known that a thiol group coordinates and adsorbs to a metal to form a metal-sulfur bond. Utilizing this reaction, thiol forms a self-assembled film on the metal surface. When the active material compound has a thiol group as a substituent and is brought into contact with a metal, a coordination reaction proceeds and a metal-sulfur bond is formed. As the base material, in addition to the metal, a resin having a metal ion on the surface, a carbon material, or the like can be used.
活物質化合物と基材との間の化学結合としては、上記のほかに、炭素−炭素単結合、炭素−炭素二重結合、炭素−カルコゲン原子結合、硫黄−硫黄結合、金属−炭素結合などが挙げられる。
基材に担持された活物質化合物を電極活物質として用いる場合、電極構成材料の結着性を向上させるために、結着剤を用いてもよい。基材に担持された活物質化合物に結着剤等を添加して、ペレット状に成形することもできる。
In addition to the above, the chemical bond between the active material compound and the substrate includes a carbon-carbon single bond, a carbon-carbon double bond, a carbon-chalcogen atom bond, a sulfur-sulfur bond, a metal-carbon bond, and the like. Can be mentioned.
When the active material compound supported on the substrate is used as the electrode active material, a binder may be used to improve the binding property of the electrode constituent material. A binder or the like can be added to the active material compound supported on the base material to form a pellet.
次に、本発明について実施例に基づいて詳細に説明する。
各実施例では、コイン型電池を作製して電極活物質の評価を行った。評価方法は通常の二次電池の評価方法と同様とした。以下に、試験電極の作製方法、コイン型電池の作製方法および電池の特性評価について順次に説明する。
Next, the present invention will be described in detail based on examples.
In each example, a coin-type battery was produced and the electrode active material was evaluated. The evaluation method was the same as the evaluation method for ordinary secondary batteries. Hereinafter, a test electrode manufacturing method, a coin-type battery manufacturing method, and battery characteristic evaluation will be described in order.
（i）試験電極の作製方法
ガス精製装置を備えたドライボックスを用い、アルゴンガス雰囲気下において以下の操作を行った。電極活物質として化学式（７）：
(I) Preparation method of test electrode The following operation was performed in argon gas atmosphere using the dry box provided with the gas purification apparatus. Chemical formula (7) as an electrode active material:
で表される化合物（テトラチアフルバレン：一般式（２）において、Ｘ １ 〜Ｘ ４ が硫黄原子であり、Ｒ３〜Ｒ６が水素原子の化合物）３０ｍｇと、導電補助剤としてアセチレンブラック３０ｍｇとを均一になるまで混合し、溶剤としてＮ−メチル−２−ピロリドンを１ｍＬ加えた。得られた混合物に、活物質と導電補助剤とを結着させる目的で、結着剤としてポリフッ化ビニリデン５ｍｇを加え、均一になるまで混合し、黒色のスラリーを得た。これをアルミニウム箔集電体上にキャストし、室温にて１時間真空乾燥を行った。乾燥後、これを１３．５ｍｍの円盤状に打ち抜いて試験電極とした。 30 mg of a compound represented by the formula (tetrathiafulvalene: a compound in which X 1 to X 4 are sulfur atoms and R 3 to R 6 are hydrogen atoms in the general formula (2)), and 30 mg of acetylene black as a conductive auxiliary agent, Were mixed until uniform, and 1 mL of N-methyl-2-pyrrolidone was added as a solvent. For the purpose of binding the active material and the conductive auxiliary agent to the obtained mixture, 5 mg of polyvinylidene fluoride was added as a binder and mixed until uniform to obtain a black slurry. This was cast on an aluminum foil current collector and vacuum dried at room temperature for 1 hour. After drying, this was punched out into a 13.5 mm disk shape to obtain a test electrode.
（ii）コイン型電池の作製方法
上記方法で作製した試験電極を正極に用いて、リチウム金属（厚さ：３００μｍ）を負極とするコイン型電池を以下の手順で作製した。得られたコイン型電池の縦断面図を図１に示す。まず、ケース１１の内面に試験電極１２を配置し、試験電極（正極）１２の上に多孔質ポリエチレンシートからなるセパレータ１３を設置した。次に、電解液をケース１１内に注液した。電解液には、エチレンカーボネートとジエチルカーボネートとの重量比１：１の混合溶媒に、１モル／Ｌの濃度で６フッ化リン酸リチウム（ＬｉＰＦ６）を溶解したものを用いた。また、内面に金属リチウム（負極）１４が圧着され、周縁部に封止リング１５を装着した封口板１６を準備した。そして、金属リチウム１４を試験電極１２と対面させてケース１１を封口板１６で封口し、プレス機でケース１１の開口端部を封止リング１５にかしめて、評価用のコイン型電池を得た。
(Ii) Method for Producing Coin-Type Battery Using the test electrode produced by the above method as a positive electrode, a coin-type battery having lithium metal (thickness: 300 μm) as a negative electrode was produced according to the following procedure. A longitudinal sectional view of the obtained coin-type battery is shown in FIG. First, the
（iii）電池の特性評価
作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ求めた。また、リチウムの酸化還元電位（Ｌｉ／Ｌｉ＋）に対する平均放電電圧を求めた。平均放電電圧は、１サイクル目の放電時の電圧の平均値を用いた。なお、３００サイクル目まで放電電圧にほとんど変化はなかった。２段階の放電反応により放電カーブが階段状になっている場合にも、全体の平均値を求めた。結果を表１に示す。
(Iii) Battery Characteristic Evaluation The prepared coin-type battery was charged and discharged at a constant current at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the 1, 50, 100 and 300th cycles were as follows. I asked for each. Moreover, the average discharge voltage with respect to the oxidation-reduction potential (Li / Li + ) of lithium was calculated | required. As the average discharge voltage, the average value of the voltage at the time of discharge in the first cycle was used. The discharge voltage hardly changed until the 300th cycle. Even when the discharge curve is stepped due to the two-stage discharge reaction, the average value of the whole was obtained. The results are shown in Table 1.
また、充放電レート特性を評価した。ここでは、作製したコイン型電池の定電流充放電を、電流値０．６６５、１．３３または２．６６ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、各電流値における５０サイクル目の放電容量をそれぞれ求めた。結果を表２に示す。 Moreover, the charge / discharge rate characteristics were evaluated. Here, constant current charging / discharging of the manufactured coin-type battery is performed at a current value of 0.665, 1.33 or 2.66 mA, a voltage range of 2.5 V to 4.5 V, and discharge at the 50th cycle at each current value. Each capacity was determined. The results are shown in Table 2.
《比較例１》
試験電極の活物質として有機硫黄系化合物である２，５−ジメルカプト−１，３，４−チアジアゾール（以下、ＤＭｃＴ）（Aldrich社製）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。
<< Comparative Example 1 >>
Coin-shaped in the same manner as in Example 1, except that 2,5-dimercapto-1,3,4-thiadiazole (hereinafter referred to as DMcT) (manufactured by Aldrich), which is an organic sulfur compound, was used as the active material of the test electrode. A battery was prepared and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（８）： Instead of the compound represented by the chemical formula (7), the chemical formula (8):
で表される化合物（テトラメチルテトラチアフルバレン：一般式（２）において、Ｘ １ 〜Ｘ ４ が硫黄原子であり、Ｒ３〜Ｒ６がメチル基の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 Example 1 except that a compound represented by the formula (tetramethyltetrathiafulvalene: a compound in which X 1 to X 4 are sulfur atoms and R 3 to R 6 are methyl groups in the general formula (2)) is used. A coin-type battery was produced in the same manner as described above and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（９）： Instead of the compound represented by the chemical formula (7), the chemical formula (9):
で表される化合物（一般式（２）において、Ｘ １ 〜Ｘ ４ が硫黄原子であり、Ｒ３〜Ｒ６がチオメチル基の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 In the same manner as in Example 1, except that a compound represented by the formula (a compound in which X 1 to X 4 are sulfur atoms and R 3 to R 6 are thiomethyl groups in the general formula (2)) is used, a coin type A battery was prepared and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１５）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 15 ):
で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 Except that in using the compound represented by A coin type battery was produced in the same manner as in Example 1, it was evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１６）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 16 ):
で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 Except that in using a compound represented by, to prepare a coin-type battery in the same manner as in Example 1 was evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１７）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 17 ):
で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 Except that in using the compound represented by A coin type battery was produced in the same manner as in Example 1, it was evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１０）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 10 ):
で表される化合物（一般式（３）において、Ｘ １ 〜Ｘ ４ が硫黄原子であり、ＸおよびＹがそれぞれ炭素原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 A coin-type battery in the same manner as in Example 1 except that a compound represented by the formula (a compound in which X 1 to X 4 are sulfur atoms and X and Y are each a carbon atom in the general formula ( 3 )) was used Were prepared and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１１）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 11 ):
で表される化合物（一般式（３）において、Ｘ １ 〜Ｘ ４ 、ＸおよびＹがそれぞれイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 A coin-type battery was prepared in the same manner as in Example 1 except that a compound represented by the formula (in the general formula ( 3 ) , X 1 to X 4 , X and Y are each sulfur compounds) was used. Evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１２）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 12 ):
で表される化合物（一般式（３）において、Ｘが酸素原子、Ｘ １ 〜Ｘ ４ およびＹがイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In formula (3), X is an oxygen atom, X 1 to X 4 and Y are compounds of sulfur atoms) compound represented by except using, to prepare a coin-type battery in the same manner as in Example 1 , Evaluated in the same way. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１３）： Instead of the compound represented by the chemical formula (7), the chemical formula ( 13 ):
で表される化合物（一般式（４）において、Ｘ １ 〜Ｘ ４ が硫黄原子であり、Ｒ９およびＲ１０がヒドロキシメチル基、ｎ＝３の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 Example 1 except that a compound represented by the formula (compound of general formula ( 4 ), wherein X 1 to X 4 are sulfur atoms, R 9 and R 10 are hydroxymethyl groups, n = 3) is used. Similarly, a coin-type battery was produced and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（６）： Instead of the compound represented by the chemical formula (7), the chemical formula (6):
で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 A coin-type battery was prepared and evaluated in the same manner as in Example 1 except that the compound represented by The results are shown in Tables 1 and 2.
［評価結果の考察］
表１の結果から、有機硫黄系化合物を電極活物質に用いた比較例１では、初期放電時には２００ｍＡｈ／ｇの容量が得られたものの、５０サイクル目には５０ｍＡｈ／ｇまで減少し、１００サイクル目にはわずか１０ｍＡｈ／ｇ程度の容量しか得られなかった。一方、一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質に用いた実施例１〜実施例８では、いずれも３．５Ｖ付近の高い平均放電電圧が得られ、３００サイクル目でもほとんど放電容量の減少が観察されなかった。
[Consideration of evaluation results]
From the results of Table 1, in Comparative Example 1 using an organic sulfur-based compound as an electrode active material, a capacity of 200 mAh / g was obtained at the time of initial discharge, but decreased to 50 mAh / g at the 50th cycle and 100 cycles. Only a capacity of about 10 mAh / g was obtained in the eyes. On the other hand, in Examples 1 to 8 in which the compound having the structure represented by any one of the general formulas (2) to (5) is used as the electrode active material, a high average discharge voltage in the vicinity of 3.5 V is used. As a result, almost no decrease in discharge capacity was observed even at the 300th cycle.
比較例１で用いた有機硫黄系化合物は、その充放電反応機構がＳ−Ｓ結合の解列・再結合反応に基づいている。この反応は反応頻度が低いこと、充放電反応により分子構造が大きく変化することから、再結合性は低くなる。そのため、サイクル初期では高い放電容量が得られたものの、１００サイクル目には、ほとんど放電容量が得られなくなってしまったと考えられる。以上より、Ｓ−Ｓ結合の解列・再結合反応に基づく反応機構を有する化合物をそのままの状態で電極活物質に用いても、高いサイクル特性が得られないことがわかる。 The charge-discharge reaction mechanism of the organic sulfur compound used in Comparative Example 1 is based on the SS bond separation / recombination reaction. This reaction has low recombination properties because the reaction frequency is low and the molecular structure is greatly changed by the charge / discharge reaction. Therefore, although a high discharge capacity was obtained at the beginning of the cycle, it is considered that almost no discharge capacity was obtained at the 100th cycle. From the above, it can be seen that even if a compound having a reaction mechanism based on SS bond dissociation / recombination reaction is used as it is for the electrode active material, high cycle characteristics cannot be obtained.
一方、本発明の実施例１〜８で用いた一般式（２）〜（５）のいずれかで表される構造を有する化合物は、３００サイクル経過後においても、ほとんど放電容量が減少することはなかった。これらの化合物は、充放電反応において、分子上にアニオンやカチオンが配位するだけであり、分子構造の大きな変化を起こさないことから、サイクル経過に伴う化合物自身の劣化が起こらなかったためと考えられる。 On the other hand, the compound having the structure represented by any one of the general formulas (2) to (5) used in Examples 1 to 8 of the present invention has a substantially reduced discharge capacity even after 300 cycles. There wasn't. These compounds are thought to be because the compounds themselves do not deteriorate with the progress of the cycle because only anions and cations are coordinated on the molecules in the charge / discharge reaction, and the molecular structure does not change significantly. .
以上の結果から、一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質とする電気化学素子は、高いサイクル特性を有することがわかる。また、表２の結果から明らかなように、一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質とする電気化学素子は、高い充放電レート特性を有することがわかった。 From the above results, it can be seen that an electrochemical device using a compound having a structure represented by any one of the general formulas (2) to (5) as an electrode active material has high cycle characteristics. In addition, as is apparent from the results in Table 2, an electrochemical device using a compound having a structure represented by any of the general formulas (2) to (5) as an electrode active material has high charge / discharge rate characteristics. I understood it.
次に、一般式（２）〜（５）のいずれかで表される構造を複数有する高分子化合物を電極活物質に用いた実施例について説明する。ここでは、ポリアセチレン鎖を主鎖として有し、テトラチアフルバレン構造を有する化合物として、化学式（１４）： Next, examples in which a polymer compound having a plurality of structures represented by any one of the general formulas (2) to (5) is used as an electrode active material will be described. Here, as a compound having a polyacetylene chain as a main chain and having a tetrathiafulvalene structure, a chemical formula ( 14 ):
で表される化合物を用いた。３０ｍｇの化学式（７）で表される化合物の代わりに、４０ｍｇの化学式（１４）で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表３に示す。表３の結果より、一般式（２）〜（５）のいずれかで表される構造を複数有する高分子化合物を電極活物質に用いた電気化学素子も、高いサイクル特性を示すことがわかる。 The compound represented by this was used. A coin-type battery was fabricated in the same manner as in Example 1, except that 40 mg of the compound represented by the chemical formula ( 14 ) was used instead of 30 mg of the compound represented by the chemical formula (7). Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities of the first, 50, 100, and 300th cycles were the same as in Example 1. It asked similarly. The results are shown in Table 3. From the results in Table 3, it can be seen that an electrochemical device using a polymer compound having a plurality of structures represented by any of the general formulas (2) to (5) as an electrode active material also exhibits high cycle characteristics.
次に、負極としてリチウム含有複合窒化物を用いた実施例について説明する。以下に示す負極を用いたこと以外は、実施例１と同様にしてコイン型電池を作製した。正極には、実施例１で作製したものと同じ試験電極を用いた。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表４に示す。 Next, an example using a lithium-containing composite nitride as the negative electrode will be described. A coin-type battery was produced in the same manner as in Example 1 except that the following negative electrode was used. As the positive electrode, the same test electrode as that prepared in Example 1 was used. Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the first, 50, 100, and 300th cycles were the same as those of Example 1. It asked similarly. The results are shown in Table 4.
ここで、リチウム含有複合窒化物は、Ｌｉ／Ｃｏのモル比が２．６／０．４のリチウムコバルト合金を銅製の容器に入れ、窒素雰囲気中、８００℃２時間保持することにより、前記合金を窒素と反応させて調製した。反応後、得られた黒灰色の窒化物を粉末状に粉砕し、負極活物質として用いた。 Here, the lithium-containing composite nitride is obtained by placing a lithium cobalt alloy having a Li / Co molar ratio of 2.6 / 0.4 in a copper container and holding the alloy in a nitrogen atmosphere at 800 ° C. for 2 hours. Was prepared by reacting with nitrogen. After the reaction, the obtained black gray nitride was pulverized into a powder and used as a negative electrode active material.
得られた負極活物質の粉末Ｘ線回折測定をＣｕＫα線を用いて行ったところ、窒化リチウム（Ｌｉ３Ｎ）と同じ六方晶に基づく回折パターンが観測された。このことから、Ｃｏが窒化リチウムの結晶構造に取り込まれた状態の、単一相の固溶体が得られていることが確認された。合成したリチウム含有複合窒化物の組成はＬｉ２．６Ｃｏ０．４Ｎであった。 When the powder X-ray diffraction measurement of the obtained negative electrode active material was performed using CuKα ray, a diffraction pattern based on the same hexagonal crystal as lithium nitride (Li 3 N) was observed. From this, it was confirmed that a single-phase solid solution in which Co was incorporated in the crystal structure of lithium nitride was obtained. The composition of the synthesized lithium-containing composite nitride was Li 2.6 Co 0.4 N.
Ｌｉ２．６Ｃｏ０．４Ｎの粉末、炭素粉末、および結着剤としてのポリテトラフルオロエチレン粉末を、重量比１００：２５：５で充分に混合して、負極合剤を得た。この負極合剤を銅シート上に塗布し、圧延し、得られた極板を直径１３．５ｍｍの円盤状に打ち抜いて負極とした。 Li 2.6 Co 0.4 N powder, carbon powder, and polytetrafluoroethylene powder as a binder were sufficiently mixed at a weight ratio of 100: 25: 5 to obtain a negative electrode mixture. This negative electrode mixture was applied on a copper sheet, rolled, and the obtained electrode plate was punched into a disk shape having a diameter of 13.5 mm to obtain a negative electrode.
次に、負極としてリチウム含有チタン酸化物を用いた実施例について説明する。以下に示す負極を用いたこと以外は、実施例１と同様にしてコイン型電池を作製した。正極には、実施例１で作製したものと同じ試験電極を用いた。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表４に示す。 Next, examples using lithium-containing titanium oxide as the negative electrode will be described. A coin-type battery was produced in the same manner as in Example 1 except that the following negative electrode was used. As the positive electrode, the same test electrode as that prepared in Example 1 was used. Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the first, 50, 100, and 300th cycles were the same as those of Example 1. It asked similarly. The results are shown in Table 4.
ここで、リチウム含有チタン酸化物には、ＬｉＴｉ５Ｏ１２粉末を用いた。ＬｉＴｉ５Ｏ１２の粉末、炭素粉末、および結着剤としてのポリテトラフルオロエチレン粉末を、重量比１００：２５：５で充分に混合して、負極合剤を得た。この負極合剤を銅シート上に塗布し、圧延し、得られた極板を直径１３．５ｍｍの円盤状に打ち抜いて負極とした。 Here, LiTi 5 O 12 powder was used as the lithium-containing titanium oxide. LiTi 5 O 12 powder, carbon powder, and polytetrafluoroethylene powder as a binder were sufficiently mixed at a weight ratio of 100: 25: 5 to obtain a negative electrode mixture. This negative electrode mixture was applied on a copper sheet, rolled, and the obtained electrode plate was punched into a disk shape having a diameter of 13.5 mm to obtain a negative electrode.
表４の結果より、一般式（２）〜（５）のいずれかで表される構造を有する化合物を一方の電極活物質に用い、他方の電極活物質にリチウム含有複合窒化物またはリチウム含有チタン酸化物を用いた電気化学素子も、高いサイクル特性を示すことがわかる。 From the results of Table 4, a compound having a structure represented by any one of the general formulas (2) to (5) is used for one electrode active material, and the other electrode active material is lithium-containing composite nitride or lithium-containing titanium. It can be seen that the electrochemical element using the oxide also exhibits high cycle characteristics.
次に、一般式（２）〜（５）のいずれかで表される構造を有する化合物を、正極および負極の両方の活物質に用いた実施例について説明する。ここでは、正極活物質として化学式（１０）： Next, an example in which a compound having a structure represented by any one of the general formulas (2) to (5) is used as an active material for both positive and negative electrodes will be described. Here, the chemical formula ( 10 ):
で表される化合物を用い、負極活物質として化学式（８）： As a negative electrode active material, a chemical formula (8):
で表される化合物を用いた。正極活物質および負極活物質にこれらを用いたこと以外、実施例１と同様にしてコイン型電池を作製した。すなわち、化学式（７）で表される化合物の代わりに、それぞれ化学式（１０）で表される化合物および化学式（８）で表される化合物を用いて試験電極を作製し、前者の試験電極を正極に、後者の試験電極を負極に用いたコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲０．３Ｖ〜０．６Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表５に示す。表５の結果より、両極に一般式（２）〜（５）のいずれかで表される化合物を用いた場合にも、高いサイクル特性が得られることがわかる。 The compound represented by this was used. A coin-type battery was fabricated in the same manner as in Example 1 except that these were used for the positive electrode active material and the negative electrode active material. That is, instead of the compound represented by the chemical formula (7), a test electrode is prepared using a compound represented by the chemical formula ( 10 ) and a compound represented by the chemical formula (8), respectively, and the former test electrode is used as the positive electrode. In addition, a coin-type battery using the latter test electrode as a negative electrode was produced. Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 0.3 V to 0.6 V, and the discharge capacities of the first, 50, 100, and 300th cycles were the same as in Example 1. It asked similarly. The results are shown in Table 5. From the results in Table 5, it can be seen that high cycle characteristics can be obtained even when the compound represented by any one of the general formulas (2) to (5) is used for both electrodes.
次に、一般式（２）〜（５）のいずれかで表される構造を有し、かつ、膜を形成している高分子化合物を正極に用いた実施例について説明する。ここでは、化学式（１４）： Next, an example in which a polymer compound having a structure represented by any one of the general formulas (2) to (5) and forming a film is used for the positive electrode will be described. Here, the chemical formula ( 14 ):
で表される化合物を電解重合して膜を調製した。具体的には、化学式（１４）で表される化合物をアセトニトリルに溶解して、濃度０．１ｍｏｌ／Ｌの溶液を調製し、その溶液にアルミニウム基板を浸漬して、基板と対極との間に２．０Ｖ（対Ｌｉ／Ｌｉ＋）の定電位電解を行った。その結果、基板上に高分子化合物の膜（厚さ４０μｍ）が形成された。 A film was prepared by electrolytic polymerization of a compound represented by the formula: Specifically, the compound represented by the chemical formula ( 14 ) is dissolved in acetonitrile to prepare a solution having a concentration of 0.1 mol / L, an aluminum substrate is immersed in the solution, and the substrate is placed between the substrate and the counter electrode. A constant potential electrolysis of 2.0 V (vs. Li / Li + ) was performed. As a result, a polymer compound film (thickness 40 μm) was formed on the substrate.
この膜を所定の形状に打ち抜き、これを正極として用いたこと以外、実施例１と同様にしてコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲３．０Ｖ〜３．８Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表５に示す。表５の結果より、電解重合により得られた高分子化合物からなる膜を用いても、高いサイクル特性が得られることがわかる。 A coin-type battery was fabricated in the same manner as in Example 1 except that this film was punched into a predetermined shape and used as the positive electrode. Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 3.0 V to 3.8 V, and the discharge capacities of the first, 50, 100, and 300th cycles were the same as in Example 1. It asked similarly. The results are shown in Table 5. From the results in Table 5, it can be seen that high cycle characteristics can be obtained even when a film made of a polymer compound obtained by electrolytic polymerization is used.
活物質化合物を基材に担持する場合について説明する。
（i）試験電極の作製方法
電極活物質としては、置換基としてアルキルトリメトキシシラン基を有する化学式（１８）：
The case where an active material compound is carried on a substrate will be described.
(I) Method for producing test electrode As an electrode active material, chemical formula (18) having an alkyltrimethoxysilane group as a substituent:
で表される化合物を用いた。また、基材としては活性炭を用いた。ヘキサデカンとクロロホルムとの体積比４：１の混合溶媒１００重量部と、化学式（１８）で表される化合物を５重量部とを混合し、処理液を調製した。この処理液１００ｍＬに、１２０℃で１０分間オゾン処理を行った活性炭１０ｇを浸漬し、１２時間攪拌を行った。オゾン処理は、活性炭表面上に多く存在する官能基を水酸基に変換する目的で行った。 The compound represented by this was used. Moreover, activated carbon was used as the substrate. A processing solution was prepared by mixing 100 parts by weight of a mixed solvent of hexadecane and chloroform in a volume ratio of 4: 1 and 5 parts by weight of the compound represented by the chemical formula (18). In 100 mL of this treatment solution, 10 g of activated carbon that had been subjected to ozone treatment at 120 ° C. for 10 minutes was immersed and stirred for 12 hours. The ozone treatment was performed for the purpose of converting functional groups present on the activated carbon surface into hydroxyl groups.
活性炭を処理液から濾別し、さらにクロロホルム１００ｍＬ中に浸漬して１時間攪拌した。その後、活性炭をクロロホルムから濾別し、再度クロロホルム１００ｍＬ中に浸漬して１時間攪拌を行うことにより、洗浄を行った。洗浄後の活性炭を濾別し、１０時間真空乾燥を行うことにより、電極活物質を担持した活性炭を得た。なお、これらの処理は、すべてアルゴン雰囲気下、湿度−３０度以下の条件下で行った。 Activated carbon was filtered off from the treatment liquid, and further immersed in 100 mL of chloroform and stirred for 1 hour. Thereafter, the activated carbon was separated from chloroform, washed again by being immersed in 100 mL of chloroform and stirred for 1 hour. The activated carbon after washing was filtered off and vacuum-dried for 10 hours to obtain activated carbon carrying an electrode active material. These treatments were all performed under an argon atmosphere and a humidity of -30 degrees or less.
活性炭上に電極活物質が化学結合を介して担持されているかを分光学的手法を用いて確認した。具体的には、電極活物質を担持した活性炭のＩＲ測定を行うと、２５００ｃｍ−１付近にＳ−Ｈに由来するピーク、７５０ｃｍ−１および１２５０ｃｍ−１付近にＣ−Ｓ−Ｃ結合に由来するピーク、３０００ｃｍ−１付近にＣＨ２に由来するピーク、１１００ｃｍ−１付近にＳｉ−Ｏ−Ｓｉ結合に由来するピークがそれぞれ観察された。これらのピークは、活性炭のみの場合には、いずれも観測されなかった。以上より、上記処理によって、活性炭上に電極活物質が化学結合を介して担持されていることが確認された。 Whether or not the electrode active material was supported on the activated carbon via a chemical bond was confirmed using a spectroscopic method. Specifically, when the IR measurement of the activated carbon carrying an electrode active material, from the vicinity of 2500 cm -1 peak derived from S-H, the C-S-C bond in the vicinity of 750 cm -1 and 1250 cm -1 A peak derived from CH 2 was observed near 3000 cm −1 , and a peak derived from Si—O—Si bond was observed near 1100 cm −1 . None of these peaks were observed when only activated carbon was used. From the above, it was confirmed that the electrode active material was supported on the activated carbon via a chemical bond by the above treatment.
（ii）コイン型電池の作製方法
化学式（７）で表される化合物単独の代わりに、こうして得られた基材と電極活物質との複合材料７０ｍｇを用い、導電補助剤としてアセチレンブラック２０ｍｇ、結着剤としてポリフッ化ビニリデン１０ｍｇを用いたこと以外、実施例１と同様にして、コイン型電池を作成した。
(Ii) Method for producing coin-type battery Instead of the compound represented by the chemical formula (7) alone, 70 mg of the composite material of the base material and the electrode active material thus obtained was used, and 20 mg of acetylene black as a conductive auxiliary agent, A coin-type battery was prepared in the same manner as in Example 1 except that 10 mg of polyvinylidene fluoride was used as the adhesive.
（iii）電池の特性評価
作製したコイン型電池の充放電試験を、電流値１．０ｍＡで、電圧範囲４．２Ｖから２．５Ｖで繰り返した。充放電は雰囲気温度２０℃で行った。１、５０、１００および３００サイクル目における放電容量（ｍＡｈ／ｇ）を求めた。結果を理論容量とともに表６に示す。
(Iii) Battery Characteristic Evaluation The charge / discharge test of the manufactured coin battery was repeated at a current value of 1.0 mA and a voltage range of 4.2 V to 2.5 V. Charging / discharging was performed at an atmospheric temperature of 20 ° C. The discharge capacity (mAh / g) at 1, 50, 100 and 300th cycles was determined. The results are shown in Table 6 together with the theoretical capacity.
表６中、理論容量および測定された放電容量は、活物質重量あたりの容量であるが、ここでは活物質重量に基材重量を含めていない。表６の結果から、−Ｓｉ−Ｏ−結合により導電性基材である活性炭上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。 In Table 6, the theoretical capacity and the measured discharge capacity are the capacity per weight of the active material, but here the base material weight is not included in the weight of the active material. From the results of Table 6, it can be seen that by carrying an electrode active material on activated carbon, which is a conductive base material, by -Si-O- bonds, there is almost no capacity deterioration due to charge / discharge cycles. In this example, stable cycle characteristics were confirmed even after 300 cycles.
化学式（１８）で表される化合物の代わりに、化学式（１９）： Instead of the compound represented by the chemical formula (18), the chemical formula (19):
で表される化合物を用いたこと以外、実施例１４と同様にして、基材と電極活物質との複合材料を作製した。化学式（１９）で表される化合物は、置換基としてアミノ基を有する。このアミノ基は、基材である活性炭上のカルボキシル基とアミド結合を形成することができる。 A composite material of a base material and an electrode active material was produced in the same manner as in Example 14 except that the compound represented by The compound represented by the chemical formula (19) has an amino group as a substituent. This amino group can form an amide bond with a carboxyl group on activated carbon as a base material.
活性炭上に電極活物質が化学結合を介して担持されているかを分光学的手法を用いて確認した。具体的には、電極活物質を担持した活性炭の場合、３０００ｃｍ−１付近にＮ−Ｈに由来するピーク、８５０ｃｍ−１付近にＣ−Ｎ結合に由来するピーク、３０００ｃｍ−１付近にＣＨ２に由来するピーク、３４００ｃｍ−１付近にＮＨ−ＣＯ結合に由来するピークがそれぞれ観察された。これらのピークは、活性炭のみの場合には、いずれも観測されなかった。以上より、上記処理によって、活性炭上に電極活物質が化学結合を介して担持されていることが確認された。 Whether or not the electrode active material was supported on the activated carbon via a chemical bond was confirmed using a spectroscopic method. More specifically, in the case of activated carbon which carries an electrode active material, a peak derived from the N-H in the vicinity of 3000 cm -1, a peak derived from the C-N bond in the vicinity of 850 cm -1, the CH 2 in the vicinity of 3000 cm -1 A peak derived from an NH—CO bond was observed in the vicinity of 3400 cm −1 . None of these peaks were observed when only activated carbon was used. From the above, it was confirmed that the electrode active material was supported on the activated carbon via a chemical bond by the above treatment.
こうして得られた複合材料を用いたこと以外、実施例１４と同様にして、コイン型電池を作製し、同様に評価した。結果を理論容量とともに表６に示す。表６の結果から、アミド結合により導電性基材である活性炭上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。 A coin-type battery was prepared and evaluated in the same manner as in Example 14 except that the composite material thus obtained was used. The results are shown in Table 6 together with the theoretical capacity. From the results of Table 6, it can be seen that by carrying an electrode active material on activated carbon which is a conductive base material by an amide bond, there is almost no capacity deterioration due to charge / discharge cycles. In this example, stable cycle characteristics were confirmed even after 300 cycles.
（i）試験電極の作製方法
電極活物質としては、置換基としてチオール基を有する化学式（２０）：
(I) Method for preparing test electrode As an electrode active material, chemical formula (20) having a thiol group as a substituent:
で表される化合物を用いた。また、基材としては金微粒子を用いた。金微粒子（平均粒径１０μｍ）１重量％のＮ−メチル−２−ピロリドン（ＮＭＰ）溶液１００重量部と、化学式（２０）で表される化合物を３重量部とを混合し、２５℃で１２時間攪拌を行った。その後、金微粒子をＮＭＰから濾別し、１０時間真空乾燥を行うことにより、電極活物質を担持した金微粒子を得た。なお、これらの処理は、すべてアルゴン雰囲気下、湿度−３０度以下の条件下で行った。 The compound represented by this was used. Further, gold fine particles were used as the substrate. 100 parts by weight of an N-methyl-2-pyrrolidone (NMP) solution containing 1% by weight of gold fine particles (average particle size 10 μm) and 3 parts by weight of the compound represented by the chemical formula (20) are mixed and mixed at 12 ° C. at 12 ° C. Stir for hours. Thereafter, the gold fine particles were separated from NMP and vacuum-dried for 10 hours to obtain gold fine particles carrying an electrode active material. These treatments were all performed under an argon atmosphere and a humidity of -30 degrees or less.
金微粒子上に電極活物質が化学結合を介して担持されているかを、ＩＲ測定およびＸＰＳ測定により確認した。具体的には、ＩＲ測定においては、３０００ｃｍ−１付近にＣＨ２に由来すると考えられるピーク、７５０ｃｍ−１および１２５０ｃｍ−１付近にＣ−Ｓ−Ｃ結合に由来すると考えられるピークが観測された。これらのピークは、金微粒子のみの場合には、いずれも観測されなかった。また、ＸＰＳ測定においては、金微粒子のみからは全く観測されなかったＳ（２ｐ）のピークが観測された。以上より、上記処理によって、金微粒子上に電極活物質が化学結合を介して担持されていることが確認された。 It was confirmed by IR measurement and XPS measurement whether the electrode active material was supported on the gold fine particles through chemical bonds. Specifically, in the IR measurement, a peak considered to be derived from CH 2 in the vicinity of 3000 cm −1 and a peak considered to be derived from the C—S—C bond were observed in the vicinity of 750 cm −1 and 1250 cm −1 . None of these peaks were observed when only gold fine particles were used. In XPS measurement, an S (2p) peak that was not observed at all from the gold fine particles alone was observed. From the above, it was confirmed that the electrode active material was supported on the gold fine particles through chemical bonds by the above treatment.
こうして得られた金微粒子と電極活物質との複合材料を用いたこと以外、実施例１４と同様にして、コイン型電池を作製し、同様に評価した。結果を理論容量とともに表６に示す。表６の結果から、金-硫黄結合により導電性基材である金微粒子上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。
実施例１４〜１６は、基材に化学結合を介して電極活物質を担持することにより、高いサイクル特性が得られることを示している。
A coin-type battery was produced and evaluated in the same manner as in Example 14 except that the composite material of the gold fine particles and the electrode active material thus obtained was used. The results are shown in Table 6 together with the theoretical capacity. From the results of Table 6, it can be seen that the capacity deterioration accompanying the charge / discharge cycle hardly occurs when the electrode active material is supported on the gold fine particles as the conductive substrate by the gold-sulfur bond. In this example, stable cycle characteristics were confirmed even after 300 cycles.
Examples 14 to 16 show that high cycle characteristics can be obtained by supporting an electrode active material on a substrate via a chemical bond.
以上のように、本発明は、一般式（２）〜（５）のいずれかで表される構造を有する化合物を電極活物質に用いることから、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子に適用することができる。 As described above, the present invention uses a compound having a structure represented by any one of the general formulas (2) to (5) as an electrode active material, so that it is light and has high energy density and excellent cycle characteristics. It can be applied to chemical elements.
１１ ケース
１２ 試験電極
１３ セパレータ
１４ 金属リチウム
１５ 封止リング
１６ 封口板
11
Claims (16)
負極と、
リチウムの、ハロゲン化物の塩、過塩素酸塩および含フッ素化合物の塩よりなる群から選択された少なくとも１種のリチウム塩が含まれる電解質とを含み、
前記電解質は、有機溶媒に溶解した塩、固体電解質またはゲル電解質であり、
酸化還元反応に伴う電子移動を電気エネルギーとして取り出し、充放電可能な電気化学素子であって、
前記活物質が、以下の一般式（１）：
前記化合物が、以下の一般式（２）：
A negative electrode,
An electrolyte containing at least one lithium salt selected from the group consisting of lithium halide salts, perchlorate salts and fluorine-containing compound salts ,
The electrolyte is a salt, solid electrolyte or gel electrolyte dissolved in an organic solvent,
Electrochemical elements that can be charged and discharged by taking out the electron transfer associated with the oxidation-reduction reaction as electric energy,
The active material has the following general formula (1):
The compound is represented by the following general formula (2):
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| US8993708B2 (en) | 2012-01-23 | 2015-03-31 | Nissan Chemical Industries, Ltd. | Carbazole polymer |
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|---|---|---|---|---|
| US8993708B2 (en) | 2012-01-23 | 2015-03-31 | Nissan Chemical Industries, Ltd. | Carbazole polymer |
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