TW201014021A - Storage device - Google Patents
Storage device Download PDFInfo
- Publication number
- TW201014021A TW201014021A TW098125540A TW98125540A TW201014021A TW 201014021 A TW201014021 A TW 201014021A TW 098125540 A TW098125540 A TW 098125540A TW 98125540 A TW98125540 A TW 98125540A TW 201014021 A TW201014021 A TW 201014021A
- Authority
- TW
- Taiwan
- Prior art keywords
- hydrated
- oxide
- storage device
- titanium dioxide
- power storage
- Prior art date
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims 1
- 159000000002 lithium salts Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000007773 negative electrode material Substances 0.000 abstract description 8
- 230000005611 electricity Effects 0.000 abstract description 6
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002002 slurry Substances 0.000 description 14
- -1 titanium hydroxide compound Chemical class 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LTSCTHUCRBEPEX-UHFFFAOYSA-N 1,3-dioxolan-2-one;hydrate Chemical compound O.O=C1OCCO1 LTSCTHUCRBEPEX-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- BPTVPJAXELOJGL-UHFFFAOYSA-N FC(C(C(C(C(C1=C(C(F)=C2F)F)=C2F)(F)F)=C1C(F)=C1F)=C1F)(F)F Chemical compound FC(C(C(C(C(C1=C(C(F)=C2F)F)=C2F)(F)F)=C1C(F)=C1F)=C1F)(F)F BPTVPJAXELOJGL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
- ZYWWPNFRBNSWIS-UHFFFAOYSA-K [Sb](Cl)(Cl)Cl.[Sn] Chemical class [Sb](Cl)(Cl)Cl.[Sn] ZYWWPNFRBNSWIS-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JCMGUODNZMETBM-UHFFFAOYSA-N arsenic trifluoride Chemical compound F[As](F)F JCMGUODNZMETBM-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical class [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UGWBWPXTGFPEFG-UHFFFAOYSA-N chloro hypochlorite chromium Chemical compound [Cr].ClOCl UGWBWPXTGFPEFG-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 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
- 239000007822 coupling agent Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ASQQEOXYFGEFKQ-UHFFFAOYSA-N dioxirane Chemical compound C1OO1 ASQQEOXYFGEFKQ-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical class [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical class [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- PPPHYGCRGMTZNA-UHFFFAOYSA-N trifluoromethyl hydrogen sulfate Chemical compound OS(=O)(=O)OC(F)(F)F PPPHYGCRGMTZNA-UHFFFAOYSA-N 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical class [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
Description
201014021 六、發明說明： 【發明所屬之技術領域】 本發明係有關電容量大的蓄電裝置。 【先前技術】 以正極、負極及非水電解液爲主之構成要素的蓄電裝 置截至目前被揭示有各種構成，實用化者有··移動機器等 Φ 之電源、再生用蓄電系統、個人電腦之支撐電源等。其中 又以，使石墨用於正極材料、二氧化鈦等之金屬氧化物用 於負極材料之蓄電裝置，其電容量較大（專利文獻1)。 該技術中，係以銳鈦礦型之二氧化鈦作爲負極材料使用後 ，特別可得到電容量大的蓄電裝置。 [專利文獻1]特開2008-1 24012號公報 【發明內容】 ❷ 本發明係於專利文獻1所記載之蓄電裝置中，提供一 種更高容量，且賦予良好的循環特性者爲其目的。 本發明者爲解決該課題，進行精密硏討後結果發現， 該蓄電裝置中，使銳鈦礦型之二氧化鈦經由特定方法所得 者，可改善循環特性，進而完成本發明。 亦即，本發明係含有含石墨之正極材料、含二氧化鈦 之負極材料及含電解液之蓄電裝置，該二氧化鈦係於水合 氧化鈦之表面上被覆除鈦之外的金屬之水合氧化物後，加 熱處理得到銳鈦礦型之二氧化鈦者爲其特徵之蓄電裝置。 -5- 201014021 本發明之蓄電裝置其電容量大，具良好的循環特性 且使二氧化鈦用於負極材料，故成本低。 【實施方式】 [發明實施之最佳形態] 本發明之蓄電裝置係含有含石墨之正極材料，含二氧 化鈦之負極材料以及電解液之蓄電裝置，該二氧化鈦係於 水合氧化鈦之表面上被覆除鈦之外的金屬之水合氧化物後 ，加熱處理得到銳鈦礦型之二氧化鈦者爲其特徵。 銳鈦礦型二氧化鈦由於其導電性高，故作成電容量大 之蓄電裝置時，此者極爲適用。又，通常藉由鋰電池之充 放電所造成之電池容量的降低被指爲係由於鋰離子的插入 脫離所造成之重覆膨脹、收縮而對電極活物質之構造造成 負荷，因此認爲結晶性高者較不易造成負荷。爲提供大的 電容量，具良好的循環特性之蓄電裝置時，被認爲使用結 晶性高的銳鈦礦型二氧化鈦者較爲理想。 銳鈦礦型二氧化鈦係使水合氧化鈦於適度的溫度下， 進行加熱處理後得到之熱履歷愈高，結晶性愈高。惟，當 熱履歷太高時，將轉化成金紅石型，則導致不易取得具有 所期待之高結晶性之銳鈦礦型二氧化鈦之問題點。 於本發明之水合氧化鈦之表面上被覆除鈦以外之金屬 的水合氧化物處理後，加熱處理得到銳鈦礦型二氧化鈦作 爲負極材料使用之蓄電裝置中，其電容量大，循環特性良 好之主要原因尙未明朗。 -6- 201014021 而’本發明者藉由該水合氧化物之被覆，即使受到高 度熱履歷’仍不易使銳鈦礦型轉化爲金紅石型，故使水合 氧化鈦充分加熱處理後被推測可得到結晶性良好之銳鈦礦 型二氧化鈦。 又，對於被覆除鈦以外之金屬的水合氧化鈦與對於被 覆銳鈦礦型氧化鈦不同，但意外地不致於對蓄電裝置之特 性產生不良影響。 Φ 本發明所使用之水合氧化鈦係除一般的氧化鈦之水合 物之外，亦含氫氧化鈦之化合物。此等水合氧化鈦係將如 :鈦鐵礦、鈦渣、等之含鈦鑛石於必要時，進行粉碎，於 硫酸進行溶解，同時使鈦成份與硫酸進行反應，生成硫酸 氧化鈦（Ti0S04 )，靜置分級、過濾後，使硫酸氧化鈦加 熱水解後取得。 被覆水合氧化鈦之該水合氧化物只要是水合氧化鈦以 外者即可，並未特別受限，如：水合氧化矽、水合氧化鋁 Φ 、水合氧化鉻、水合氧化錫、水合氧化銻、水合氧化鋅等 例。可將1種選自此等之水合氧化物進行被覆’可將2種 以上之水合氧化物層合而進行被覆，亦可將2種以上之水 合氧化物混合而進行被覆。其中又以水合氧化矽’其提昇 循環特性效果較高，爲較佳者，以緻密水合氧化矽者更爲 理想。 該水合氧化物之被覆量對於Ti〇2換算之水合氧化欽 而言，氧化物換算下（如：水合氧化矽以Si〇2換算、水 合氧化鋁以Al2〇3換算、水合氧化鉻以Zr〇2、水合氧化錫 201014021 以Sn〇2、水合氧化銻以sb2〇3換算、水合氧化鋅以Zn〇 換算等）爲0.01〜30重量％者宜。被覆量少於上述範圍時 ’將無法得到充分改良循環特性之效果，反之太多時，則 電極中二氧化鈦含量減少，降低電容量。更理想之被覆量 範圍爲0.05〜10重量份，以〇.1〜5重量份者最佳。 該水合氧化物之被覆係將水合氧化鈦分散於水等之媒 液作成漿料，必要時進行濕式粉碎後，對漿料中添加所期 待之包含於水合氧化物之金屬鹽溶液，添加酸性化合物或 鹼性化合物，或同時添加金屬鹽溶液與酸性化合物或鹼性 化合物等，於中和反應下進行。 作爲本發明可使用之金屬鹽者，如：矽鹽之矽酸鈉、 矽酸鉀等’鋁鹽之鋁酸鈉、硫酸鋁、硝酸鋁、氯化鋁、鉻 鹽之硫酸锆、硝酸锆、氯化鉻、氯氧化鉻等，錫鹽之硫酸 錫、硝酸錫、乙酸錫、錫醯氯等，銻鹽之氯化銻、硫酸銻 等、鲜鹽之硫酸辞等例。 又，作爲酸性化合物者如：硫酸、鹽酸等之無機酸、 乙酸等之有機酸，作爲鹼性化合物者如：氫氧化鈉、氫氧 化鉀、碳酸鈉等之鹼金屬或鹸土類金屬之氫氧化物或碳酸 化物、氨等之銨化合.物、胺類等之公知化合物可被使用。 被覆該水合氧化物後，脫水、洗淨，進行加熱處理者佳。 被覆緻密水合氧化矽時，作爲該被覆方法者，可應用 如特開昭53-33228號公報、特開平7-8971號公報等所載 之二氧化鈦中被覆緻密水合矽之公知的方法= 特開昭53 -33228號公報所載之方法係使二氧化欽之 201014021 獎料維持於80〜i〇(TC範圍之溫度，同時較佳調整漿料之 pH於9〜1〇·5之範圍，急速加入矽酸鈉後，於9〜1〇 5 範圍之pH下進行中和，之後，保持溫度8〇〜1〇(rc範圍 內50〜60分鐘。特開平7_897ι號公報所載之方法係使二 氧化鈦之漿料的pH調整爲9.5〜1 1之範圍後，於60°C以 上’較佳者70。(：以上，更佳者爲9〇。(：以上之溫度下，以 30〜120分鐘之時間緩慢添加矽酸鹽後，進行中和，之後 φ 維持漿料溫度，同時保持60〜120分鐘。 加熱處理之溫度爲800°C以上，未達1 000°C之範圍者 宜。低於該範圍時，則延緩水合氧化鈦之脫水，不易生成 銳鈦礦型二氧化鈦，若爲1 〇〇〇°c以上則，即使是本發明仍 不易防止轉化金紅石型。理想的加熱溫度範圍爲800〜980 t。加熱處理時間依其處理量而言，而適當設定之，作業 上以1〜20小時爲宜。加熱處理時，可使用流動層裝置、 旋轉窖爐、隧道窖等之公知者’特別以旋轉窖爐較佳。加 φ 熱處理後，必要時藉由公知之方法’進行乾式粉碎亦可’ 或漿料化後，進行濕式粉碎、脫水、乾燥’亦可進行乾式 粉碎。濕式粉碎時以縱型混砂機、橫型混砂機等’乾燥時 以黏合式加熱器、間歇式加熱器等、乾式粉碎時以錘磨機 、插接機等之撞擊粉碎機、解碎機等之磨碎粉碎機、噴射 磨等氣流粉碎機、噴霧乾燥機等機器。 胃自以上方法所得之二氧化鈦係具有銳鈦礦塑之結晶 構造，其粒子形狀可任意爲球狀、多面體狀等之各向同性 形狀、棒狀、纖維狀、薄片狀等之各向異性形狀等’並未 -9- 201014021 特別受限。又，具有經由除鈦以外之金屬的水合氧化物之 被覆之加熱處理之無水氧化物之被覆層。加熱處理後’在 不阻擾本發明效果之範圍下，進一步可於金屬之水合氧化 物、磷酸鹽等之無機化合物、界面活性劑、偶合劑等之有 機化合物下進行被覆表面。又，將所得之二氧化鈦進行噴 霧乾燥等，進行二次粒子之造粒後，亦可使用之。此二氧 化鈦之比表面積（經由BET法）爲5〜5 00m2/g之範圍， 更擴大電容量爲較佳，更佳者爲5〜3 50m2/g之範圍。 接著，用於本發明中正極材料之石墨並未特別受限。 另外，本發明中石墨係指由X線衍射002面之波峰位置所 求出之（1(。〇2)爲0.3 3 5〜0.344nm之範圍者。其中又以使用 比表面積（經由BET法）爲0.5〜300 m2/g之範圍的石墨 者宜，更佳者爲5〜100m2/g之範圍者。 作爲浸漬該正極及負極之電解液者，可使用如：使溶 質溶於非水溶媒中者。作爲作用於電解液之陰離子者如： 1種選自4氟化硼酸離子（BFV) 、6氟化憐酸離子（ρρ6· )、過氯酸離子（CIO〆）、6氟化砷（AsF6_) 、6氟化錬 (SbFe )、全氟甲擴醯（CF3S〇2_)、全氟甲基硫酸鹽（ CF3S〇T)所成群之例。 又’作爲陽離子者爲選自對稱、非對稱之四級錢離子 、乙基甲基咪唑鑰、螺旋（1，1’）雙吡咯鑰等之咪哩鐵衍 生物離子、鋰離子所成群。其中又以含鋰離子者較佳。 另外’作爲非水溶媒者，如：1種選自四氫呋喃（ THF )、甲基四氫呋喃（MeTHF )、甲基甲醯胺、甲基乙 201014021 醯胺、二乙基碳酸酯、二甲醚（DME )、丙烯碳酸酯（pc )、二甲基碳酸酯（DMC)、二乙基 碳酸酯（DEC)、乙烯碳酸酯（EC)、乙基甲基碳酸酯（ EMC)等之碳酸酯類、乙腈（AN)、環丁碼（SL)或部 份分子含有氟之此等非水溶媒所成群。 本發明之蓄電裝置爲含有上述之正極、負極、電解液 及分隔器，具體例如：電氣化學的電容器、混合電容器、 • 氧化還原電容器、電氣雙層電容器、鋰電池等例。正極、 負極係於正極材料、負極材料中各自加入碳黑、乙炔碳黑 、乙烯碳黑等之導電材料與氟樹脂、水溶性橡膠系樹脂等 之黏合劑，適當成形或塗佈後所得。分離器係利用多孔性 聚乙烯薄膜、聚丙烯薄膜等。 [實施例] 以下顯示本發明之實施例，而本發明未受限於此等。 [實施例1] (正極之製造） 將X線衍射所求出之<1(002)爲〇.3355nm之石墨、乙炔 碳黑及聚氟化亞乙烯樹脂以重量比70 : 20 : 1 〇進行混煉 。將所得之混煉物塗佈於作爲集電體之鋁箔後’於1 20°C 下進行乾燥10分鐘後，切取直徑16mm之圓形’於 1 7MPa進行加壓得到正極。該正極之活化物質重量爲 1 0 m g ° -11 - 201014021 (負極之製造） 將水合氧化鈦以Ti〇2換算爲300g懸浮於11純 作成漿料’以氫氧化鈉水溶液調整該漿料之pH爲 著使漿料溫度加溫爲70°C後，以2小時的時間滴入 水溶液。接著，使漿料溫度加溫爲90 °C後，以2小 間滴入稀釋硫酸，進行中和成PH5，更維持30分 覆緻密水合氧化矽（Si02爲0.3重量％)。之後， 洗淨’進一步於空氣中8501下進行加熱5小時， 鈦礦型二氧化鈦（試料a)。此者之比表面積爲1 。將具有所得緻密無水氧化矽之被覆層之銳鈦礦型 鈦、乙炔碳黑及聚氟化亞乙烯樹脂以重量比70: 進行混煉。將所得混煉物塗佈於作爲集電體使用之 ，於120°C下進行乾燥10分鐘後，切成直徑16mm ，於17MPa進行加壓，得到負極。該負極之活化物 爲 1 Omg。 (蓄電裝置之製造） 將該正極、負極於150°C下進行真空乾燥4小 於露點-70 °C以下之手套箱中，組裝可密閉之銅幣 用槽。試驗用槽中使用不鏽鋼製材質（SUS316) 20mm、高度3.2mm者。正極置於評定用槽的下部 上放置分隔器之玻璃纖維性濾紙，由其上面滴入以 莫耳/1之非水電解液濃度使LiPF6溶解之乙烯碳酸 水中， 10，接 矽酸鈉 時的時 鐘，被 脫水、 得到銳 5.5m2/g 二氧化 20 ： 10 銅箔後 之圓形 質重量 時後， 型試驗 、外徑 罐，其 作成1 酯與乙 201014021 基甲基碳酸酯之混合溶液（體積比爲3:7混合）。其上 面載上負極及厚度調整用之0.5mm厚的隔板與鋼板（均爲 SUS316製），覆蓋附有丙烯製墊圈之上部罐，咬緊外周 緣部進行密封，得到本發明之蓄電裝置（試料A)。 [實施例2] 實施例1中，使緻密水合氧化矽之被覆量爲7〇重量 φ %之Si〇2 ’加熱處理溫度爲l〇〇〇°C，得到銳鈦礦型二氧化 欽（試料b)除外’與實施例1同法，得到本發明之蓄電 裝置（試料B)。另外，試料b之比表面積爲l4 5m2/gs [比較例1] 實施例1中，使用市售之銳鈦礦型氧化欽（ST_21 : 石原產業製、比表面積62m2/g、無被覆）取代試料a之外 ，與實施例1同法，得到比較對象之蓄電裝置（試料c) ❹ [比較例2] 實施例1中，使用市售之銳鈦礦型氧化飲 石原產業製、比表面積10m2/g、無被覆）取代試料之外 ，與實施例1同法，得到比較對象之蓄電裝置r _ 、 识[轼料D ) [比較例3] -13- 201014021 使市售之銳鈦礦型氧化鈦（ST-41 :石原產業製）以 Ti〇2換算爲300g懸浮於11純水中作成漿料，以氫氧化鈉 水溶液調整該漿料之pH爲10，接著使漿料溫度加溫爲70 °C後’以2小時之時間滴入矽酸鈉水溶液。持續使漿料溫 度加溫爲90 °C後，2小時之時間滴入稀釋硫酸，中和爲 PH5，更維持30分鐘，被覆緻密水合氧化矽（Si02爲0.3 重量％)。之後，脫水、洗淨，進一步於空氣中3001下 加熱處理5小時，得到具有緻密無水氧化矽之被覆層之銳 鈦礦型二氧化鈦（試料e)。實施例1中使用試料e取代 試料a之外’與實施例1同法，得到比較對象之蓄電裝置 (試料E)。另外，試料e之比表面積爲4.6 8m2/g。 [比較例4] 比較例3中，得到緻密水合氧化矽之被覆量爲4.0重 量％之Si02之銳鈦礦型二氧化鈦（試料f)之外，與比較 例3同法，得到比較對象之蓄電裝置（試料F)。另外， 試料f之比表面積爲7.33m2/g。 [評定1 :循環特性之測定（1 )] 針對實施例1及比較例1、2所得之蓄電裝置（試料 A、C、D)，進行循環特性之評定。對於各試料，設定充 放電電流爲0.3mA，於定電流以3.3B進行充電後，同樣 的，放電至1.0V，重覆進行此充放電循環30循環。測定 第2循環與第30循環之放電容量，此作爲各自之電容量 -14- 201014021 ，以（第30循環之電容量/第2循環之電容量）χ1〇〇作爲 循環特性。結果示於表1。又，將各自之容量維持率之變 化示於圖1〜3。比較例2雖外表顯示高度循環特性，而此 原本就是因爲其電容量爲低。 [表1] 試料 電容量(mAh/g) 循環特性 第2循環 第30循環 實施例1 A 55.5 53.4 97.3 比較例1 C 54.1 50.0 92.4 比較例2 D 43.6 42.9 98.6 [評定2 :循環特性之測定（2)]201014021 VI. Description of the Invention: [Technical Field According to the Invention] The present invention relates to a power storage device having a large capacity. [Prior Art] A power storage device that is mainly composed of a positive electrode, a negative electrode, and a non-aqueous electrolyte has been disclosed in various configurations. The user has a power supply such as a mobile device, a power storage system for reproduction, and a personal computer. Support power supply, etc. In addition, graphite is used for a power storage device for a negative electrode material, such as a metal oxide such as a positive electrode material or titanium dioxide, and has a large capacitance (Patent Document 1). In this technique, after anatase type titanium dioxide is used as a negative electrode material, a power storage device having a large capacitance can be obtained in particular. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-124012. The present invention is directed to a power storage device described in Patent Document 1, which provides a higher capacity and imparts excellent cycle characteristics. In order to solve this problem, the inventors of the present invention have found that the anatase type titanium dioxide can be obtained by a specific method, and the cycle characteristics can be improved, and the present invention can be completed. That is, the present invention comprises a cathode material containing graphite, a cathode material containing titanium oxide, and a storage device containing an electrolyte which is coated on the surface of the hydrous titanium oxide to coat a hydrated oxide of a metal other than titanium, and then heated. A power storage device characterized by obtaining anatase type titanium dioxide is processed. -5-201014021 The power storage device of the present invention has a large capacity, has good cycle characteristics, and uses titanium dioxide for a negative electrode material, so that the cost is low. [Embodiment] The best mode for carrying out the invention The electric storage device of the present invention comprises a cathode material containing graphite, a negative electrode material containing titanium oxide, and an electrolyte storage device, and the titanium dioxide is coated on the surface of the hydrous titanium oxide to remove titanium. After the hydrated oxide of the metal is removed, the anatase type titanium dioxide is characterized by heat treatment. Anatase type titanium dioxide is highly suitable for use as a power storage device having a large capacitance because of its high conductivity. In addition, the decrease in the battery capacity caused by the charge and discharge of the lithium battery is generally referred to as the load on the structure of the electrode active material due to the repeated expansion and contraction caused by the insertion and detachment of lithium ions, and therefore the crystallinity is considered to be high. It is less likely to cause a load. In order to provide a large electric capacity and a power storage device having a good cycle characteristic, it is considered to be preferable to use an anatase type titanium dioxide having high crystallinity. The anatase type titanium dioxide system heats the hydrous titanium oxide at a moderate temperature, and the heat history is higher, and the crystallinity is higher. However, when the heat history is too high, it will be converted into a rutile type, which results in a problem that it is difficult to obtain anatase type titanium dioxide having a desired high crystallinity. In the electric storage device in which the surface of the hydrous titanium oxide of the present invention is coated with a hydrated oxide of a metal other than titanium and then heat-treated to obtain anatase-type titanium dioxide as a negative electrode material, the electric capacity is large and the cycle characteristics are good. The reason is not clear. -6- 201014021 And the 'inventors of the present invention are not able to convert the anatase type into a rutile type even if it is subjected to the coating of the hydrated oxide, so it is presumed that the hydrated titanium oxide is sufficiently heat-treated. Anatase type titanium dioxide having good crystallinity. Further, the hydrous titanium oxide coated with a metal other than titanium is different from the coated anatase titanium oxide, but unexpectedly does not adversely affect the characteristics of the electrical storage device. Φ The hydrous titanium oxide used in the present invention contains a titanium hydroxide compound in addition to the general titanium oxide hydrate. Such hydrous titanium oxides are pulverized if necessary, such as ilmenite, titanium slag, or the like, and are dissolved in sulfuric acid, and the titanium component is reacted with sulfuric acid to form titanium sulfate (Ti0S04). After standing and grading and filtering, the titanium sulfate sulfate is heated and hydrolyzed. The hydrated oxide of the coated hydrous titanium oxide is not particularly limited as long as it is hydrated titanium oxide, such as hydrated cerium oxide, hydrated alumina Φ, hydrated chromium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated oxidation. Examples of zinc and the like. One type of hydrated oxide selected from these may be coated. 'Two or more kinds of hydrated oxides may be laminated and coated, or two or more kinds of hydrated oxides may be mixed and coated. Among them, hydrated cerium oxide has a higher effect on improving the cycle characteristics, and is preferred, and a dense hydrated cerium oxide is more desirable. The amount of the hydrated oxide to be coated is oxidized in terms of Ti 〇 2, in terms of oxide (for example, hydrated cerium oxide in terms of Si 〇 2, hydrated alumina in terms of Al 2 〇 3, hydrated chromium oxide in Zr 〇) 2. Hydrated tin oxide 201014021 is preferably 0.01 to 30% by weight of Sn 〇 2, hydrated cerium oxide in terms of sb 2 〇 3, hydrated zinc oxide in terms of Zn 〇, etc.). When the amount of coating is less than the above range, the effect of sufficiently improving the cycle characteristics will not be obtained, and if it is too large, the content of titanium dioxide in the electrode will be reduced to lower the capacitance. More preferably, the coating amount is in the range of 0.05 to 10 parts by weight, preferably 〇.1 to 5 parts by weight. In the coating of the hydrated oxide, the hydrous titanium oxide is dispersed in a vehicle liquid such as water to form a slurry, and if necessary, after wet pulverization, a desired metal salt solution contained in the hydrated oxide is added to the slurry, and acidity is added. The compound or the basic compound or a metal salt solution and an acidic compound or a basic compound are simultaneously added under a neutralization reaction. As the metal salt which can be used in the present invention, for example, sodium citrate of strontium salt, potassium aluminate, etc., aluminum aluminate of aluminum salt, aluminum sulfate, aluminum nitrate, aluminum chloride, zirconium sulfate of chromium salt, zirconium nitrate, Examples of chromium chloride, chromium oxychloride, etc., tin salts of tin sulfate, tin nitrate, tin acetate, tin antimony chloride, barium chloride, barium sulfate, barium sulfate, and the like. Further, as the acidic compound, for example, an inorganic acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid, or a basic compound such as an alkali metal such as sodium hydroxide, potassium hydroxide or sodium carbonate or a hydrogen of an alumina-based metal. A known compound such as an ammonium compound or an amine such as an oxide or a carbonate or ammonia can be used. After the hydrated oxide is coated, it is preferably dehydrated, washed, and heat treated. When a dense hydrated ruthenium oxide is coated, a known method of coating a dense hydrated ruthenium in titanium dioxide contained in JP-A-53-33228, JP-A-7-8971, and the like can be applied. The method described in the Gazette No. 53-33228 maintains the 201014021 prize of the Dioxide Chinensis at 80~i〇 (the temperature in the range of TC, and preferably adjusts the pH of the slurry in the range of 9~1〇·5, and joins rapidly. After sodium citrate, neutralization is carried out at a pH ranging from 9 to 1 〇 5, and thereafter, the temperature is maintained at 8 Torr to 1 Torr (50 to 60 minutes in the range of rc. The method described in Japanese Patent Laid-Open Publication No. Hei 7-897. The pH of the slurry is adjusted to a range of 9.5 to 1 1 and is preferably 60 or higher at 70 ° C. (: above, more preferably 9 〇. (: at the above temperature, for 30 to 120 minutes) After the citrate is slowly added, the neutralization is carried out, and then φ maintains the slurry temperature while maintaining the temperature for 60 to 120 minutes. The temperature of the heat treatment is 800 ° C or more, and the range of less than 1 000 ° C is suitable. Below this range When it delays the dehydration of hydrated titanium oxide, it is difficult to form anatase titanium dioxide, if 1 以上 °c or more, even in the present invention, it is not easy to prevent the conversion of rutile type. The ideal heating temperature range is 800 to 980 t. The heat treatment time is appropriately set according to the amount of the treatment, and the operation is appropriately set. 1 to 20 hours is preferable. When heat treatment, a known person such as a fluidized bed device, a rotary crucible furnace, a tunnel crucible or the like can be used. In particular, a rotary crucible furnace is preferably used. After heat treatment with φ, if necessary, by a known method Dry pulverization can also be carried out after wet pulverization, dehydration and drying after slurrying. Dry pulverization can be carried out by wet pulverization, such as vertical sand mixer, horizontal sand mixer, etc. For the dry pulverization, such as a hammer mill, a crusher such as a hammer mill, a pulverizer such as a pulverizer, a jet mill such as a jet mill, a spray dryer, etc. The titanium dioxide obtained by the above method has an anatase plastic crystal structure, and the particle shape thereof can be any isotropic shape such as a spherical shape or a polyhedral shape, an anisotropic shape such as a rod shape, a fiber shape or a flake shape, etc. -9- 201014021 is particularly limited. Further, there is a coating layer of a heat-treated anhydrous oxide which is coated with a hydrated oxide of a metal other than titanium. After the heat treatment, 'without obstructing the effects of the present invention, further The surface of the coating can be applied to an organic compound such as an inorganic compound such as a metal hydrated oxide or a phosphate, a surfactant, or a coupling agent, and the obtained titanium dioxide is spray-dried or the like to granulate the secondary particles. The specific surface area of the titanium dioxide (via the BET method) is in the range of 5 to 500 m 2 /g, and the capacity is more preferably expanded, more preferably in the range of 5 to 3 50 m 2 /g. The graphite of the positive electrode material in the present invention is not particularly limited. Further, in the present invention, the graphite refers to a range of (3 (. 〇 2) of 0.3 3 5 to 0.344 nm which is obtained by the peak position of the 002 plane of the X-ray diffraction. Among them, the specific surface area (via the BET method) is used. It is preferably in the range of 0.5 to 300 m 2 /g of graphite, more preferably in the range of 5 to 100 m 2 /g. As the electrolyte for impregnating the positive electrode and the negative electrode, for example, the solute can be dissolved in a non-aqueous solvent. As an anion acting on the electrolyte, one is selected from the group consisting of 4 fluorinated boronic acid ions (BFV), 6 fluorinated acid ions (ρρ6· ), perchloric acid ions (CIO〆), and 6 arsenic fluoride ( Examples of groups of AsF6_), bismuth fluoride (SbFe), perfluoromethyl fluorene (CF3S〇2_), and perfluoromethyl sulfate (CF3S〇T). Symmetrical four-stage money ion, ethyl methyl imidazole key, spiral (1,1') double pyrrole key, etc., which are grouped with lithium ion ions, and those containing lithium ions are preferred. 'As a non-aqueous solvent, such as: one selected from tetrahydrofuran (THF), methyltetrahydrofuran (MeTHF), methylformamide, methyl ethyl 20101402 1 decylamine, diethyl carbonate, dimethyl ether (DME), propylene carbonate (pc), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), B A carbonate group such as methyl carbonate (EMC), acetonitrile (AN), cyclobutyl (SL) or a non-aqueous solvent containing a part of a molecule containing fluorine. The power storage device of the present invention contains the above-mentioned Examples of the positive electrode, the negative electrode, the electrolyte, and the separator, for example, an electrochemical capacitor, a hybrid capacitor, a redox capacitor, an electric double layer capacitor, a lithium battery, etc. The positive electrode and the negative electrode are each added to the positive electrode material and the negative electrode material. A binder of a conductive material such as black, acetylene black or ethylene carbon black, a fluororesin or a water-soluble rubber-based resin, which is obtained by suitable molding or coating, is obtained by using a porous polyethylene film or a polypropylene film. [Examples] The examples of the present invention are shown below, but the present invention is not limited thereto. [Example 1] (Production of positive electrode) The <1 (002) obtained by X-ray diffraction was 〇.3355 nm. Graphite, acetylene black and polyfluorinated ethylene The resin was kneaded at a weight ratio of 70:20:1. The obtained kneaded product was applied to an aluminum foil as a current collector, and then dried at 10 ° C for 10 minutes, and then cut into a circle having a diameter of 16 mm. Pressurizing at 17 MPa to obtain a positive electrode. The weight of the active material of the positive electrode is 10 mg ° -11 - 201014021 (manufactured by a negative electrode). The hydrous titanium oxide is converted into 300 g of Ti 〇 2 in a pure slurry. The pH of the slurry was adjusted with an aqueous solution of sodium oxide so that the temperature of the slurry was increased to 70 ° C, and then the aqueous solution was dropped over a period of 2 hours. Then, after the slurry temperature was raised to 90 °C, the diluted sulfuric acid was dropped into the mixture for 2 hours to neutralize to pH 5, and the densely hydrated cerium oxide (SiO 2 was 0.3% by weight) was further maintained for 30 minutes. Thereafter, the mixture was further heated in an air at 8501 for 5 hours to form a titanium oxide type titanium oxide (sample a). This has a specific surface area of 1. The anatase titanium, acetylene black and polyvinylidene fluoride resin having the coating layer of the obtained dense anhydrous cerium oxide were kneaded at a weight ratio of 70:. The obtained kneaded product was applied to a current collector, dried at 120 ° C for 10 minutes, cut into a diameter of 16 mm, and pressurized at 17 MPa to obtain a negative electrode. The active material of the negative electrode was 1 Omg. (Manufacturing of Power Storage Device) The positive electrode and the negative electrode were vacuum-dried at 150 ° C for 4 times in a glove box having a dew point of -70 ° C or lower to assemble a sealable copper coin tank. A stainless steel material (SUS316) of 20 mm and a height of 3.2 mm were used for the test tank. The positive electrode is placed on the lower portion of the evaluation tank, and the separator is placed on the glass fiber filter paper, and the ethylene carbonate water in which the LiPF6 is dissolved in the concentration of the non-aqueous electrolyte of Mohr/1 is dropped thereon, 10, when sodium citrate is added After the clock is dehydrated and obtained a sharp mass of 5.5m2/g 20:10 copper foil, the type test, outer diameter tank, is made into a mixed solution of 1 ester and B 201014021 methyl carbonate ( The volume ratio is 3:7 mixed). A 0.5 mm thick separator and a steel plate (all manufactured by SUS316) for carrying the negative electrode and the thickness adjustment are placed thereon, and the upper can is covered with a propylene gasket, and the outer peripheral portion is bit-sealed to be sealed, thereby obtaining the electricity storage device of the present invention ( Sample A). [Example 2] In Example 1, the coating amount of the dense hydrated cerium oxide was 7 〇 weight φ % of Si 〇 2 'heat treatment temperature was 10 ° C, and anatase type dioxirane was obtained (sample) b) Except for the same method as in Example 1, the electricity storage device (sample B) of the present invention was obtained. Further, the specific surface area of the sample b was 14 5 m 2 /gs [Comparative Example 1] In Example 1, a commercially available anatase type oxidized chin (ST_21: manufactured by Ishihara Shoei, specific surface area: 62 m 2 /g, uncoated) was used instead of the sample. In the same manner as in Example 1, a power storage device (sample c) was obtained in the same manner as in Example 1 [Comparative Example 2] In Example 1, a commercially available anatase-type oxidized drinking stone was used, and a specific surface area of 10 m 2 / g, no coating), in addition to the sample, in the same manner as in the first embodiment, the power storage device r _ , which is the object of comparison, was obtained [Comparative Example 3] -13 - 201014021 The commercially available anatase type oxidation Titanium (ST-41: manufactured by Ishihara Sangyo Co., Ltd.) was suspended in 11 pure water in a slurry of 300 g of Ti〇2 to prepare a slurry, and the pH of the slurry was adjusted to 10 with an aqueous sodium hydroxide solution, and then the temperature of the slurry was heated to 70. After °C, 'aqueous sodium citrate solution was added dropwise over 2 hours. After continuously heating the slurry temperature to 90 ° C, dilute sulfuric acid was added dropwise over 2 hours, neutralized to pH 5, and maintained for 30 minutes, and the dense hydrated cerium oxide (0.3% by weight of SiO 2 ) was coated. Thereafter, the mixture was dehydrated, washed, and further heat-treated in air at 3001 for 5 hours to obtain anatase-type titanium oxide (sample e) having a coating layer of dense anhydrous cerium oxide. In the first embodiment, the sample e was used instead of the sample a. In the same manner as in the first embodiment, a power storage device (sample E) to be compared was obtained. Further, the specific surface area of the sample e was 4.6 8 m 2 /g. [Comparative Example 4] In Comparative Example 3, a storage device of a comparative object was obtained in the same manner as in Comparative Example 3 except that an anatase type titanium dioxide (sample f) having a coating amount of 4.0% by weight of dense hydrated cerium oxide was obtained. (Sample F). Further, the specific surface area of the sample f was 7.33 m 2 /g. [Evaluation 1 : Measurement of cycle characteristics (1 )] The electrical storage devices (samples A, C, and D) obtained in Example 1 and Comparative Examples 1 and 2 were evaluated for cycle characteristics. For each sample, the charge/discharge current was set to 0.3 mA, and after the constant current was charged at 3.3 B, the battery was discharged to 1.0 V in the same manner, and the charge and discharge cycle was repeated for 30 cycles. The discharge capacities of the second cycle and the 30th cycle were measured, and as the respective capacitance -14 - 201014021, (the capacity of the 30th cycle / the capacity of the second cycle) χ 1 〇〇 was used as the cycle characteristic. The results are shown in Table 1. Further, changes in the respective capacity retention ratios are shown in Figs. 1 to 3. Comparative Example 2 showed a high cycle characteristic, which was originally due to its low capacitance. [Table 1] Sample capacity (mAh/g) Cycle characteristics Second cycle 30th cycle Example 1 A 55.5 53.4 97.3 Comparative example 1 C 54.1 50.0 92.4 Comparative example 2 D 43.6 42.9 98.6 [Evaluation 2: Measurement of cycle characteristics ( 2)]
針對實施例1、2及比較例3、4 (試料A、B、E、F )，與評定1同法，進行循環特性之評定，對於第2循環 (初期電容量）之電容量，算出第10、20、30循環之電 容量，以乘以1 〇〇之値作爲循環特性（％ )。結果示於表With respect to Examples 1 and 2 and Comparative Examples 3 and 4 (samples A, B, E, and F), the same cycle as in Evaluation 1, the cycle characteristics were evaluated, and the capacitance of the second cycle (initial capacitance) was calculated. The capacitance of the 10, 20, and 30 cycles is multiplied by 1 値 as the cycle characteristic (%). The results are shown in the table
A 胃[表2] 1。 試料 初期電容量 (mAh/g) 循環特性(％) 第10循環/ 第2循環 第20循環/ 第2循環 第30循環/ 第2循環 實施例1 A 44.4 101 100 100 實施例2 B 45.3 101 100 100 比較例3 E 49.8 96 71 53 比較例4 F 1.9 35 35 24 由評定1、2證明，本發明之蓄電裝置爲高容量，具 良好的循環特性。 -15- 201014021 [產業上可利用性] 本發明之蓄電裝置係適用於電氣汽車等之移動體用之 電源、電氣事業用之電力儲存系統等。 1所得之蓄電裝置 1所得之蓄電裝置 2所得之蓄電裝置 【圖式簡單說明】 [圖1 ]代表實施例 環特性的曲線圖。 [圖2 ]代表比較例 環特性的曲線圖。 [圖3 ]代表比較例 環特性的曲線圖。 (試料A)之循 鲁 (試料C)之循 (試料D )之循A stomach [Table 2] 1. Sample initial capacity (mAh/g) Cycle characteristics (%) 10th cycle / 2nd cycle 20th cycle / 2nd cycle 30th cycle / 2nd cycle Example 1 A 44.4 101 100 100 Example 2 B 45.3 101 100 100 Comparative Example 3 E 49.8 96 71 53 Comparative Example 4 F 1.9 35 35 24 As evidenced by the evaluations 1 and 2, the electricity storage device of the present invention has a high capacity and good cycle characteristics. -15- 201014021 [Industrial Applicability] The power storage device of the present invention is applied to a power source for a mobile body such as an electric car or an electric power storage system for an electric business. (1) A power storage device obtained by the power storage device 1 obtained by the present invention. [Fig. 1] A graph showing the ring characteristics of the embodiment. [Fig. 2] A graph representing the ring characteristics of the comparative example. [Fig. 3] A graph representing the ring characteristics of the comparative example. (sample A) follow the cycle (sample C) (sample D)
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| JP5208244B2 (en) * | 2011-05-06 | 2013-06-12 | 株式会社豊田自動織機 | Negative electrode active material for lithium ion secondary battery and method for producing the same, lithium ion secondary battery and method for producing the same |
| JP5586553B2 (en) * | 2011-09-22 | 2014-09-10 | 株式会社東芝 | Active material and manufacturing method thereof, non-aqueous electrolyte battery and battery pack |
| JP6062445B2 (en) * | 2011-10-25 | 2017-01-18 | タイワン ホパックス ケミカルズ マニュファクチャリング カンパニー リミテッド | Manufacturing method of negative electrode material and negative electrode material by the same method |
| JP2014130717A (en) | 2012-12-28 | 2014-07-10 | Ricoh Co Ltd | Nonaqueous electrolyte storage element |
| JP6448807B2 (en) * | 2015-09-11 | 2019-01-09 | 株式会社東芝 | NEGATIVE ELECTRODE ACTIVE MATERIAL AND ITS MANUFACTURING METHOD, NON-AQUEOUS ELECTROLYTE BATTERY, AND BATTERY PACK |
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| JP5095939B2 (en) * | 2004-12-28 | 2012-12-12 | 石原産業株式会社 | Black titanium oxynitride |
| JP5399623B2 (en) * | 2006-10-20 | 2014-01-29 | 石原産業株式会社 | Power storage device |
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- 2009-07-29 WO PCT/JP2009/063459 patent/WO2010013726A1/en active Application Filing
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| JP5419874B2 (en) | 2014-02-19 |
| WO2010013726A1 (en) | 2010-02-04 |
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