JP5937151B2 - Zirconium-containing olivine-type positive electrode material and method for producing the same - Google Patents
Zirconium-containing olivine-type positive electrode material and method for producing the same Download PDFInfo
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- JP5937151B2 JP5937151B2 JP2014154515A JP2014154515A JP5937151B2 JP 5937151 B2 JP5937151 B2 JP 5937151B2 JP 2014154515 A JP2014154515 A JP 2014154515A JP 2014154515 A JP2014154515 A JP 2014154515A JP 5937151 B2 JP5937151 B2 JP 5937151B2
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- zirconium
- lithium
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- 239000007774 positive electrode material Substances 0.000 title claims description 69
- 229910052726 zirconium Inorganic materials 0.000 title claims description 39
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- -1 silicate compound Chemical class 0.000 claims description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 40
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 150000002642 lithium compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000010450 olivine Substances 0.000 claims description 10
- 229910052609 olivine Inorganic materials 0.000 claims description 10
- 150000003755 zirconium compounds Chemical class 0.000 claims description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 7
- 150000007524 organic acids Chemical group 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 238000001027 hydrothermal synthesis Methods 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 230000002093 peripheral effect Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910004066 NOB-MINI Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DZKLJFWEISCYLR-UHFFFAOYSA-J C(CCCCCCCCCCC)(=[O+][O-])[O-].[Zr+4].C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCC)(=[O+][O-])[O-] Chemical compound C(CCCCCCCCCCC)(=[O+][O-])[O-].[Zr+4].C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCCCCCCCCCC)(=[O+][O-])[O-] DZKLJFWEISCYLR-UHFFFAOYSA-J 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910011083 Li2Fe0.09Mn0.85Zr0.03SiO4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- JINJMFAIGCWUDW-UHFFFAOYSA-L zirconium(2+);diacetate Chemical compound [Zr+2].CC([O-])=O.CC([O-])=O JINJMFAIGCWUDW-UHFFFAOYSA-L 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、高い電池物性を発現し得るジルコニウム含有オリビン型正極材料及びその製造方法に関する。 The present invention relates to a zirconium-containing olivine-type positive electrode material capable of expressing high battery properties and a method for producing the same.
リチウムイオン電池は、非水電解質電池の１種であり、携帯電話、デジタルカメラ、ノートＰＣ、ハイブリッド自動車、電気自動車等広い分野に利用されている。リチウムイオン電池は、正極材料としてリチウム金属酸化物を用い、負極材料としてグラファイト等の炭素材を用いるものが主流となっている。 Lithium ion batteries are a type of non-aqueous electrolyte battery and are used in a wide range of fields such as mobile phones, digital cameras, notebook PCs, hybrid cars, and electric cars. Lithium ion batteries mainly use lithium metal oxide as a positive electrode material and a carbon material such as graphite as a negative electrode material.
この正極材料としては、コバルト酸リチウム（ＬｉＣｏＯ2）、マンガン酸リチウム（ＬｉＭｎＯ2）、リン酸鉄リチウム（ＬｉＦｅＰＯ4）、ケイ酸鉄リチウム（Ｌｉ2ＦｅＳｉＯ4）等が知られている。このうち、ＬｉＦｅＰＯ4やＬｉ2ＦｅＳｉＯ4等は、オリビン構造を有し、高容量のリチウムイオン二次電池用正極材料として有用であり、種々の開発がなされている。 As this positive electrode material, lithium cobaltate (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium iron phosphate (LiFePO 4 ), lithium iron silicate (Li 2 FeSiO 4 ) and the like are known. Among these, LiFePO 4 and Li 2 FeSiO 4 have an olivine structure and are useful as positive electrode materials for high-capacity lithium ion secondary batteries, and various developments have been made.
例えば、特許文献１には、ケイ酸金属リチウムにジルコニウムをドープしたオリビン型シリケート化合物が開示されており、これによって電池物性の向上を図っている。 For example, Patent Document 1 discloses an olivine-type silicate compound obtained by doping lithium metal silicate with zirconium, thereby improving battery physical properties.
しかしながら、リチウムイオン二次電池の充放電容量は、正極材料の種類によっても大きく変動することもあり、より電池物性を高めることのできる、上記特許文献に記載のものとは異なる新たな種類の正極材料の実現が望まれている。 However, the charge / discharge capacity of the lithium ion secondary battery may vary greatly depending on the type of the positive electrode material, and a new type of positive electrode different from that described in the above-mentioned patent document can further improve the battery physical properties. Realization of materials is desired.
したがって、本発明の課題は、より優れた電池物性を発現することのできるジルコニウム含有オリビン型正極材料及びその製造方法を提供することにある。 Therefore, the subject of this invention is providing the zirconium containing olivine type positive electrode material which can express the more outstanding battery physical property, and its manufacturing method.
そこで本発明者らは、種々検討したところ、Ｓｉ原子やＯ原子に加え、Ｐ原子及び／又はＦ原子を含むジルコニウム含有のオリビン型正極材料であれば、大きな充放電容量を示す二次電池が得られることを見出し、本発明を完成させるに至った。 Therefore, the present inventors have made various studies, and if a zirconium-containing olivine-type positive electrode material containing P atoms and / or F atoms in addition to Si atoms and O atoms, a secondary battery exhibiting a large charge / discharge capacity can be obtained. The inventors have found that the present invention can be obtained and have completed the present invention.
すなわち、本発明は、次式（１）：
Ｌｉ2ＦｅaＮｉbＣｏcＭｎdＺｒxＳｉ1-zＰ0.8zＯ4-yＦ2y・・・（１）
（式（１）中、ａ、ｂ、ｃ及びｄはａ＋ｂ＋ｃ＋ｄ=１−２ｘを満たし、ｘは０＜ｘ＜０．５であり、ｙは０≦ｙ≦２であり、ｚは０≦ｚ≦０．１であり、かつｙ及びｚは０＜ｙ＋ｚを満たす）
で表されるジルコニウム含有オリビン型正極材料を提供するものである。
また、本発明は、リチウム化合物、ケイ酸化合物、ジルコニウム化合物、及び遷移金属（Ｍ）塩（Ｍは、Ｆｅ、Ｎｉ、Ｃｏ又はＭｎを示す）を含有し、かつリン酸化合物及び／又はフッ素化合物を含有する塩基性水分散液を水熱反応させる工程を含む、上記ジルコニウム含有オリビン型正極材料の製造方法を提供するものである。
That is, the present invention provides the following formula (1):
Li 2 Fe a Ni b Co c Mn d Zr x Si 1-z P 0.8z O 4-y F 2y ··· (1)
(In the formula (1), a, b, c and d satisfy a + b + c + d = 1−2x, x is 0 <x <0.5, y is 0 ≦ y ≦ 2, and z is 0 ≦ z. ≦ 0.1, and y and z satisfy 0 <y + z)
The zirconium-containing olivine-type positive electrode material represented by these is provided.
The present invention also includes a lithium compound, a silicate compound, a zirconium compound, and a transition metal (M) salt (M represents Fe, Ni, Co, or Mn), and a phosphate compound and / or a fluorine compound. The manufacturing method of the said zirconium containing olivine type | mold positive electrode material including the process of carrying out the hydrothermal reaction of the basic aqueous dispersion containing this is provided.
本発明のジルコニウム含有オリビン型正極材料によれば、優れた充放電容量を発現する二次電池を得ることができる。 According to the zirconium-containing olivine-type positive electrode material of the present invention, a secondary battery exhibiting excellent charge / discharge capacity can be obtained.
以下、本発明について詳細に説明する。
本発明のジルコニウム含有オリビン型正極材料は、次式（１）：
Ｌｉ2ＦｅaＮｉbＣｏcＭｎdＺｒxＳｉ1-zＰ0.8zＯ4-yＦ2y・・・（１）
（式（１）中、ａ、ｂ、ｃ及びｄはａ＋ｂ＋ｃ＋ｄ=１−２ｘを満たし、ｘは０＜ｘ＜０．５であり、ｙは０≦ｙ≦２であり、ｚは０≦ｚ≦０．１であり、かつｙ及びｚは０＜ｙ＋ｚを満たす）
で表される。
式（１）中、ｘは０＜ｘ＜０．５であって、Ｚｒは必須である。また、ａ、ｂ、ｃ及びｄは、ａ＋ｂ＋ｃ＋ｄ＝１−２ｘであるので、ａ、ｂ、ｃ及びｄのうち、少なくとも１つは０ではなく、すなわちＦｅ、Ｎｉ、Ｃｏ及びＭｎの遷移金属うち、少なくとも１種は必須である。さらに、ｙは０≦ｙ≦２であり、ｚは０≦ｚ≦０．１であり、かつｙ及びｚは０＜ｙ＋ｚを満たすものであり、すなわちｙとｚは同時に０となることはなく、本発明のジルコニウム含有オリビン型正極材料は、Ｐ原子又はＦ原子の一方を含み、或いはＰ原子及びＦ原子の双方を含む。なかでも、より高い電池物性を発現する観点から、ｙ及びｚともに０ではないのが好ましく、すなわちＰ原子及びＦ原子の双方を含むのが好ましい。
本発明のジルコニウム含有オリビン型正極材料（１）には、具体的には、例えば以下のような態様が含まれる。
Hereinafter, the present invention will be described in detail.
The zirconium-containing olivine-type positive electrode material of the present invention has the following formula (1):
Li 2 Fe a Ni b Co c Mn d Zr x Si 1-z P 0.8z O 4-y F 2y ··· (1)
(In the formula (1), a, b, c and d satisfy a + b + c + d = 1−2x, x is 0 <x <0.5, y is 0 ≦ y ≦ 2, and z is 0 ≦ z. ≦ 0.1, and y and z satisfy 0 <y + z)
It is represented by
In the formula (1), x is 0 <x <0.5, and Zr is essential. Moreover, since a, b, c and d are a + b + c + d = 1−2x, at least one of a, b, c and d is not 0, that is, among transition metals of Fe, Ni, Co and Mn. At least one of them is essential. Furthermore, y is 0 ≦ y ≦ 2, z is 0 ≦ z ≦ 0.1, and y and z satisfy 0 <y + z, that is, y and z are not 0 simultaneously. The zirconium-containing olivine-type positive electrode material of the present invention contains either P atoms or F atoms, or contains both P atoms and F atoms. Among these, from the viewpoint of developing higher battery physical properties, it is preferable that both y and z are not 0, that is, it includes both P atoms and F atoms.
Specific examples of the zirconium-containing olivine-type positive electrode material (1) of the present invention include the following aspects.
Ｌｉ2ＦｅaＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8z・・・（１ａ）
（式（１ａ）中、ａは、ａ＝１−２ｘであり、ｘ及びｚは、式（１）と同義である）
Ｌｉ2ＦｅaＺｒxＳｉＯ4-yＦ2y・・・（１ａ’）
（式（１ａ’）中、ａは、ａ＝１−２ｘであり、ｘ及びｙは、式（１）と同義である）
Ｌｉ2ＦｅaＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8zＦ2y・・・（１ａ’’）
（式（１ａ’’）中、ａは、ａ＝１−２ｘであり、ｘ、ｙ及びｚは、式（１）と同義である）
Ｌｉ2ＮｉbＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8z・・・（１ｂ）
（式（１ｂ）中、ｂは、ｂ＝１−２ｘであり、ｘ及びｚは、式（１）と同義である）
Ｌｉ2ＮｉbＺｒxＳｉＯ4-yＦ2y・・・（１ｂ’）
（式（１ｂ’）中、ｂは、ｂ＝１−２ｘであり、ｘ及びｙは、式（１）と同義である）
Ｌｉ2ＮｉbＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8zＦ2y・・・（１ｂ’’）
（式（１ｂ’’）中、ｂは、ｂ＝１−２ｘであり、ｘ、ｙ及びｚは、式（１）と同義である）
Ｌｉ2ＣｏcＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8z・・・（１ｃ）
（式（１ｃ）中、ｃは、ｃ＝１−２ｘであり、ｘ及びｚは、式（１）と同義である）
Ｌｉ2ＣｏcＺｒxＳｉＯ4-yＦ2y・・・（１ｃ’）
（式（１ｃ’）中、ｃは、ｃ＝１−２ｘであり、ｘ及びｙは、式（１）と同義である）
Ｌｉ2ＣｏcＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8zＦ2y・・・（１ｃ’’）
（式（１ｃ’’）中、ｃは、ｃ＝１−２ｘであり、ｘ、ｙ及びｚは、式（１）と同義である）
Ｌｉ2ＮｉbＭｎdＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8z・・・（１ｄ）
（式（１ｄ）中、ｂ及びｄは、ｂ＋ｄ＝１−２ｘであり、ｘ及びｚは、式（１）と同義である）
Ｌｉ2ＮｉbＭｎdＺｒxＳｉＯ4-yＦ2y・・・（１ｄ’）
（式（１ｄ’）中、ｂ及びｄは、ｂ＋ｄ＝１−２ｘであり、ｘ及びｙは、式（１）と同義である）
Ｌｉ2ＮｉbＭｎdＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8zＦ2y・・・（１ｄ’’）
（式（１ｄ’’）中、ｂ及びｄは、ｂ＋ｄ＝１−２ｘであり、ｘ、ｙ及びｚは、式（１）と同義である）
Ｌｉ2ＦｅaＭｎdＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8z・・・（１ｅ）
（式（１ｅ）中、ａ及びｄは、ａ＋ｄ＝１−２ｘであり、ｘ及びｚは、式（１）と同義である）
Ｌｉ2ＦｅaＭｎdＺｒxＳｉＯ4-yＦ2y・・・（１ｅ’）
（式（１ｅ’）中、ａ及びｄは、ａ＋ｄ＝１−２ｘであり、ｘ及びｙは、式（１）と同義である）
Ｌｉ2ＦｅaＭｎdＺｒx（ＳｉＯ4）1-z（ＰＯ4）0.8zＦ2y・・・（１ｅ’’）
（式（１ｅ’’）中、ａ及びｄは、ａ＋ｄ＝１−２ｘであり、ｘ、ｙ及びｚは、式（１）と同義である）
Li 2 Fe a Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z (1a)
(In Formula (1a), a is a = 1-2x, and x and z are synonymous with Formula (1).)
Li 2 Fe a Zr x SiO 4 -y F 2y ··· (1a ')
(In Formula (1a ′), a is a = 1−2x, and x and y are synonymous with Formula (1)).
Li 2 Fe a Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z F 2y (1a ″)
(In Formula (1a ″), a is a = 1−2x, and x, y, and z are synonymous with Formula (1)).
Li 2 Ni b Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z (1b)
(In formula (1b), b is b = 1-2x, and x and z are synonymous with formula (1)).
Li 2 Ni b Zr x SiO 4 -y F 2y ··· (1b ')
(In formula (1b ′), b is b = 1−2x, and x and y are synonymous with formula (1)).
Li 2 Ni b Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z F 2y (1b ″)
(In Formula (1b ″), b is b = 1−2x, and x, y, and z are synonymous with Formula (1)).
Li 2 Co c Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z (1c)
(In formula (1c), c is c = 1−2x, and x and z are synonymous with formula (1)).
Li 2 Co c Zr x SiO 4 -y F 2y ··· (1c ')
(In the formula (1c ′), c is c = 1−2x, and x and y are synonymous with the formula (1)).
Li 2 Co c Zr x (SiO 4 ) 1-z (PO 4 ) 0.8z F 2y (1c ″)
(In the formula (1c ″), c is c = 1−2x, and x, y, and z are synonymous with the formula (1)).
Li 2 Ni b Mn d Zr x (SiO 4) 1-z (PO 4) 0.8z ··· (1d)
(In formula (1d), b and d are b + d = 1−2x, and x and z are synonymous with formula (1)).
Li 2 Ni b Mn d Zr x SiO 4-y F 2y ··· (1d ')
(In formula (1d ′), b and d are b + d = 1−2x, and x and y have the same meanings as in formula (1)).
Li 2 Ni b Mn d Zr x (SiO 4) 1-z (PO 4) 0.8z F 2y ··· (1d '')
(In the formula (1d ″), b and d are b + d = 1−2x, and x, y, and z are synonymous with the formula (1)).
Li 2 Fe a Mn d Zr x (SiO 4) 1-z (PO 4) 0.8z ··· (1e)
(In formula (1e), a and d are a + d = 1−2x, and x and z are synonymous with formula (1)).
Li 2 Fe a Mn d Zr x SiO 4-y F 2y ··· (1e ')
(In formula (1e ′), a and d are a + d = 1−2x, and x and y have the same meanings as in formula (1)).
Li 2 Fe a Mn d Zr x (SiO 4) 1-z (PO 4) 0.8z F 2y ··· (1e '')
(In the formula (1e ″), a and d are a + d = 1−2x, and x, y, and z are synonymous with the formula (1)).
これらジルコニウム含有オリビン型正極材料（１）の具体例としては、例えば、Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03ＳｉＯ3.95Ｆ0.1、Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03Ｓｉ0.925Ｐ0.1Ｏ3.95Ｆ0.1、Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03（ＳｉＯ4）0.925（ＰＯ4）0.1等が挙げられる。なかでも、原料コスト及び放電容量の点から、式（１）中のａが０でない正極材料、すなわち少なくともＦｅを含む正極材料であるのが好ましく、具体的には式（１ａ）、（１ａ’）、（１ａ’’）、（１ｅ）、（１ｅ’）、又は（１ｅ’’）の正極材料であるのがより好ましい。 Specific examples of these zirconium-containing olivine-type positive electrode materials (1) include, for example, Li 2 Fe 0.09 Mn 0.85 Zr 0.03 SiO 3.95 F 0.1 , Li 2 Fe 0.09 Mn 0.85 Zr 0.03 Si 0.925 P 0.1 O 3.95 F 0.1 , Li 2 Fe 0.09 Mn 0.85 Zr 0.03 (SiO 4 ) 0.925 (PO 4 ) 0.1 and the like. Among these, from the viewpoint of raw material cost and discharge capacity, a positive electrode material in which a in Formula (1) is not 0, that is, a positive electrode material containing at least Fe is preferable. Specifically, Formula (1a), (1a ′ ), (1a ″), (1e), (1e ′), or (1e ″).
ｘの好ましい範囲は、０．００１〜０．１であり、放電容量の点から、０．００５〜０．０８がより好ましく、０．０１〜０．０５がさらに好ましい。 The preferable range of x is 0.001 to 0.1, 0.005 to 0.08 is more preferable, and 0.01 to 0.05 is more preferable from the viewpoint of discharge capacity.
本発明のジルコニウム含有オリビン型正極材料（１）は、リチウム化合物、ケイ酸化合物、ジルコニウム化合物、及び遷移金属（Ｍ）塩（Ｍは、Ｆｅ、Ｎｉ、Ｃｏ又はＭｎを示す）を含有し、かつリン酸化合物及び／又はフッ素化合物を含有する塩基性水分散液を水熱反応させる工程（Ｉ）を含む製造方法により得ることができる。 The zirconium-containing olivine-type positive electrode material (1) of the present invention contains a lithium compound, a silicate compound, a zirconium compound, and a transition metal (M) salt (M represents Fe, Ni, Co, or Mn), and It can be obtained by a production method including a step (I) of hydrothermal reaction of a basic aqueous dispersion containing a phosphoric acid compound and / or a fluorine compound.
リチウム化合物としては、水酸化リチウム（例えばＬｉＯＨ・Ｈ2Ｏ）、炭酸リチウム（Ｌｉ2ＣＯ3）、硫酸リチウム、酢酸リチウムが挙げられるが、水酸化リチウムが特に好ましい。水酸化リチウムとしては、例えば、ＬｉＯＨ・Ｈ2Ｏ等の水和物を用いることができる。水分散液中のリチウム化合物の濃度は、０．３〜４ｍｏｌ／ｌが好ましく、さらに１〜３ｍｏｌ／ｌが好ましい。 Examples of the lithium compound include lithium hydroxide (for example, LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium sulfate, and lithium acetate, and lithium hydroxide is particularly preferable. As lithium hydroxide, for example, a hydrate such as LiOH.H 2 O can be used. The concentration of the lithium compound in the aqueous dispersion is preferably 0.3 to 4 mol / l, more preferably 1 to 3 mol / l.
ケイ酸化合物としては、反応性のあるシリカ化合物であれば特に限定されず、オルトケイ酸テトラエチル、非晶質シリカ、Ｎａ4ＳｉＯ4やＮａ4ＳｉＯ4・ｎＨ2Ｏ（例えばＮａ4ＳｉＯ4・Ｈ2Ｏ）が挙げられる。なかでも、水分散液が容易に塩基性になる観点から、Ｎａ4ＳｉＯ4を用いるのがより好ましく、加水分解を介して容易にＳｉＯ2へ変化させることができる観点から、オルトケイ酸テトラエチルを用いるのがより好ましい。水分散液中のケイ酸化合物の濃度は、０．１５〜２ｍｏｌ／ｌが好ましく、さらに０．５〜１．５ｍｏｌ／ｌが好ましい。 The silicic acid compound is not particularly limited as long as it is a reactive silica compound. Tetraethyl orthosilicate, amorphous silica, Na 4 SiO 4 or Na 4 SiO 4 .nH 2 O (for example, Na 4 SiO 4 .H 2 O). Among these, Na 4 SiO 4 is more preferably used from the viewpoint that the aqueous dispersion easily becomes basic, and tetraethyl orthosilicate is used from the viewpoint that it can be easily changed to SiO 2 through hydrolysis. Is more preferable. The concentration of the silicate compound in the aqueous dispersion is preferably 0.15 to 2 mol / l, more preferably 0.5 to 1.5 mol / l.
また、ケイ酸化合物として、予めカーボンＸを担持させたケイ酸化合物を用いてもよい。予めケイ酸化合物にカーボンＸを担持させるには、具体的には、カーボンＸ及びケイ酸化合物を含むスラリー水Ｘを水熱反応に付すことにより、複合体を得た後、かかる複合体、リチウム化合物、ジルコニウム化合物、及び遷移金属（Ｍ）塩（Ｍは、Ｆｅ、Ｎｉ、Ｃｏ又はＭｎを示す）を含有し、かつリン酸化合物及び／又はフッ素化合物を含有する塩基性水分散液を水熱反応に付すのがよい。すなわち、工程（Ｉ）は、カーボン及びケイ酸化合物を含むスラリー水を水熱反応させる工程を含むのが好ましい。 Moreover, you may use the silicic acid compound which carry | supported carbon X previously as a silicic acid compound. In order to make the silicate compound support the carbon X in advance, specifically, after the composite is obtained by subjecting the slurry water X containing the carbon X and the silicate compound to a hydrothermal reaction, the composite, lithium Hydrophilic basic aqueous dispersion containing a compound, a zirconium compound, and a transition metal (M) salt (M represents Fe, Ni, Co or Mn) and containing a phosphate compound and / or a fluorine compound It is good to attach to reaction. That is, step (I) preferably includes a step of hydrothermally reacting slurry water containing carbon and a silicate compound.
また、かかる水熱反応において用いるカーボンＸ及びケイ酸化合物を含むスラリー水Ｘは、水のほか、有機溶媒を含むのが好ましい。かかる有機溶媒としては、エタノール、エチレングリコール、グリセリンが挙げられる。なかでもエタノールが好ましい。かかる有機溶媒の量は、スラリー水Ｘに含まれる水及び有機溶媒の全量中、好ましくは５〜５０質量％であり、より好ましくは１０〜３０質量％である。また、スラリー水Ｘ中におけるカーボンＸ及びケイ酸化合物の合計量は、水１００質量部に対し、好ましくは５〜３０質量部であり、より好ましくは７〜１５質量部である。また、スラリー水Ｘ中におけるカーボンＸとケイ酸化合物との質量比（カーボンＸ：ケイ酸化合物）は、好ましくは１：３〜１：１２であり、より好ましくは１：６〜１：１２である。 Moreover, it is preferable that the slurry water X containing the carbon X and silicic acid compound used in this hydrothermal reaction contains an organic solvent in addition to water. Such organic solvents include ethanol, ethylene glycol, and glycerin. Of these, ethanol is preferable. The amount of the organic solvent is preferably 5 to 50% by mass and more preferably 10 to 30% by mass in the total amount of water and organic solvent contained in the slurry water X. Moreover, the total amount of the carbon X and the silicic acid compound in the slurry water X is preferably 5 to 30 parts by mass, more preferably 7 to 15 parts by mass with respect to 100 parts by mass of water. The mass ratio of carbon X to silicic acid compound in the slurry water X (carbon X: silicic acid compound) is preferably 1: 3 to 1:12, more preferably 1: 6 to 1:12. is there.
カーボンＸ及びケイ酸化合物を用いた水熱反応での温度は、電池物性を高める観点から、好ましくは１３０〜２００℃であり、より好ましくは１４０〜１７０℃である。また、水熱反応時間は、好ましくは１〜１２時間であり、より好ましくは３〜９時間である。反応時の圧力は、好ましくは０．２〜１．５ＭＰａであり、より好ましくは０．３〜０．７ＭＰａである。なお、かかる水熱反応に付して得られた混合液をそのまま用いて塩基性水分散液を調製するのが好ましい。 The temperature in the hydrothermal reaction using carbon X and the silicate compound is preferably 130 to 200 ° C, more preferably 140 to 170 ° C, from the viewpoint of improving battery physical properties. Moreover, hydrothermal reaction time becomes like this. Preferably it is 1 to 12 hours, More preferably, it is 3 to 9 hours. The pressure during the reaction is preferably 0.2 to 1.5 MPa, more preferably 0.3 to 0.7 MPa. In addition, it is preferable to prepare a basic aqueous dispersion by using the mixed solution obtained by the hydrothermal reaction as it is.
このように、予めカーボンＸを担持させたケイ酸化合物を用いることにより、さらに電池物性を高めることができる。この場合に用いるカーボンＸとしては、水熱反応を介する上での取扱い性に優れる観点、及び電池物性を高める観点から、グラフェンオキサイドが好ましい。グラフェンオキサイドはグラフェンの酸化物であり、グラフェンオキサイドそのものは導電性を有さないものの、親水性であるので水熱反応を介する上での取扱い性に優れる。かかるグラフェンオキサイドを還元することによって、疎水性ではあるものの、ハニカム格子状に炭素原子がＳＰ2結合した単層構造を有し、導電性に優れたグラフェンを得ることができ、ジルコニウム含有オリビン型正極材料における電池物性の向上に大いに寄与することができる。 Thus, by using a silicic acid compound on which carbon X is supported in advance, battery physical properties can be further improved. The carbon X used in this case is preferably graphene oxide from the viewpoint of excellent handleability through a hydrothermal reaction and the viewpoint of improving battery physical properties. Graphene oxide is an oxide of graphene, and although graphene oxide itself has no electrical conductivity, it is hydrophilic and therefore has excellent handling properties through a hydrothermal reaction. By reducing such graphene oxide, although it is hydrophobic, it has a monolayer structure in which carbon atoms are SP 2 bonded in a honeycomb lattice shape, and graphene excellent in conductivity can be obtained. A zirconium-containing olivine-type positive electrode This can greatly contribute to the improvement of battery physical properties.
なお、グラフェンオキサイドは、層状、膜状、塊状等の形状を呈し得るが、本発明で用いるグラフェンオキサイドは、いずれの形状を呈していてもよい。かかるグラフェンオキサイドは、硝酸ナトリウムを含む濃硫酸中で過マンガン酸カリウムによって天然グラファイト等の原料黒鉛を酸化する方法であるハマーズ（Ｈｕｍｍｅｒｓ）法や、ブロディー（Ｂｒｏｄｉｅ）法、スタウデンマイヤー（Ｓｔａｕｄｅｎｍａｉｅｒ）法等により、製造することができる。 In addition, although graphene oxide can exhibit shapes, such as a layer form, a film | membrane form, and a lump shape, the graphene oxide used by this invention may exhibit any shape. Such graphene oxide is a method in which raw graphite such as natural graphite is oxidized with potassium permanganate in concentrated sulfuric acid containing sodium nitrate. It can be manufactured by law.
ジルコニウム化合物としては、４価の化合物であればよく、例えば、ハロゲン化ジルコニウム、硫酸ジルコニウム、二酢酸酸化ジルコニウム、オクタン酸ジルコニウム、ラウリン酸酸化ジルコニウム等の有機酸塩が挙げられる。水分散液中のジルコニウム化合物の濃度は、０．００１〜２ｍｏｌ／ｌが好ましく、さらに０．００１〜０．５ｍｏｌ／ｌが好ましい。 The zirconium compound may be a tetravalent compound, and examples thereof include organic acid salts such as zirconium halide, zirconium sulfate, zirconium diacetate oxide, zirconium octoate, and zirconium laurate oxide. The concentration of the zirconium compound in the aqueous dispersion is preferably 0.001 to 2 mol / l, more preferably 0.001 to 0.5 mol / l.
遷移金属（Ｍ）塩（Ｍは、Ｆｅ、Ｎｉ、Ｃｏ又はＭｎを示す）としては、ＭＳＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される遷移金属硫酸塩又は（Ｒ）2Ｍ（式中、Ｒは有機酸残基を示し、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される有機酸遷移金属塩を用いるのが好ましい。遷移金属硫酸塩ＭＳＯ4としては、ＦｅＳＯ4、ＮｉＳＯ4、ＣｏＳＯ4又はＭｎＳＯ4が挙げられ、これらは１種単独でも２種以上を混合して用いてもよい。これらのうち、ＦｅＳＯ4、ＭｎＳＯ4がより好ましい。
なお、遷移金属（Ｍ）塩として遷移金属硫酸塩ＭＳＯ4を用いる場合における反応混合液中のＬｉは、遷移金属に対してモル比で２倍以上用いることが好ましく、Ｌｉ：Ｍが２：１〜３：１程度がより好ましい。
As transition metal (M) salt (M represents Fe, Ni, Co or Mn), transition metal sulfate represented by MSO 4 (wherein M represents Fe, Ni, Co or Mn) or It is preferable to use an organic acid transition metal salt represented by (R) 2 M (wherein R represents an organic acid residue, and M represents Fe, Ni, Co, or Mn). Examples of the transition metal sulfate MSO 4 include FeSO 4 , NiSO 4 , CoSO 4, and MnSO 4 , and these may be used alone or in combination of two or more. Of these, FeSO 4 and MnSO 4 are more preferable.
In the case where transition metal sulfate MSO 4 is used as the transition metal (M) salt, Li in the reaction mixture is preferably used in a molar ratio of 2 times or more with respect to the transition metal, and Li: M is 2: 1. About ~ 3: 1 is more preferable.
有機酸遷移金属塩（Ｒ）2ＭのＲで示される有機酸としては、炭素数１〜２０の有機酸が好ましく、炭素数２〜１２の有機酸がより好ましい。より具体的な有機酸としては、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。
なお、遷移金属（Ｍ）塩として（Ｒ）2Ｍを用いる場合における反応混合液中のＬｉは、遷移金属に対してモル比で２倍以上用いることが好ましく、Ｌｉ：Ｍが２．５：１〜５：１程度がより好ましい。
The organic acid represented by an organic acid transition metal salt (R) of 2 M R, preferably an organic acid having 1 to 20 carbon atoms, more preferably an organic acid having 2 to 12 carbon atoms. More specific organic acids include dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
In addition, when (R) 2 M is used as the transition metal (M) salt, Li in the reaction mixture is preferably used in a molar ratio with respect to the transition metal at least twice, and Li: M is 2.5: About 1 to 5: 1 is more preferable.
リン酸化合物としては、リン酸、リン酸２水素アンモニウム、リン酸水素２アンモニウム等が挙げられる。なかでも、電池物性を高める観点から、リン酸が好ましい。リン酸化合物を用いる場合、反応混合液中のリンは、ケイ素に対してモル比で０．０１〜０．１倍用いるのが好ましく、０．０２〜０．０８倍がより好ましい。 Examples of the phosphoric acid compound include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the like. Among these, phosphoric acid is preferable from the viewpoint of improving battery physical properties. When using a phosphoric acid compound, the phosphorus in the reaction mixture is preferably used in a molar ratio of 0.01 to 0.1 times, more preferably 0.02 to 0.08 times the silicon.
フッ素化合物としては、フッ化アンモニウム、フッ化ナトリウム、フッ化カリウム等が挙げられる。なかでも、電池物性を高める観点から、フッ化アンモニウムが好ましい。フッ素化合物を用いる場合、反応混合液中のフッ素は、リチウムに対してモル比で０．０５〜１倍用いるのが好ましく、０．０５〜０．８倍がより好ましい。
なお、より高い電池物性を発現する観点から、Ｐ原子及びＦ原子の双方を含むジルコニウム含有オリビン型正極材料（１）を得るのが好ましく、この場合、リン酸化合物及びフッ素化合物の双方を含有する塩基性水分散液とする。
Examples of the fluorine compound include ammonium fluoride, sodium fluoride, potassium fluoride and the like. Of these, ammonium fluoride is preferable from the viewpoint of improving battery physical properties. When using a fluorine compound, the fluorine in the reaction mixture is preferably used in a molar ratio of 0.05 to 1 times, more preferably 0.05 to 0.8 times that of lithium.
From the viewpoint of developing higher battery properties, it is preferable to obtain a zirconium-containing olivine-type positive electrode material (1) containing both P atoms and F atoms. In this case, both a phosphoric acid compound and a fluorine compound are contained. A basic aqueous dispersion is used.
水分散液のｐＨは、塩基性であればよいが、１２．０〜１３．５であるのが副反応（例えば、Ｆｅ3Ｏ4等の生成）の防止、ケイ酸化合物の溶解性及び反応の進行の点でより好ましい。該水分散液のｐＨの調整は、塩基、例えば、水酸化ナトリウムを添加することにより行ってもよく、ケイ酸化合物としてＮａ4ＳｉＯ4を用いてもよく、不純物の生成を効果的に抑制する観点から、水酸化ナトリウムを含有するのが好ましい。水酸化ナトリウムを用いる場合、具体的には、水分散液におけるリチウム化合物及び水酸化ナトリウムの合計量は、水１００質量部に対し、好ましくは８〜４０質量部であり、より好ましくは８〜３８質量部であり、さらに好ましくは８〜３６質量部である。また、リチウムとナトリウムのモル比（Ｌｉ：Ｎａ）は、好ましくは２：３〜１：６であり、より好ましくは１：２〜１：４である。さらに、水分散液中におけるケイ酸化合物と水酸化ナトリウムのモル比は、好ましくは１：３〜１：６であり、より好ましくは１：３〜１：５である。 The pH of the aqueous dispersion may be basic, but it is 12.0 to 13.5 to prevent side reactions (for example, formation of Fe 3 O 4 etc.), solubility and reaction of silicic acid compounds. It is more preferable in terms of progression. The pH of the aqueous dispersion may be adjusted by adding a base, for example, sodium hydroxide, or Na 4 SiO 4 may be used as the silicic acid compound, effectively suppressing the generation of impurities. From the viewpoint, it is preferable to contain sodium hydroxide. When using sodium hydroxide, specifically, the total amount of the lithium compound and sodium hydroxide in the aqueous dispersion is preferably 8 to 40 parts by mass, more preferably 8 to 38, with respect to 100 parts by mass of water. It is a mass part, More preferably, it is 8-36 mass parts. The molar ratio of lithium to sodium (Li: Na) is preferably 2: 3 to 1: 6, more preferably 1: 2 to 1: 4. Furthermore, the molar ratio of the silicic acid compound and sodium hydroxide in the aqueous dispersion is preferably 1: 3 to 1: 6, more preferably 1: 3 to 1: 5.
なお、リチウム化合物として水酸化リチウムを用いる場合、上記合計量における水酸化リチウムの量は、水酸化リチウム（ＬｉＯＨ）量に換算した値となる。また、化学量論上、かかる水酸化リチウムのＬｉ源としての量は、ジルコニウム含有オリビン型正極材料（１）におけるジルコニウム化合物及び遷移金属（Ｍ）塩の合計モル量を基準として、２〜４倍であるのが好ましく、２〜３．５倍であるのがより好ましい。 When lithium hydroxide is used as the lithium compound, the amount of lithium hydroxide in the total amount is a value converted to the amount of lithium hydroxide (LiOH). Further, in terms of stoichiometry, the amount of lithium hydroxide as a Li source is 2 to 4 times based on the total molar amount of the zirconium compound and the transition metal (M) salt in the zirconium-containing olivine-type positive electrode material (1). It is preferable that it is 2 to 3.5 times.
リチウム化合物、ケイ酸化合物、ジルコニウム化合物、及び遷移金属（Ｍ）塩、並びにリン酸化合物及び／又はフッ素化合物の添加順序は特に限定されないが、遷移金属源として遷移金属硫酸塩ＭＳＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）を用いる場合、副反応を抑制する点から、遷移金属硫酸塩とは別に、リチウム化合物、ケイ酸化合物を含有する塩基性水分散液を予め調製してもよい。この場合、該水分散液と、遷移金属硫酸塩、及びジルコニウム化合物、並びにリン酸化合物及び／又はフッ素化合物とを混合して水熱反応に付せばよい。 The order of addition of the lithium compound, the silicate compound, the zirconium compound, and the transition metal (M) salt, and the phosphate compound and / or the fluorine compound is not particularly limited, but the transition metal sulfate MSO 4 (wherein In the case of using M, Fe, Ni, Co or Mn), a basic aqueous dispersion containing a lithium compound and a silicate compound is prepared separately from the transition metal sulfate from the viewpoint of suppressing side reactions. May be. In this case, the aqueous dispersion, transition metal sulfate, zirconium compound, phosphate compound and / or fluorine compound may be mixed and subjected to a hydrothermal reaction.
水熱反応は、１００℃以上であればよく、１３０〜１８０℃が好ましく、さらに１４０〜１６０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０〜１８０℃で反応を行う場合、この時の圧力は０．３〜０．９ＭＰａとなり、１４０〜１６０℃で反応を行う場合の圧力は０．３〜０．４ＭＰａとなる。水熱反応時間は１〜２４時間が好ましく、さらに３〜１２時間が好ましい。 The hydrothermal reaction should just be 100 degreeC or more, 130-180 degreeC is preferable and 140-160 degreeC is more preferable. The hydrothermal reaction is preferably performed in a pressure vessel. When the reaction is performed at 130 to 180 ° C, the pressure at this time is 0.3 to 0.9 MPa, and the pressure when the reaction is performed at 140 to 160 ° C is 0. .3 to 0.4 MPa. The hydrothermal reaction time is preferably 1 to 24 hours, more preferably 3 to 12 hours.
当該水熱反応により、式（１）のジルコニウム含有オリビン型正極材料が高収率で得られる。また、得られた正極材料の平均粒径は１０〜１００ｎｍとなり、その結晶度も高い。
得られた式（１）のジルコニウム含有オリビン型正極材料は、ろ過後、乾燥することにより単離できる。乾燥手段は、凍結乾燥、真空乾燥が用いられる。
By the hydrothermal reaction, the zirconium-containing olivine-type positive electrode material of the formula (1) is obtained with a high yield. Moreover, the average particle diameter of the obtained positive electrode material becomes 10-100 nm, and the crystallinity is also high.
The obtained zirconium-containing olivine positive electrode material of the formula (1) can be isolated by drying after filtration. As the drying means, freeze drying or vacuum drying is used.
工程（Ｉ）において得られた式（１）のジルコニウム含有オリビン型正極材料は、さらにカーボンＹを担持する工程（II）、及び焼成する工程（III）を経ることにより、ジルコニウム含有オリビン型正極材料（１）を含有する二次電池用正極活物質を得ることができる。工程（II）では、ジルコニウム含有オリビン型正極材料に常法により、カーボンＹ及び水を添加し、次いで工程（III）に移行すればよい。工程（II）において用いるカーボンＹとしては、カーボンブラックが好ましく、例えば、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等が挙げられる。なかでも、良好な導電性を付与する観点から、アセチレンブラック、ケッチェンブラックが好ましい。 The zirconium-containing olivine-type positive electrode material of the formula (1) obtained in the step (I) is further subjected to a step (II) for supporting carbon Y and a step (III) for firing, whereby a zirconium-containing olivine-type positive electrode material The positive electrode active material for secondary batteries containing (1) can be obtained. In step (II), carbon Y and water may be added to the zirconium-containing olivine-type positive electrode material by a conventional method, and then the process may proceed to step (III). The carbon Y used in the step (II) is preferably carbon black, and examples thereof include acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Of these, acetylene black and ketjen black are preferred from the viewpoint of imparting good conductivity.
なお、工程（II）は、ジルコニウム含有オリビン型正極材料（１）とカーボンＹとが均一に分散したまま堅固に凝集し、かつ効率的に配置されて、より空隙が低減された正極活物質を得る観点から、ジルコニウム含有オリビン型正極材料（１）及びカーボンＹを混合した後、圧縮力及びせん断力を付加しながら混合する工程であるのが好ましい。また、工程（Ｉ）においてグラフェンオキサイド等のカーボンＸを担持させたケイ酸化合物を用いた場合、カーボンＸとカーボンＹの質量比（カーボンＸ：カーボンＹ）は、好ましくは５１：４９〜７０：３０であり、より好ましくは５５：４５〜７０：３０である。 In the step (II), the positive electrode active material in which the zirconium-containing olivine-type positive electrode material (1) and the carbon Y are firmly agglomerated while being uniformly dispersed and is efficiently arranged to further reduce the voids. From the viewpoint of obtaining, it is preferable that the zirconium-containing olivine-type positive electrode material (1) and carbon Y are mixed and then mixed while applying compressive force and shearing force. Moreover, when the silicic acid compound carrying carbon X such as graphene oxide is used in the step (I), the mass ratio of carbon X to carbon Y (carbon X: carbon Y) is preferably 51:49 to 70: 30, more preferably 55:45 to 70:30.
圧縮力及びせん断力を付加しながら混合する処理は、周速度２５〜４０ｍ／ｓで回転するインペラを備えた密閉容器内で行うのが好ましい。かかるインペラの周速度は、得られる正極活物質のタップ密度を高めて電池物性の向上を図る観点から、好ましくは２７〜３５ｍ／ｓである。なお、インペラの周速度とは、回転式攪拌翼（インペラ）の最外端部の速度を意味し、下記式（Ｉ）により表すことができる。
インペラの周速度（ｍ／ｓ）＝
インペラの半径（ｍ）×２×π×回転数（ｒｐｍ）÷６０・・・（Ｉ）
圧縮力及びせん断力を付加しながら混合する処理を行う時間は、インペラの周速度が遅いほど長くなるように、インペラの周速度によっても変動し得るが、好ましくは５〜９０分間であり、より好ましくは１０〜６０分である。
The process of mixing while applying a compressive force and a shearing force is preferably carried out in a closed container equipped with an impeller that rotates at a peripheral speed of 25 to 40 m / s. The peripheral speed of the impeller is preferably 27 to 35 m / s from the viewpoint of improving the battery physical properties by increasing the tap density of the obtained positive electrode active material. In addition, the peripheral speed of an impeller means the speed of the outermost edge part of a rotary stirring blade (impeller), and can be represented by following formula (I).
Impeller peripheral speed (m / s) =
Impeller radius (m) × 2 × π × rotational speed (rpm) ÷ 60 (I)
The time for performing the mixing process while applying compressive force and shearing force may vary depending on the peripheral speed of the impeller so that the slower the peripheral speed of the impeller, the more preferably it is 5 to 90 minutes. Preferably it is 10 to 60 minutes.
圧縮力及びせん断力を付加しながら混合する処理における、インペラの周速度及び／又は処理時間は、容器に投入するジルコニウム含有オリビン型正極材料（１）及びカーボンＹの量に応じて適宜調整する必要がある。そして、容器を稼動させることにより、インペラと容器内壁との間でこれら混合物に圧縮力及びせん断力が付加されつつ、これを混合する処理を行うことが可能となり、粒子の表面又は間隙において、カーボンが緻密かつ均一に分散した正極活物質を得ることができる。
例えば、上記混合する処理を周速度２５〜４０ｍ／ｓで回転するインペラを備える密閉容器内で、５〜９０分間行う場合、容器に投入するジルコニウム含有オリビン型正極材料（１）及びカーボンＹの合計量は、有効容器（インペラを備える密閉容器のうち、ジルコニウム含有オリビン型正極材料（１）及びカーボンを収容可能な部位に相当する容器）１ｃｍ3当たり、好ましくは０．１〜０．７ｇであり、より好ましくは０．１５〜０．４ｇである。
The impeller peripheral speed and / or processing time in the process of mixing while applying compressive force and shearing force must be appropriately adjusted according to the amount of zirconium-containing olivine-type positive electrode material (1) and carbon Y to be charged into the container. There is. By operating the container, it becomes possible to perform a process of mixing the mixture while applying compressive force and shearing force between the impeller and the inner wall of the container. Can be obtained in a dense and uniformly dispersed positive electrode active material.
For example, when the mixing process is performed for 5 to 90 minutes in an airtight container equipped with an impeller rotating at a peripheral speed of 25 to 40 m / s, the total of zirconium-containing olivine-type positive electrode material (1) and carbon Y charged into the container The amount is preferably 0.1 to 0.7 g per 1 cm 3 of an effective container (a container corresponding to a part capable of containing a zirconium-containing olivine-type positive electrode material (1) and carbon in a closed container including an impeller). More preferably, it is 0.15-0.4g.
工程（II）を経た後、工程（III）の焼成する工程を経るのが好ましい。焼成条件は、不活性ガス雰囲気下又は還元条件下にて行うのが好ましく、また焼成温度は、好ましくは７００℃以下、より好ましくは３００〜６００℃であり、焼成時間は、好ましくは１０分〜３時間、より好ましくは０．５〜１．５時間である。 After passing through the step (II), it is preferable to go through the step of firing in the step (III). The firing conditions are preferably carried out under an inert gas atmosphere or under reducing conditions, and the firing temperature is preferably 700 ° C. or less, more preferably 300 to 600 ° C., and the firing time is preferably 10 minutes to 3 hours, more preferably 0.5 to 1.5 hours.
本発明で得られる正極活物質は、工程（Ｉ）において、カーボンＸを担持してなるケイ酸化合物用いつつ、工程（III）においてカーボンＹを担持するのが好ましい。これにより、ジルコニウム含有オリビン型正極材料（１）表面にカーボンＸ及びカーボンＹの異なる種類のカーボンが堅固に担持された高い電池物性を発現し得る正極活物質とすることができる。ジルコニウム含有オリビン型シリケート化合物（１）に担持されたカーボンＸ及カーボンＹの合計量は、二次電池用正極活物質中に、好ましくは５〜１５質量％であり、より好ましくは８〜１３質量％である。また、カーボンＸの量はカーボンＹよりも多いのが好ましく、カーボンＸとカーボンＹの質量比（カーボンＸ：カーボンＹ）が、好ましくは５１：４９〜７０：３０であり、より好ましくは５５：４５〜７０：３０である。なお、カーボンＸとしてグラフェンオキサイドを用いる場合、上記合計量及び質量比は、還元されてなるグラフェンに換算した量とする。 The positive electrode active material obtained by the present invention preferably supports carbon Y in step (III) while using a silicate compound in which carbon X is supported in step (I). Thereby, it can be set as the positive electrode active material which can express the high battery physical property by which the carbon of different kind of carbon X and carbon Y was carry | supported firmly on the surface of a zirconium containing olivine type positive electrode material (1). The total amount of carbon X and carbon Y supported on the zirconium-containing olivine type silicate compound (1) is preferably 5 to 15% by mass, more preferably 8 to 13% by mass in the positive electrode active material for a secondary battery. %. The amount of carbon X is preferably larger than that of carbon Y, and the mass ratio of carbon X to carbon Y (carbon X: carbon Y) is preferably 51:49 to 70:30, more preferably 55: 45-70: 30. In addition, when using graphene oxide as carbon X, the said total amount and mass ratio shall be the quantity converted into the graphene reduced.
得られた正極活物質は、放電容量の点で優れており、二次電池の正極材料として有用である。かかる正極活物質の平均粒子径は、好ましくは１０〜３００ｎｍであり、より好ましくは２０〜２００ｎｍである。本発明の正極活物質を適用できる二次電池としては、リチウムイオン二次電池であればよく、正極と負極と電解液とセパレータを必須構成とするものであれば特に限定されない。 The obtained positive electrode active material is excellent in terms of discharge capacity, and is useful as a positive electrode material for a secondary battery. The average particle size of the positive electrode active material is preferably 10 to 300 nm, and more preferably 20 to 200 nm. The secondary battery to which the positive electrode active material of the present invention can be applied may be a lithium ion secondary battery, and is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components.
ここで、負極については、リチウムイオンを充電時には吸蔵し、かつ放電時には放出することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。たとえば、リチウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムを電気化学的に吸蔵・放出し得るインターカレート材料で形成された電極、特に炭素材料を用いることが好ましい。 Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.
電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常二次電池の電解液の用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。 The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones, oxolanes, A compound or the like can be used.
支持塩は、その種類が特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2及びＬｉＮ（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2及びＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。 The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 and LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and organic salt derivatives It is preferable that it is at least 1 type of these.
セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。 The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［実施例１］
ＬｉＯＨ・Ｈ2Ｏ ４．２０ｇ、Ｎａ4ＳｉＯ4・ｎＨ2Ｏ １２．５８ｇに超純水３７．５ｃｍ3を加えて混合した（この時のｐＨは約１３）。この水分散液にＦｅＳＯ4・７Ｈ2Ｏ １．３１ｇ、ＭｎＳＯ4・５Ｈ2Ｏ １０．２０ｇ、ＺｒＳＯ4・４Ｈ2Ｏ ０．５３ｇ、ＮａＯＨ ０．６０ｇ及びＨ3ＰＯ4 ０．５８ｇを添加し、混合した。得られた混合液をオートクレーブに投入し、０．７ＭＰａの圧力下、１５０℃で１２ｈｒ水熱反応を行った。反応液をろ過後、−５０℃で１２時間凍結乾燥した。凍結乾燥（約１２時間）して粉末を得た。
続いて、得られた粉末に、カーボンブラック（カーボンＥＣＰ、ライオン社製）をかかる粉末とカーボンブラックの全量中に１０質量％となる量で添加して混合し、混合物を得た。得られた混合物を微粒子複合化装置 ノビルタ（ＮＯＢ−ＭＩＮＩ、ホソカワミクロン社製、動力０．７５ｋｗ）に投入し、処理温度を２５〜３５℃として、インペラの周速度を３９ｍ／ｓ、処理時間を２０分として混合した。
次いで、窒素ガスをパージした電気炉を用い、得られた混合物を温度７００℃で１時間焼成して、正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03（ＳｉＯ4）0.925（ＰＯ4）0.1／Ｃ、平均粒径５０ｎｍ）を得た。
[Example 1]
37.5 cm 3 of ultrapure water was added to and mixed with 4.20 g of LiOH.H 2 O and 12.58 g of Na 4 SiO 4 .nH 2 O (pH at this time was about 13). To this aqueous dispersion, 1.31 g of FeSO 4 .7H 2 O, 10.20 g of MnSO 4 .5H 2 O, 0.53 g of ZrSO 4 .4H 2 O, 0.60 g of NaOH and 0.58 g of H 3 PO 4 were added. , Mixed. The obtained mixed liquid was put into an autoclave and subjected to a hydrothermal reaction for 12 hours at 150 ° C. under a pressure of 0.7 MPa. The reaction solution was filtered and lyophilized at −50 ° C. for 12 hours. Freeze drying (about 12 hours) gave a powder.
Subsequently, carbon black (carbon ECP, manufactured by Lion Corporation) was added to the obtained powder in an amount of 10% by mass in the total amount of the powder and carbon black, and mixed to obtain a mixture. The obtained mixture was put into a fine particle composite apparatus Nobilta (NOB-MINI, manufactured by Hosokawa Micron Corporation, power 0.75 kW), the processing temperature was set to 25 to 35 ° C., the impeller peripheral speed was 39 m / s, and the processing time was 20 Mixed as minutes.
Next, using an electric furnace purged with nitrogen gas, the obtained mixture was fired at a temperature of 700 ° C. for 1 hour to produce a positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 (SiO 4 ) 0.925 (PO 4 ) 0.1 / C, average particle size 50 nm).
［実施例２］
Ｎａ4ＳｉＯ4・ｎＨ2Ｏを１３．９７ｇとし、Ｈ3ＰＯ4の代わりにＮＨ4Ｆ ０．０９ｇを用いた以外、実施例１と同様にして正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03ＳｉＯ3.95Ｆ0.1／Ｃ、平均粒径５０ｎｍ）を得た。
[Example 2]
A positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr) was prepared in the same manner as in Example 1 except that 13.97 g of Na 4 SiO 4 .nH 2 O was used and 0.09 g of NH 4 F was used instead of H 3 PO 4. 0.03 SiO 3.95 F 0.1 / C, average particle size 50 nm).
［実施例３］
Ｈ3ＰＯ4 ０．５８ｇに加え、さらにＮＨ4 ０．０９ｇを用いた以外、実施例４と同様にして正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03Ｓｉ0.925Ｐ0.1Ｏ3.95Ｆ0.1／Ｃ、平均粒径５０ｎｍ）を得た。
[Example 3]
A positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 Si 0.925 P 0.1 O 3.95 F 0.1 / C) was used in the same manner as in Example 4 except that 0.59 g of NH 4 was used in addition to 0.58 g of H 3 PO 4. The average particle size was 50 nm).
［実施例４］
天然黒鉛（ＳＰ−２７０、日本黒鉛（株）製）の粉砕物を用いてハマーズ法により作製したグラフェンオキサイド ０．２０ｇ、オルトケイ酸テトラエチル ２．４１ｇ、エタノール ５．０ｇ、及び水 ３２．５ｍＬを混合し、スラリー水Ｘを調製した。
得られたスラリー水Ｘをオートクレーブに投入し、０．７ＭＰａの圧力下、１５０℃で１０時間水熱反応を行い、生成した複合体を含む混合液を得た。
[Example 4]
Mixing 0.20 g of graphene oxide, 2.41 g of tetraethyl orthosilicate, 5.0 g of ethanol, and 32.5 mL of water, prepared by a Hammers method using a pulverized product of natural graphite (SP-270, manufactured by Nippon Graphite Co., Ltd.) Slurry water X was prepared.
The obtained slurry water X was put into an autoclave and subjected to a hydrothermal reaction at 150 ° C. for 10 hours under a pressure of 0.7 MPa to obtain a mixed solution containing the produced composite.
次いで、水熱反応後に得られた混合液をそのまま用い、かかる混合液にＬｉＯＨ・Ｈ2Ｏ １．０５ｇ、Ｚｒ（ＳＯ4）2・４Ｈ2Ｏ ０．１３ｇ、ＭｎＳＯ4・５Ｈ2Ｏ ２．５５ｇ、ＦｅＳＯ4・７Ｈ2Ｏ ０．３３ｇ、ＮａＯＨ ２．０ｇ、及びＨ3ＰＯ4 ０．１５ｇを添加して混合し、ｐＨ１３のスラリー水Ｙを得た。かかるスラリー水Ｙにおける、水１００質量部に対する水酸化リチウム及び水酸化ナトリウムの合計量は９質量部であり、モル比（Ｌｉ：Ｎａ）は１：２であり、またオルトケイ酸テトラエチルと水酸化ナトリウムのモル比は１：４であった。さらに、ジルコニウム化合物及び遷移金属（Ｍ）塩の合計モル量を基準とする水酸化リチウムのＬｉ源としての量は、２倍であった。
得られたスラリー水Ｙをオートクレーブに投入し、０．７ＭＰａの圧力下、１５０℃で１２時間水熱反応を行い、複合体Ｙを生成した。生成した複合体Ｙをろ過し、次いで質量比（結晶：水）が１：１２となる量の水により洗浄した後、−５０℃で１２時間凍結乾燥して粉末を得た。
Then, it uses the resulting mixture after the hydrothermal reaction, LiOH · H 2 O 1.05g in such mixture, Zr (SO 4) 2 · 4H 2 O 0.13g, MnSO 4 · 5H 2 O 2. 55 g of FeSO 4 .7H 2 O 0.33 g, NaOH 2.0 g, and H 3 PO 4 0.15 g were added and mixed to obtain slurry water Y having a pH of 13. In the slurry water Y, the total amount of lithium hydroxide and sodium hydroxide with respect to 100 parts by mass of water is 9 parts by mass, the molar ratio (Li: Na) is 1: 2, and tetraethyl orthosilicate and sodium hydroxide The molar ratio was 1: 4. Furthermore, the amount of lithium hydroxide as a Li source based on the total molar amount of the zirconium compound and the transition metal (M) salt was doubled.
The obtained slurry water Y was put into an autoclave, and a hydrothermal reaction was performed at 150 ° C. for 12 hours under a pressure of 0.7 MPa to produce a composite Y. The produced complex Y was filtered, washed with water in an amount such that the mass ratio (crystal: water) was 1:12, and then lyophilized at −50 ° C. for 12 hours to obtain a powder.
続いて、得られた粉末に、カーボンブラック（カーボンＥＣＰ、ライオン社製）をかかる粉末とカーボンブラックの全量中に５質量％となる量（０．１ｇ）で添加して混合し、混合物を得た。得られた混合物を微粒子複合化装置 ノビルタ（ＮＯＢ−ＭＩＮＩ、ホソカワミクロン社製、動力０．７５ｋｗ）に投入し、処理温度を２５〜３５℃として、インペラの周速度を３９ｍ／ｓ、処理時間を２０分として混合した。
次いで、窒素ガスをパージした電気炉を用い、得られた混合物を温度７００℃で１時間焼成して、正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03（ＳｉＯ4）0.925（ＰＯ4）0.1／Ｃ、平均粒径５０ｎｍ）を得た。得られた正極活物質中に担持されてなるグラフェン及びカーボンブラックの合計量は、１５質量％であり、グラフェンとカーボンブラックの質量比（グラフェン：カーボンブラック）は、２：１であった。
Subsequently, carbon black (carbon ECP, manufactured by Lion Corporation) is added to the obtained powder and the total amount of carbon black in an amount (0.1 g) of 5% by mass and mixed to obtain a mixture. It was. The obtained mixture was put into a fine particle composite apparatus Nobilta (NOB-MINI, manufactured by Hosokawa Micron Corporation, power 0.75 kW), the processing temperature was set to 25 to 35 ° C., the impeller peripheral speed was 39 m / s, and the processing time was 20 Mixed as minutes.
Next, using an electric furnace purged with nitrogen gas, the obtained mixture was fired at a temperature of 700 ° C. for 1 hour to produce a positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 (SiO 4 ) 0.925 (PO 4 ) 0.1 / C, average particle size 50 nm). The total amount of graphene and carbon black supported in the obtained positive electrode active material was 15% by mass, and the mass ratio of graphene to carbon black (graphene: carbon black) was 2: 1.
［実施例５］
Ｈ3ＰＯ4の代わりにＮＨ4 ０．０２ｇを用いた以外、実施例４と同様にして正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03ＳｉＯ3.95Ｆ0.1／Ｃ、平均粒径５０ｎｍ）を得た。得られた正極活物質中に担持されてなるグラフェン及びカーボンブラックの合計量は、１５質量％であり、グラフェンとカーボンブラックの質量比（グラフェン：カーボンブラック）は、２：１であった。
[Example 5]
A positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 SiO 3.95 F 0.1 / C, average particle size 50 nm) was obtained in the same manner as in Example 4 except that 0.02 g of NH 4 was used instead of H 3 PO 4. It was. The total amount of graphene and carbon black supported in the obtained positive electrode active material was 15% by mass, and the mass ratio of graphene to carbon black (graphene: carbon black) was 2: 1.
［実施例６］
Ｈ3ＰＯ4 ０．１５ｇに加え、さらにＮＨ4 ０．０２ｇを用いた以外、実施例４と同様にして正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03Ｓｉ0.925Ｐ0.1Ｏ3.95Ｆ0.1／Ｃ、平均粒径５０ｎｍ）を得た。得られた正極活物質中に担持されてなるグラフェン及びカーボンブラックの合計量は、１５質量％であり、グラフェンとカーボンブラックの質量比（グラフェン：カーボンブラック）は、６６．７：３３．３であった。
[Example 6]
A positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 Si 0.925 P 0.1 O 3.95 F 0.1 / C) was used in the same manner as in Example 4 except that 0.14 g of H 3 PO 4 and 0.02 g of NH 4 were used. The average particle size was 50 nm). The total amount of graphene and carbon black supported in the obtained positive electrode active material is 15% by mass, and the mass ratio of graphene to carbon black (graphene: carbon black) is 66.7: 33.3. there were.
［比較例１］
ＮａＯＨ及びＨ3ＰＯ4を用いなかった以外、実施例１と同様にして正極活物質（Ｌｉ2Ｆｅ0.09Ｍｎ0.85Ｚｒ0.03ＳｉＯ4／Ｃ、平均粒径５０ｎｍ）を得た。
[Comparative Example 1]
A positive electrode active material (Li 2 Fe 0.09 Mn 0.85 Zr 0.03 SiO 4 / C, average particle size 50 nm) was obtained in the same manner as in Example 1 except that NaOH and H 3 PO 4 were not used.
［試験例１］
実施例１〜６及び比較例１で得られた正極活物質を用い、リチウムイオン二次電池の正極を作製した。具体的には、実施例１及び比較例１〜２で得られた正極活物質、ケッチェンブラック（導電剤）、ポリフッ化ビニリデン（粘結剤）を重量比７５：１５：１０の配合割合で混合し、これにＮ−メチル−２−ピロリドンを加えて充分混練し、正極スラリーを調製した。正極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、正極とした。
[Test Example 1]
Using the positive electrode active materials obtained in Examples 1 to 6 and Comparative Example 1, positive electrodes for lithium ion secondary batteries were produced. Specifically, the positive electrode active material, ketjen black (conductive agent), and polyvinylidene fluoride (binder) obtained in Example 1 and Comparative Examples 1 and 2 were mixed at a weight ratio of 75:15:10. After mixing, N-methyl-2-pyrrolidone was added thereto and kneaded sufficiently to prepare a positive electrode slurry. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.
次いで、上記の正極を用いてコイン型リチウムイオン二次電池を構築した。負極には、φ１５ｍｍに打ち抜いたリチウム箔を用いた。電解液には、エチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒に、ＬｉＰＦ6を１ｍｏｌ／ｌの濃度で溶解したものを用いた。セパレータには、ポリプロピレンなどの高分子多孔フィルムなど、公知のものを用いた。これらの電池部品を露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。 Next, a coin-type lithium ion secondary battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / l in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
製造したリチウムイオン電池を用いて定電流密度での充放電を１サイクル行った。このときの充電条件は電流０．１ＣＡ（３３．３ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件は電流０．１ＣＡ、終止電圧１．５Ｖの定電流放電とした。温度は全て３０℃とした。
結果を表１に示す。
One cycle of charge and discharge at a constant current density was performed using the manufactured lithium ion battery. The charging conditions at this time were constant current and constant voltage charging with a current of 0.1 CA (33.3 mA / g) and a voltage of 4.5 V, and the discharging conditions were constant current discharging with a current of 0.1 CA and a final voltage of 1.5 V. All temperatures were 30 ° C.
The results are shown in Table 1.
表１の結果より、本発明の二次電池用正極活物質を用いたリチウムイオン電池は、比較例のそれに比べて優れた電池特性を有することがわかる。 From the results in Table 1, it can be seen that the lithium ion battery using the positive electrode active material for the secondary battery of the present invention has battery characteristics superior to those of the comparative example.
Claims (11)
（式（１）中、ａ、ｂ、ｃ及びｄはａ＋ｂ＋ｃ＋ｄ=１−２ｘを満たし、ｘは０＜ｘ＜０．５であり、ｙは０≦ｙ≦２であり、ｚは０≦ｚ≦０．１であり、かつｙ及びｚは０＜ｙ＋ｚを満たす）
で表されるリチウム二次電池のジルコニウム含有オリビン型正極材料。 Formula (1): Li 2 Fe a Ni b Co c Mn d Zr x Si 1-z P 0.8z O 4-y F 2y (1)
(In the formula (1), a, b, c and d satisfy a + b + c + d = 1−2x, x is 0 <x <0.5, y is 0 ≦ y ≦ 2, and z is 0 ≦ z. ≦ 0.1, and y and z satisfy 0 <y + z)
A zirconium-containing olivine-type positive electrode material for a lithium secondary battery represented by :
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