JP6057402B2 - Electrode active material, method for producing the same, and lithium ion battery - Google Patents
Electrode active material, method for producing the same, and lithium ion battery Download PDFInfo
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- JP6057402B2 JP6057402B2 JP2010045235A JP2010045235A JP6057402B2 JP 6057402 B2 JP6057402 B2 JP 6057402B2 JP 2010045235 A JP2010045235 A JP 2010045235A JP 2010045235 A JP2010045235 A JP 2010045235A JP 6057402 B2 JP6057402 B2 JP 6057402B2
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- 239000007772 electrode material Substances 0.000 title claims description 137
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims description 97
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 63
- 229910052799 carbon Inorganic materials 0.000 claims description 61
- 239000011247 coating layer Substances 0.000 claims description 56
- 239000000126 substance Substances 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012298 atmosphere Substances 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 239000004020 conductor Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 49
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 230000007774 longterm Effects 0.000 description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 14
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 13
- 239000003575 carbonaceous material Substances 0.000 description 13
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000010335 hydrothermal treatment Methods 0.000 description 10
- -1 nickel metal hydride Chemical class 0.000 description 10
- 239000011149 active material Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000010450 olivine Substances 0.000 description 6
- 229910052609 olivine Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 241000080590 Niso Species 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FWLKYEAOOIPJRL-UHFFFAOYSA-N prop-1-yn-1-ol Chemical compound CC#CO FWLKYEAOOIPJRL-UHFFFAOYSA-N 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy 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
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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
Description
本発明は、電極活物質とその製造方法及びリチウムイオン電池に関し、特に詳しくは、オリビン構造を有するリン酸塩系電極活物質の１種であり、負荷特性、サイクル特性及びエネルギー密度に優れたリチウムイオン電池の電極材料として用いて好適な電極活物質とその製造方法、及び、この電極活物質を用いた電極を備えているリチウムイオン電池に関するものである。 TECHNICAL FIELD The present invention relates to an electrode active material , a method for producing the same, and a lithium ion battery, and more particularly, is a lithium electrode active material having an olivine structure and is excellent in load characteristics, cycle characteristics, and energy density. The present invention relates to an electrode active material suitable for use as an electrode material for an ion battery, a method for producing the same , and a lithium ion battery including an electrode using the electrode active material.
近年、小型化、軽量化、高容量化が期待される電池として、リチウムイオン電池等の非水電解液系の二次電池が提案され、実用に供されている。
リチウムイオン電池は、リチウムイオンを可逆的に脱挿入可能な性質を有する正極及び負極と、非水系の電解質とにより構成されている。
リチウムイオン電池は、従来の鉛電池、ニッケルカドミウム電池、ニッケル水素電池等の二次電池と比べて、軽量かつ小型で高エネルギーを有しており、携帯用電話機、ノート型パーソナルコンピュータ等の携帯用電子機器の電源として用いられているが、近年、電気自動車、ハイブリッド自動車、電動工具等の高出力電源としても検討されている。これらの高出力電源として用いられる電池の電極活物質には、高速の充放電特性が求められている。また、発電負荷の平滑化、定置用電源、バックアップ電源等の大型電池への応用も検討されており、長期の安全性、信頼性と共に、資源的に豊富で安価であること（資源量の問題が無いこと）も重要視されている。
In recent years, non-aqueous electrolyte secondary batteries such as lithium ion batteries have been proposed and put into practical use as batteries that are expected to be reduced in size, weight, and capacity.
A lithium ion battery is composed of a positive electrode and a negative electrode having a property capable of reversibly inserting and removing lithium ions, and a non-aqueous electrolyte.
Lithium-ion batteries are lighter, smaller, and have higher energy than secondary batteries such as conventional lead batteries, nickel cadmium batteries, and nickel metal hydride batteries, and are portable for portable telephones, notebook personal computers, etc. Although it is used as a power source for electronic devices, it has recently been studied as a high-output power source for electric vehicles, hybrid vehicles, electric tools, and the like. High-speed charge / discharge characteristics are required for the electrode active materials of batteries used as these high-output power supplies. Application to large batteries such as smoothing of power generation load, stationary power supply, backup power supply, etc. is also being studied, and it is resource-rich and inexpensive with long-term safety and reliability. Is also considered important.
リチウムイオン電池の正極は、正極活物質と称されるリチウムイオンを可逆的に脱挿入可能な性質を有するリチウム含有金属酸化物、導電助剤及びバインダーを含む電極材料により構成されており、この電極材料を集電体と称される金属箔の表面に塗布することにより正極とされている。
このリチウムイオン電池の正極活物質としては、通常、コバルト酸リチウム（ＬｉＣｏＯ２）が用いられているが、その他、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）、リン酸鉄リチウム（ＬｉＦｅＰＯ４）等のリチウム（Ｌｉ）化合物が用いられている。
これらのリチウム化合物のうち、コバルト酸リチウムやニッケル酸リチウムは、人体や環境に対する毒性、資源量、充電状態の不安定性等の種々の問題点を有している。また、マンガン酸リチウムは、高温下で電解液中へ溶解するという問題点が指摘されている。
そこで、近年では、長期の安全性、信頼性に優れた、リン酸鉄リチウムに代表されるオリビン構造を有するリン酸塩系電極活物質が注目を集めている。
The positive electrode of a lithium ion battery is composed of an electrode material including a lithium-containing metal oxide called a positive electrode active material, which has a property of reversibly removing and inserting lithium ions, a conductive additive, and a binder. The material is applied to the surface of a metal foil called a current collector to form a positive electrode.
As the positive electrode active material of this lithium ion battery, lithium cobaltate (LiCoO 2 ) is usually used, but in addition, lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), iron phosphate Lithium (Li) compounds such as lithium (LiFePO 4 ) are used.
Among these lithium compounds, lithium cobaltate and lithium nickelate have various problems such as toxicity to the human body and the environment, the amount of resources, and instability of the charged state. Further, it has been pointed out that lithium manganate is dissolved in an electrolytic solution at a high temperature.
Therefore, in recent years, a phosphate-based electrode active material having an olivine structure typified by lithium iron phosphate, which has excellent long-term safety and reliability, has attracted attention.
このリン酸塩系電極活物質は電子伝導性が十分ではないために、大電流の充放電を行うためには、粒子の微細化、導電性物質との複合化等さまざまな工夫が必要であり、多くの努力がなされている。
しかしながら、粒子の微細化や導電性物質を多量に用いた複合化を行った場合、電極密度の低下を招き、引いては電池の密度低下、即ち単位容積当たりの容量低下を引き起こしてしまうという問題点がある。そこで、この問題点を解決する方法として、電子導電性物質である炭素前駆体として有機物溶液を用い、この有機物溶液と電極活物質粒子とを混合した後、乾燥し、得られた乾燥物を非酸化性雰囲気下にて熱処理し、有機物を炭化させることにより、電極活物質粒子の表面を炭素で被覆する炭素被覆法が見出された。
Since this phosphate-based electrode active material does not have sufficient electron conductivity, various measures such as finer particles and compounding with conductive materials are required to charge and discharge a large current. Many efforts have been made.
However, there is a problem in that when particles are refined or complexed using a large amount of a conductive substance, the electrode density is lowered, which in turn causes a decrease in battery density, that is, a decrease in capacity per unit volume. There is a point. Therefore, as a method for solving this problem, an organic solution is used as a carbon precursor, which is an electronically conductive material, the organic solution and electrode active material particles are mixed, dried, and the resulting dried product is non-coated. A carbon coating method has been found in which the surface of the electrode active material particles is coated with carbon by heat treatment in an oxidizing atmosphere to carbonize the organic matter.
この炭素被覆法は、電極活物質粒子の表面に、必要最少限の量の炭素を極めて効率良く被覆させることが可能で、電極密度を大きく低下させること無く、導電性の向上を図ることができるという優れた特徴を有することから、様々な提案がなされている。
これらの提案の１つに、ＬｉＦｅＰＯ４からなる粒子の表面を、還元糖の熱分解により生成した炭素により被覆した電極材料がある（特許文献１）。
この電極材料は、リチウム成分と、Ｆｅ成分と、Ｐ成分と、還元糖とを含む溶液または懸濁液を噴霧し、加熱することにより、容易に合成することができる。
In this carbon coating method, the surface of the electrode active material particles can be coated with the minimum amount of carbon extremely efficiently, and the conductivity can be improved without greatly reducing the electrode density. Therefore, various proposals have been made.
One of these proposals is an electrode material in which the surface of particles made of LiFePO 4 is coated with carbon generated by thermal decomposition of reducing sugar (Patent Document 1).
This electrode material can be easily synthesized by spraying and heating a solution or suspension containing a lithium component, an Fe component, a P component, and a reducing sugar.
しかしながら、従来の炭素被覆法で得られた多くの電極材料は、ＬｉＦｅＰＯ４単体、もしくはＬｉＦｅＰＯ４単体に若干の異種元素を含む化合物を添加したものであり、ＬｉＦｅＰＯ４以外の電極材料、例えば、比較的資源量が豊富であり、かつ、より高電圧で動作することから、より高エネルギー密度の電極材料としてＬｉＭｎＰＯ４やＬｉＣｏＰＯ４が期待されているが、充分な特性を有するＬｉＭｎＰＯ４やＬｉＣｏＰＯ４は、いまだに得られていない。
例えば、ＬｉＭｎＰＯ４の場合、Ｍｎが炭化反応を抑制する負触媒として働くために、ＬｉＭｎＰＯ４にＬｉＦｅＰＯ４で効果的な有機物による炭素被覆法を適用しても、十分な効果を得ることができない。
However, many electrode materials obtained by the conventional carbon coating method are LiFePO 4 simple substance or LiFePO 4 simple substance added with a compound containing some different elements, and electrode materials other than LiFePO 4 , for example, comparison LiMnPO 4 and LiCoPO 4 are expected as electrode materials with higher energy density because they have abundant resources and operate at higher voltages, but LiMnPO 4 and LiCoPO 4 having sufficient characteristics are expected It has not been obtained yet.
For example, in the case of LiMnPO 4 , Mn acts as a negative catalyst that suppresses the carbonization reaction. Therefore, even if a carbon coating method using an organic substance effective with LiFePO 4 is applied to LiMnPO 4 , a sufficient effect cannot be obtained.
もちろん、ＬｉＭｎＰＯ４にＬｉＦｅＰＯ４を固溶させた電極活物質に同様の炭素被覆を施した例も報告されてはいるが、この炭素被覆電極活物質では、固溶体とすることで粒子表面に炭化触媒であるＦｅが現れた結果に他ならない。
そこで、負触媒であるＭｎの作用に勝る十分な量のＦｅを電極活物質の粒子表面に生じさせるには、少なくともＦｅ／Ｍｎ比が１０／９０を超える程の多量のＦｅを固溶させる必要があり、その結果、電気化学的な反応電位の低い領域が電極活物質全体の１０％を超えることとなってしまい、高電位かつ高エネルギーというＬｉＭｎＰＯ４の有する効果を十分に発揮することができない。
Of course, an example in which a similar carbon coating is applied to an electrode active material in which LiFePO 4 is dissolved in LiMnPO 4 has been reported, but in this carbon-coated electrode active material, a carbonization catalyst is formed on the particle surface by forming a solid solution. This is the result of the appearance of Fe.
Thus, in order to generate a sufficient amount of Fe on the particle surface of the electrode active material that exceeds the action of Mn, which is a negative catalyst, it is necessary to dissolve a large amount of Fe at least so that the Fe / Mn ratio exceeds 10/90. As a result, the region where the electrochemical reaction potential is low exceeds 10% of the entire electrode active material, and the high-potential and high-energy effect of LiMnPO 4 cannot be fully exhibited. .
本発明は、上記の課題を解決するためになされたものであって、高負荷特性、高サイクル特性及び高エネルギー密度を実現することが可能な電極活物質及びリチウムイオン電池を提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object thereof is to provide an electrode active material and a lithium ion battery capable of realizing high load characteristics, high cycle characteristics, and high energy density. And
本発明者等は、上記課題を解決するために鋭意検討を行った結果、ＬｉｗＡｘＤＯ４（但し、ＡはＭｎ、Ｃｏの群から選択される１種または２種、ＤはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｗ≦４、０＜ｘ≦１．５）からなる粒子の表面を、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の物質と、Ｆｅ及びＮｉのいずれか１種または２種を含む物質とを含む被覆層により被覆すれば、高負荷特性、高サイクル特性及び高エネルギー密度を有する電極活物質が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have determined that Li w A x DO 4 (where A is one or two selected from the group of Mn and Co, D is P, The surface of particles composed of one or more selected from the group of Si and S, 0 <w ≦ 4, 0 <x ≦ 1.5) is carbonized by heat-treating organic matter in a non-oxidizing atmosphere. An electrode active material having high load characteristics, high cycle characteristics, and high energy density when coated with a coating layer containing an organic carbonaceous material and a material containing one or two of Fe and Ni Has been found, and the present invention has been completed.
すなわち、本発明の請求項１記載の電極活物質は、ＬｉｗＡｘＤＯ４（但し、ＡはＭｎ、Ｃｏの群から選択される１種または２種、ＤはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｗ≦４、０＜ｘ≦１．５）からなる粒子の表面を、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の電子伝導性物質及びＦｅ及びＮｉのいずれか１種または２種を含む物質を含有する被覆層により被覆してなり、前記有機系炭素質の電子伝導性物質は、前記Ｆｅ及びＮｉのいずれか１種または２種を含む物質と接触してなることを特徴とする。 That is, the electrode active material according to claim 1 of the present invention is Li w A x DO 4 (where A is one or two selected from the group of Mn and Co, D is a group of P, Si, and S) Organic carbon obtained by carbonizing the surface of particles consisting of one or more selected from the group consisting of 0 <w ≦ 4, 0 <x ≦ 1.5) in a non-oxidizing atmosphere. The organic carbonaceous electron conductive material is either Fe or Ni. The organic carbonaceous electron conductive material is coated with a coating layer containing a material containing any one or two of Fe and Ni. Or in contact with a substance containing one or two kinds.
本発明の請求項２記載の電極活物質は、請求項１記載の電極活物質において、前記Ｆｅ及びＮｉのいずれか１種または２種を含む物質は、Ｆｅ化合物またはＮｉ化合物であることを特徴とする。 The electrode active material according to claim 2 of the present invention is the electrode active material according to claim 1, wherein the substance containing any one or two of Fe and Ni is an Fe compound or a Ni compound. And
本発明の請求項３記載の電極活物質の製造方法は、請求項１または２記載の電極活物質の製造方法であって、前記ＬｉThe method for producing an electrode active material according to claim 3 of the present invention is the method for producing an electrode active material according to claim 1 or 2, wherein the Li ｗw ＡA ｘx ＤＯDO ４4 粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液を乾燥後、熱処理して、表面処理ＬｉThe particles are put into a solution obtained by dissolving the E source in a solvent containing water as a main component, and stirred to form a suspension. ｗw ＡA ｘx ＤＯDO ４4 粒子とし、この表面処理ＬｉThis surface treatment Li ｗw ＡA ｘx ＤＯDO ４4 粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体とし、この粉体を非酸化性雰囲気下にて熱処理することを特徴とする。The particles are put into a solution containing an organic substance serving as a carbon source, stirred to form a slurry, the slurry is dried to form a powder, and the powder is heat-treated in a non-oxidizing atmosphere. .
本発明の請求項４記載の電極活物質の製造方法は、請求項３記載の電極活物質の製造方法において、前記Ｅ源は、Ｆｅ、Ｎｉの群から選択される１種または２種を含む化合物であることを特徴とする。The electrode active material manufacturing method according to claim 4 of the present invention is the electrode active material manufacturing method according to claim 3, wherein the E source includes one or two selected from the group of Fe and Ni. It is a compound.
本発明の請求項５記載のリチウムイオン電池は、請求項１または２記載の電極活物質を用いた電極を備えてなることを特徴とする。 A lithium ion battery according to claim 5 of the present invention is characterized by comprising an electrode using the electrode active material according to claim 1 or 2 .
本発明の電極活物質によれば、ＬｉｗＡｘＤＯ４（但し、ＡはＭｎ、Ｃｏの群から選択される１種または２種、ＤはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｗ≦４、０＜ｘ≦１．５）からなる粒子の表面を、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の物質と、Ｆｅ及びＮｉのいずれか１種または２種を含む物質とを含む被覆層により被覆したので、オリビン構造を有するＬｉｗＡｘＤＯ４の表面が必要最少限の電子導電性を有する被覆層により被覆されることとなり、したがって、電圧、エネルギー密度、負荷特性を大幅に向上させることができ、長期のサイクル安定性及び安全性にも優れている。 According to the electrode active material of the present invention, Li w A x DO 4 (where A is one or two selected from the group of Mn and Co, and D is one selected from the group of P, Si, and S) An organic carbonaceous material obtained by heat-treating and carbonizing an organic substance in a non-oxidizing atmosphere on the surface of a particle composed of seeds or two or more, 0 <w ≦ 4, 0 <x ≦ 1.5), having covered with a covering layer which contains a substance comprising any one or two of Fe and Ni, coated with a coating layer having an electron conductivity of Li w a x surface of DO 4 requires minimum having an olivine structure Therefore, the voltage, energy density, and load characteristics can be greatly improved, and the long-term cycle stability and safety are excellent.
本発明のリチウムイオン電池によれば、本発明の電極活物質を用いた電極を備えたので、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたリチウムイオン電池を提供することができる。 According to the lithium ion battery of the present invention, since the electrode using the electrode active material of the present invention is provided, it has high voltage, high energy density, high load characteristics, and excellent long-term cycle stability and safety. A lithium ion battery can be provided.
本発明の電極活物質及びリチウムイオン電池を実施するための形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The form for implementing the electrode active material and lithium ion battery of this invention is demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
［第１の実施形態］
（電極活物質）
図１は、本発明の第１の実施形態の電極活物質を示す断面図であり、この電極活物質１は、ＬｉｗＡｘＤＯ４（但し、ＡはＭｎ、Ｃｏの群から選択される１種または２種、ＤはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｗ≦４、０＜ｘ≦１．５）からなる粒子（以下、ＬｉｗＡｘＤＯ４粒子と略称する）２の表面が、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）を含む被覆層３により被覆されている。
[First Embodiment]
(Electrode active material)
FIG. 1 is a cross-sectional view showing an electrode active material according to a first embodiment of the present invention. The electrode active material 1 is Li w A x DO 4 (where A is selected from the group of Mn and Co). 1 type or 2 types, D is 1 type or 2 types or more selected from the group of P, Si, S, 0 <w ≦ 4, 0 <x ≦ 1.5) (hereinafter referred to as Li w A x The surface of DO 2 particles is abbreviated as Li y E z GO 4 (where E is one or two selected from the group Fe, Ni, G is selected from the group P, Si, S) 1 or 2 or more, 0 <y ≦ 2, 0 <z ≦ 1.5).
上記のＡについては、Ｍｎ、Ｃｏの群から選択される１種または２種が、また、Ｄについては、Ｐ、Ｓｉ、Ｓの群から選択される１種または２種以上が、高い放電電位、豊富な資源量、安全性等の点から好ましい。
この粒子２の平均粒径は５ｎｍ以上かつ５００ｎｍ以下が好ましく、より好ましくは２０ｎｍ以上かつ２００ｎｍ以下である。
その理由は、平均粒径が５ｎｍより小さいと、充放電による体積変化により結晶構造が破壊される虞があるからであり、また、平均粒径が５００ｎｍより大きいと、粒子内部への電子の供給量が不足し、利用効率が低下するからである。
For A, one or two selected from the group of Mn and Co, and for D, one or more selected from the group of P, Si, and S are high discharge potentials. From the viewpoint of abundant resources and safety.
The average particle size of the particles 2 is preferably 5 nm or more and 500 nm or less, more preferably 20 nm or more and 200 nm or less.
The reason is that if the average particle size is smaller than 5 nm, the crystal structure may be destroyed due to the volume change due to charge / discharge, and if the average particle size is larger than 500 nm, electrons are supplied into the particles. This is because the amount is insufficient and the utilization efficiency is lowered.
被覆層３の厚みは０．１ｎｍ以上かつ２５ｎｍ以下が好ましく、より好ましくは１ｎｍ以上かつ５ｎｍ以下である。
その理由は、厚みが０．１ｎｍより薄いと、炭化触媒能が不十分となり、したがって、電子導電性が不十分となり、その結果、電子の供給量が不足するからであり、また、厚みが２５ｎｍより厚いと、電極活物質１中の活物質の割合が減少し、活物質が有効に利用され難くなるからである。
The thickness of the coating layer 3 is preferably 0.1 nm or more and 25 nm or less, more preferably 1 nm or more and 5 nm or less.
The reason is that if the thickness is less than 0.1 nm, the carbonization catalytic ability becomes insufficient, and therefore, the electronic conductivity becomes insufficient, resulting in insufficient supply of electrons, and the thickness becomes 25 nm. This is because if the thickness is larger, the ratio of the active material in the electrode active material 1 is reduced, and the active material is hardly used effectively.
このように、粒子２の平均粒径及び被覆層３の厚みを勘案すると、この電極活物質１の平均粒径は５ｎｍ以上かつ５５０ｎｍ以下、好ましくは２０ｎｍ以上かつ２５０ｎｍ以下となる。
この電極活物質１は、平均粒径の範囲がシャープで単分散性に優れているので、この電極活物質１をリチウムイオン電池の正電極に用いた場合、この正電極の電気的特性が極めて均一なものとなり、特性のバラツキも極めて小さなものとなる。したがって、得られたリチウムイオン電池は、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたものとなる。
Thus, taking into consideration the average particle diameter of the particles 2 and the thickness of the coating layer 3, the average particle diameter of the electrode active material 1 is 5 nm to 550 nm, preferably 20 nm to 250 nm.
Since the electrode active material 1 has a sharp average particle size range and excellent monodispersibility, when the electrode active material 1 is used as a positive electrode of a lithium ion battery, the electrical characteristics of the positive electrode are extremely high. It becomes uniform and the variation in characteristics becomes extremely small. Therefore, the obtained lithium ion battery has high voltage, high energy density, high load characteristics, and excellent long-term cycle stability and safety.
（電極活物質の製造方法）
本実施形態の電極活物質の製造方法は、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液に、高温、高圧下にて水熱処理を施し、ＬｉｗＡｘＤＯ４粒子の表面に、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）を含む被覆層を形成する方法である。
(Method for producing electrode active material)
In the method for producing an electrode active material of the present embodiment, Li w A x DO 4 particles are put into a solution in which an E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension. The suspension is subjected to hydrothermal treatment under high temperature and high pressure, and Li y E z GO 4 (wherein E is one selected from the group consisting of Fe and Ni) is applied to the surface of Li w A x DO 4 particles. Two, G is a method of forming a coating layer containing one or more selected from the group of P, Si, and S, 0 <y ≦ 2, 0 <z ≦ 1.5).
このＬｉｗＡｘＤＯ４粒子は、Ｌｉ源、Ａ源及びＤ源を、これらのモル比（Ｌｉ源：Ａ源：Ｄ源）がｗ：ｘ：１となるように水を主成分とする溶媒に投入し、撹拌してＬｉｗＡｘＤＯ４の前駆体溶液とし、この前駆体溶液を耐圧容器に入れ、高温、高圧下、例えば、１２０℃以上かつ２５０℃以下、０．２ＭＰａ以上にて、１時間以上かつ２４時間以下、水熱処理を行うことにより得ることができる。
Ｌｉ源としては、例えば、水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ２ＣＯ３）等のＬｉ化合物が、Ａ源としては、Ｍｎ、Ｃｏの群から選択される１種または２種の化合物が、Ｄ源としては、Ｐ、Ｓｉ、Ｓの群から選択される１種または２種以上の化合物が、用いられる。
この場合、水熱処理時の温度、圧力及び時間を調整することにより、ＬｉｗＡｘＤＯ４粒子の粒子径を所望の大きさに制御することが可能である。
The Li w A x DO 4 particles are mainly composed of water such that a Li source, an A source, and a D source have a molar ratio (Li source: A source: D source) of w: x: 1. Put into a solvent and stir to make a precursor solution of Li w A x DO 4 , put this precursor solution in a pressure vessel, and at high temperature and high pressure, for example, 120 ° C. or higher and 250 ° C. or lower, 0.2 MPa or higher In addition, it can be obtained by performing hydrothermal treatment for 1 hour or more and 24 hours or less.
Examples of the Li source include Li compounds such as lithium hydroxide (LiOH) and lithium carbonate (Li 2 CO 3 ), and examples of the A source include one or two compounds selected from the group of Mn and Co. As the D source, one or more compounds selected from the group of P, Si, and S are used.
In this case, it is possible to control the particle diameter of Li w A x DO 4 particles to a desired size by adjusting the temperature, pressure, and time during hydrothermal treatment.
このようにして得られたＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とする。
Ｅ源としては、Ｆｅ、Ｎｉの群から選択される１種または２種を含む化合物、例えば、塩化鉄（II）（ＦｅＣｌ２）、硫酸鉄（II）（ＦｅＳＯ４）、酢酸鉄（II）（Ｆｅ（ＣＨ３ＣＯＯ）２）、塩化ニッケル（II）（ＮｉＣｌ２）、硫酸ニッケル（II）（ＮｉＳＯ４）、酢酸ニッケル（II）（Ｎｉ（ＣＨ３ＣＯＯ）２）、及びこれらの水和物、の群から選択された１種または２種以上が好適に用いられる。
この水を主成分とする溶媒としては、例えば、水の他、アルコール類、ケトン類、エーテル類等を含む水溶液等を用いることができるが、使い易さ、安全性の点から水が好ましい。
The Li w A x DO 4 particles thus obtained are put into a solution in which the E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension.
As the E source, a compound containing one or two selected from the group of Fe and Ni, for example, iron (II) chloride (FeCl 2 ), iron (II) sulfate (FeSO 4 ), iron (II) acetate (Fe (CH 3 COO) 2 ), nickel chloride (II) (NiCl 2 ), nickel sulfate (II) (NiSO 4 ), nickel acetate (II) (Ni (CH 3 COO) 2 ), and their hydration One or two or more selected from the group of products are preferably used.
As the solvent containing water as a main component, for example, an aqueous solution containing alcohols, ketones, ethers and the like can be used in addition to water, but water is preferable from the viewpoint of ease of use and safety.
この懸濁液中のＥ源の濃度は、特に限定されるものではないが、ＬｉｗＡｘＤＯ４粒子の表面に、ＬｉｙＥｚＧＯ４を含む被覆層を均一に形成するためには、０．５質量％以上かつ１０質量％以下が好ましい。 The concentration of the E source in this suspension is not particularly limited, but in order to uniformly form a coating layer containing Li y E z GO 4 on the surface of Li w A x DO 4 particles, 0.5 mass% or more and 10 mass% or less are preferable.
次いで、この懸濁液に、高温、高圧下にて水熱処理を施し、粒子表面にてＡイオンとＥイオンとの交換を行わせしめ、懸濁液中のＬｉｗＡｘＤＯ４粒子の表面に、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）を含む被覆層を形成する。この場合、Ｇ＝Ｄとなる。
この高温高圧の条件は、ＬｉｙＥｚＧＯ４が生成する温度、圧力及び時間の範囲であればよく、例えば、水熱処理時の温度は１２０℃以上かつ２５０℃以下が好ましく、１５０℃以上かつ２２０℃以下がより好ましい。また、この水熱処理時の圧力は０．２ＭＰａ以上が好ましく、０．４ＭＰａ以上がより好ましい。また、水熱処理時間は、水熱処理時の温度にもよるが、１時間以上かつ２４時間以下が好ましく、３時間以上かつ１２時間以下がより好ましい。
Next, this suspension is subjected to hydrothermal treatment at high temperature and high pressure to cause exchange of A ions and E ions on the particle surface, and on the surface of Li w A x DO 4 particles in the suspension. , Li y E z GO 4 (where E is one or two selected from the group of Fe and Ni, G is one or more selected from the group of P, Si and S, 0 <y ≦ 2, 0 <z ≦ 1.5) is formed. In this case, G = D.
The high temperature and high pressure conditions may be in the range of the temperature, pressure and time at which Li y E z GO 4 is produced. For example, the temperature during hydrothermal treatment is preferably 120 ° C. or more and 250 ° C. or less, and 150 ° C. or more and 220 degrees C or less is more preferable. Further, the pressure during the hydrothermal treatment is preferably 0.2 MPa or more, and more preferably 0.4 MPa or more. The hydrothermal treatment time depends on the temperature during the hydrothermal treatment, but is preferably 1 hour to 24 hours, more preferably 3 hours to 12 hours.
以上により、ＬｉｗＡｘＤＯ４粒子２の表面が、ＬｉｙＥｚＧＯ４を含む被覆層３により被覆され、平均粒径が５ｎｍ以上かつ５５０ｎｍ以下の電極活物質１を、容易に作製することができる。 Thus, the surface of the Li w A x DO 4 particles 2, Li y E z GO 4 is coated with a coating layer 3 containing an average particle diameter electrode active material 1 of 5nm or more and 550nm or less, easily manufactured be able to.
なお、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入する代わりに、Ｌｉ源、Ｅ源及びＧ源を、モル比でｙ：ｚ：１の割合となるように、水を主成分とする溶媒中に溶解した溶液中に投入し、得られた懸濁液に、高温、高圧下にて水熱処理を施すこととしても、ＬｉｗＡｘＤＯ４粒子２の表面を、ＬｉｙＥｚＧＯ４を含む被覆層３により被覆することができる。 Instead of putting Li w A x DO 4 particles into a solution in which E source is dissolved in a solvent containing water as a main component, Li source, E source and G source are mixed at a molar ratio of y: z: so that 1 ratio, water was added to a solution dissolved in a solvent composed mainly, to the resulting suspension, high temperature, as is subjected to hydrothermal treatment under high pressure, Li w a The surface of the x DO 4 particle 2 can be coated with the coating layer 3 containing Li y E z GO 4 .
この場合、Ｌｉ源としては、例えば、水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ２ＣＯ３）、塩化リチウム（ＬｉＣｌ）、リン酸リチウム(Ｌｉ３ＰＯ４）等のリチウム無機酸塩、酢酸リチウム（ＬｉＣＨ３ＣＯＯ）、蓚酸リチウム（（ＣＯＯＬｉ）２）等のリチウム有機酸塩、及びこれらの水和物の群から選択された１種または２種以上が好適に用いられる。
また、Ｇ源としては、オルトリン酸（Ｈ３ＰＯ４）、メタリン酸（ＨＰＯ３）等のリン酸、リン酸二水素アンモニウム（ＮＨ４Ｈ２ＰＯ４）、リン酸水素二アンモニウム（（ＮＨ４）２ＨＰＯ４）、リン酸アンモニウム（（ＮＨ４）３ＰＯ４）、及びこれらの水和物等のリン酸源、酸化ケイ素（ＳｉＯ２）、シリコンテトラメトキシド（Ｓｉ（ＯＣＨ３）４）等のＳｉ源、硫酸二アンモニウム（（ＮＨ４）２ＳＯ４）、硫酸（Ｈ２ＳＯ４）等のＳ源、の群から選択された１種または２種以上が好適に用いられる。
In this case, examples of the Li source include lithium inorganic acid salts such as lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium chloride (LiCl), lithium phosphate (Li 3 PO 4 ), and lithium acetate. One or two or more selected from the group consisting of lithium organic acid salts such as (LiCH 3 COO) and lithium oxalate ((COOLi) 2 ) and hydrates thereof are preferably used.
The G source includes phosphoric acid such as orthophosphoric acid (H 3 PO 4 ) and metaphosphoric acid (HPO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium phosphate ((NH 4 ) 3 PO 4 ), and phosphate sources such as hydrates thereof, silicon oxide (SiO 2 ), silicon tetramethoxide (Si (OCH 3 ) 4 ) One or more selected from the group of Si sources such as diammonium sulfate ((NH 4 ) 2 SO 4 ) and S sources such as sulfuric acid (H 2 SO 4 ) are preferably used.
以上説明したように、本実施形態の電極活物質１によれば、ＬｉｗＡｘＤＯ４粒子２の表面を、ＬｉｙＥｚＧＯ４を含む被覆層３により被覆したので、オリビン構造を有するＬｉｗＡｘＤＯ４の表面を、必要最少限の電子導電性を有するＬｉｙＥｚＧＯ４を含む被覆層により被覆することとなり、したがって、電圧、エネルギー密度、負荷特性を大幅に向上させることができ、さらには、長期のサイクル安定性及び安全性を大幅に向上させることができる。 As described above, according to the electrode active material 1 of the present embodiment, the surface of the Li w A x DO 4 particles 2 is coated with the coating layer 3 containing Li y E z GO 4, and thus has an olivine structure. The surface of Li w A x DO 4 will be covered with a coating layer containing Li y E z GO 4 having the minimum necessary electronic conductivity, and therefore the voltage, energy density and load characteristics will be greatly improved. Furthermore, long-term cycle stability and safety can be greatly improved.
本実施形態の電極活物質の製造方法によれば、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液に、高温、高圧下にて水熱処理を施し、ＬｉｗＡｘＤＯ４粒子の表面に、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）を含む被覆層を形成するので、電圧、エネルギー密度、負荷特性が大幅に向上した電極活物質を容易に作製することができる。したがって、長期のサイクル安定性及び安全性が大幅に向上した電極活物質を、安定的に供給することができる。 According to the method for producing an electrode active material of this embodiment, Li w A x DO 4 particles are put into a solution in which an E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension. The suspension is hydrothermally treated under high temperature and high pressure, and Li y E z GO 4 (where E is selected from the group consisting of Fe and Ni) is formed on the surface of Li w A x DO 4 particles. A coating layer containing one or more species, two or more selected from the group consisting of P, Si, and S, and 0 <y ≦ 2, 0 <z ≦ 1.5). An electrode active material having greatly improved energy density and load characteristics can be easily produced. Therefore, it is possible to stably supply an electrode active material with greatly improved long-term cycle stability and safety.
本実施形態のリチウムイオン電池によれば、本実施形態の電極活物質１をリチウムイオン電池の正電極に用いたので、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたリチウムイオン電池を提供することができる。 According to the lithium ion battery of this embodiment, since the electrode active material 1 of this embodiment is used for the positive electrode of the lithium ion battery, it has high voltage, high energy density, high load characteristics, and long-term cycle stability. In addition, a lithium ion battery excellent in safety can be provided.
［第２の実施形態］
（電極活物質）
図２は、本発明の第２の実施形態の電極活物質を示す断面図であり、この電極活物質１１が第１の実施形態の電極活物質１と異なる点は、第１の実施形態の電極活物質１では、ＬｉｗＡｘＤＯ４粒子２の表面をＬｉｙＥｚＧＯ４を含む被覆層３により被覆しただけであるのに対し、本実施形態の電極活物質１１では、被覆層３の表面を、さらに、炭素質を含む（第２の）被覆層１２により被覆した点であり、この点以外の構成については、第１の実施形態の電極活物質１と全く同様であるから、説明を省略する。
[Second Embodiment]
(Electrode active material)
FIG. 2 is a cross-sectional view showing the electrode active material according to the second embodiment of the present invention. The difference between the electrode active material 11 and the electrode active material 1 according to the first embodiment is that of the first embodiment. In the electrode active material 1, the surface of the Li w A x DO 4 particles 2 is only covered with the coating layer 3 containing Li y E z GO 4 , whereas in the electrode active material 11 of the present embodiment, the coating layer 3 is further covered with a (second) coating layer 12 containing carbonaceous matter, and the configuration other than this point is exactly the same as the electrode active material 1 of the first embodiment. The description is omitted.
炭素質を含む被覆層１２は、炭素源となる有機物を非酸化性雰囲気下にて熱処理することにより生成した炭素質を含む電子導電性物質からなる導電層である。
この炭素質を含む電子導電性物質としては、炭素を３０質量％以上かつ１００質量％以下含有することが好ましく、５０質量％以上かつ１００質量％以下含有することがより好ましい。
この炭素質を含む電子導電性物質は、炭素を３０質量％以上かつ１００質量％以下含有することで、電極活物質１１に所望の電子伝導性を付与することができる。
The coating layer 12 containing carbon is a conductive layer made of an electronic conductive material containing carbon produced by heat-treating an organic substance serving as a carbon source in a non-oxidizing atmosphere.
The carbon-containing electronic conductive material preferably contains 30% by mass or more and 100% by mass or less, and more preferably contains 50% by mass or more and 100% by mass or less.
The electron conductive material containing carbonaceous matter can impart desired electron conductivity to the electrode active material 11 by containing 30% by mass or more and 100% by mass or less of carbon.
被覆層１２の厚みは０．１ｎｍ以上かつ２５ｎｍ以下が好ましく、より好ましくは１ｎｍ以上かつ５ｎｍ以下である。
その理由は、厚みが０．１ｎｍより薄いと、被覆層１２自体の電子導電性が不十分となり、その結果、電極活物質１１としての電子導電性が大きく低下するからであり、また、厚みが２５ｎｍより厚いと、電極活物質１１中の活物質の割合が減少し、活物質が有効に利用され難くなるからである。
The thickness of the coating layer 12 is preferably 0.1 nm or more and 25 nm or less, more preferably 1 nm or more and 5 nm or less.
The reason is that if the thickness is less than 0.1 nm, the electronic conductivity of the coating layer 12 itself is insufficient, and as a result, the electronic conductivity as the electrode active material 11 is greatly reduced. This is because if the thickness is larger than 25 nm, the ratio of the active material in the electrode active material 11 is reduced, and the active material is hardly used effectively.
このように、粒子２の平均粒径、被覆層３の厚み及び被覆層１２の厚みを勘案すると、この電極活物質１１の平均粒径は５ｎｍ以上かつ６００ｎｍ以下、好ましくは２０ｎｍ以上かつ３００ｎｍ以下となる。
この電極活物質１１は、平均粒径の範囲がシャープで単分散性に優れているので、この電極活物質１１をリチウムイオン電池の正電極に用いた場合、この正電極の電気的特性が極めて均一なものとなり、特性のバラツキも極めて小さなものとなる。したがって、得られたリチウムイオン電池は、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたものとなる。
Thus, taking into consideration the average particle size of the particles 2, the thickness of the coating layer 3, and the thickness of the coating layer 12, the average particle size of the electrode active material 11 is 5 nm or more and 600 nm or less, preferably 20 nm or more and 300 nm or less. Become.
Since this electrode active material 11 has a sharp average particle diameter range and excellent monodispersibility, when this electrode active material 11 is used as a positive electrode of a lithium ion battery, the electrical characteristics of this positive electrode are extremely high. It becomes uniform and the variation in characteristics becomes extremely small. Therefore, the obtained lithium ion battery has high voltage, high energy density, high load characteristics, and excellent long-term cycle stability and safety.
（電極活物質の製造方法）
本実施形態の電極活物質の製造方法は、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液に、高温、高圧下にて水熱処理を施し、ＬｉｗＡｘＤＯ４粒子の表面に、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）を含む被覆層を形成し、次いで、この被覆層が形成されたＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体を得、この粉体を非酸化性雰囲気下にて熱処理する方法である。
なお、この方法では、ＬｉｗＡｘＤＯ４粒子の表面にＬｉｙＥｚＧＯ４を含む被覆層を形成する工程までは、第１の実施形態の電極活物質の製造方法と全く同様である。
(Method for producing electrode active material)
In the method for producing an electrode active material of the present embodiment, Li w A x DO 4 particles are put into a solution in which an E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension. The suspension is subjected to hydrothermal treatment under high temperature and high pressure, and Li y E z GO 4 (wherein E is one selected from the group consisting of Fe and Ni) is applied to the surface of Li w A x DO 4 particles. 2 and G is one or more selected from the group consisting of P, Si, and S, and 0 <y ≦ 2, 0 <z ≦ 1.5), and then the coating layer The Li w A x DO 4 particles formed with is put into a solution containing an organic substance serving as a carbon source, stirred to form a slurry, and the slurry is dried to obtain a powder. The powder is made non-oxidizing This is a method of heat treatment in an atmosphere.
In this method, the process up to the step of forming a coating layer containing Li y E z GO 4 on the surface of Li w A x DO 4 particles is exactly the same as the method for producing the electrode active material of the first embodiment. .
ここでは、この被覆層が形成されたＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとする。
この炭素源となる有機物としては、非酸化性雰囲気下にて熱処理することにより炭素を生成する有機物であればよく、特に制限はされないが、例えば、ヘキサノール、オクタノール等の高級一価アルコール、アリルアルコール、プロピノール（プロパルギルアルコール）、テルピネオール等の不飽和一価アルコール、ポリビニルアルコール（ＰＶＡ）等が挙げられる。
Here, the Li w A x DO 4 particles on which the coating layer is formed are put into a solution containing an organic substance serving as a carbon source, and stirred to obtain a slurry.
The organic substance serving as the carbon source is not particularly limited as long as it is an organic substance that generates carbon by heat treatment in a non-oxidizing atmosphere. For example, higher monohydric alcohols such as hexanol and octanol, allyl alcohol , Unsaturated monohydric alcohols such as propynol (propargyl alcohol) and terpineol, polyvinyl alcohol (PVA), and the like.
このスラリー中の炭素源となる有機物の濃度は、特に限定されるものではないが、被覆層上の表面に、炭素質を含む被覆層１２を均一に形成するためには、１質量％以上かつ２５質量％以下が好ましい。 The concentration of the organic substance serving as the carbon source in the slurry is not particularly limited, but in order to uniformly form the coating layer 12 containing carbonaceous material on the surface of the coating layer, it is 1% by mass or more and 25 mass% or less is preferable.
この炭素源となる有機物を溶解させる溶媒としては、この有機物が溶解するものであればよく、特に制限されないが、例えば、水、メタノール、エタノール、１−プロパノール、２−プロパノール（イソプロピルアルコール：ＩＰＡ）、ブタノール、ペンタノール、ヘキサノール、オクタノール、ジアセトンアルコール等のアルコール類、酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、γ−ブチロラクトン等のエステル類、ジエチルエーテル、エチレングルコールモノメチルエーテル（メチルセロソルブ）、エチレングルコールモノエチルエーテル（エチルセロソルブ）、エチレングルコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテル類、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、アセチルアセトン、シクロヘキサノン等のケトン類、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミド類、エチレングリコール、ジエチレングリコール、プロピレングリコール等のグリコール類等を挙げることができる。これらは、１種のみを単独で用いてもよく、２種以上を混合して用いてもよい。 The solvent for dissolving the organic substance serving as the carbon source is not particularly limited as long as it dissolves the organic substance. For example, water, methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol: IPA) , Butanol, pentanol, hexanol, octanol, diacetone alcohol and other alcohols, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, esters such as γ-butyrolactone, diethyl ether , Ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), Ethers such as ethylene glycol monomethyl ether and diethylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetylacetone and cyclohexanone, dimethylformamide, N, N-dimethylacetoacetamide, N-methyl Examples include amides such as pyrrolidone and glycols such as ethylene glycol, diethylene glycol, and propylene glycol. These may be used alone or in combination of two or more.
次いで、このスラリーを乾燥して粉体を得、この粉体を窒素雰囲気等の非酸化性雰囲気下にて熱処理する。
この熱処理の条件は、炭素源となる有機物から炭素が生成する温度及び時間の範囲であればよく、例えば、温度は５００℃以上かつ１０００℃以下、時間は、熱処理時の温度にもよるが、１時間以上かつ２４時間以下が好ましい。
Next, the slurry is dried to obtain a powder, and the powder is heat-treated in a non-oxidizing atmosphere such as a nitrogen atmosphere.
The conditions for this heat treatment may be in the range of the temperature and time at which carbon is generated from the organic substance serving as the carbon source. For example, the temperature is 500 ° C. or more and 1000 ° C. or less, and the time depends on the temperature during the heat treatment, 1 hour or more and 24 hours or less are preferable.
以上により、ＬｉｗＡｘＤＯ４粒子２の表面が、ＬｉｙＥｚＧＯ４を含む被覆層３及び炭素質を含む被覆層１２により被覆され、平均粒径が５ｎｍ以上かつ６００ｎｍ以下、好ましくは２０ｎｍ以上かつ３００ｎｍ以下の電極活物質１１を、容易に作製することができる。 As described above, the surface of the Li w A x DO 4 particles 2 is covered with the coating layer 3 containing Li y E z GO 4 and the coating layer 12 containing carbonaceous material, and the average particle diameter is 5 nm or more and 600 nm or less, preferably The electrode active material 11 having a thickness of 20 nm or more and 300 nm or less can be easily produced.
以上説明したように、本実施形態の電極活物質１１によれば、ＬｉｗＡｘＤＯ４粒子２の表面を、ＬｉｙＥｚＧＯ４を含む被覆層３及び炭素質を含む被覆層１２により被覆したので、オリビン構造を有するＬｉｗＡｘＤＯ４の表面を、必要最少限の電子導電性を有するＬｉｙＥｚＧＯ４を含む被覆層３及び導電性に優れた炭素質を含む被覆層１２により被覆することとなり、したがって、電圧、エネルギー密度、負荷特性を大幅に向上させることができ、さらには、長期のサイクル安定性及び安全性を大幅に向上させることができる。 As described above, according to the electrode active material 11 of the present embodiment, the surface of the Li w A x DO 4 particles 2 is covered with the coating layer 3 containing Li y E z GO 4 and the coating layer 12 containing carbonaceous matter. Since the surface of Li w A x DO 4 having an olivine structure is coated, the coating layer 3 containing Li y E z GO 4 having the minimum necessary electronic conductivity and the coating layer containing carbonaceous material having excellent conductivity Therefore, the voltage, energy density, and load characteristics can be greatly improved, and the long-term cycle stability and safety can be greatly improved.
本実施形態の電極活物質の製造方法によれば、被覆層が形成されたＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、次いで、このスラリーを乾燥して粉体を得、この粉体を窒素雰囲気等の非酸化性雰囲気下にて熱処理するので、電圧、エネルギー密度、負荷特性が大幅に向上した電極活物質を容易に作製することができる。したがって、長期のサイクル安定性及び安全性が大幅に向上した電極活物質を、安定的に供給することができる。 According to the method for producing an electrode active material of the present embodiment, Li w A x DO 4 particles on which a coating layer is formed are put into a solution containing an organic substance serving as a carbon source, stirred to obtain a slurry, This slurry is dried to obtain a powder, and this powder is heat-treated in a non-oxidizing atmosphere such as a nitrogen atmosphere, so that an electrode active material with greatly improved voltage, energy density, and load characteristics can be easily produced. be able to. Therefore, it is possible to stably supply an electrode active material with greatly improved long-term cycle stability and safety.
本実施形態のリチウムイオン電池によれば、本実施形態の電極活物質１１をリチウムイオン電池の正電極に用いたので、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたリチウムイオン電池を提供することができる。 According to the lithium ion battery of this embodiment, since the electrode active material 11 of this embodiment is used for the positive electrode of the lithium ion battery, it has high voltage, high energy density, high load characteristics, and long-term cycle stability. In addition, a lithium ion battery excellent in safety can be provided.
［第３の実施形態］
（電極活物質）
図３は、本発明の第３の実施形態の電極活物質を示す断面図であり、この電極活物質２１が第１の実施形態の電極活物質１と異なる点は、第１の実施形態の電極活物質１では、ＬｉｗＡｘＤＯ４粒子２の表面をＬｉｙＥｚＧＯ４を含む被覆層３により被覆したのに対し、本実施形態の電極活物質２１では、ＬｉｗＡｘＤＯ４粒子２の表面を、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）と炭素質の電子伝導性物質との複合体からなる被覆層２２により被覆した点であり、この点以外の構成については、第１の実施形態の電極活物質１と全く同様であるから、説明を省略する。
[Third Embodiment]
(Electrode active material)
FIG. 3 is a cross-sectional view showing an electrode active material according to a third embodiment of the present invention. The difference between the electrode active material 21 and the electrode active material 1 according to the first embodiment is that of the first embodiment. In the electrode active material 1, the surface of the Li w A x DO 4 particles 2 was covered with the coating layer 3 containing Li y E z GO 4 , whereas in the electrode active material 21 of the present embodiment, Li w A x DO The surface of the four particles 2 is Li y E z GO 4 (where E is one or two selected from the group of Fe and Ni, G is one or two selected from the group of P, Si and S) Seeds or more, 0 <y ≦ 2, 0 <z ≦ 1.5) and a coating layer 22 made of a composite of a carbonaceous electron conductive material. Since it is completely the same as the electrode active material 1 of 1 embodiment, description is abbreviate | omitted.
ＬｉｙＥｚＧＯ４と炭素質の電子伝導性物質との複合体からなる被覆層２２は、ＬｉｙＥｚＧＯ４（但し、ＥはＦｅ、Ｎｉの群から選択される１種または２種、ＧはＰ、Ｓｉ、Ｓの群から選択される１種または２種以上、０＜ｙ≦２、０＜ｚ≦１．５）と、炭素源となる有機物を非酸化性雰囲気下にて熱処理することにより生成した炭素質を含む電子導電性物質とを含む導電層である。 The coating layer 22 made of a composite of Li y E z GO 4 and a carbonaceous electron conductive material is Li y E z GO 4 (where E is one or two selected from the group of Fe and Ni) , G is one or more selected from the group of P, Si, and S, 0 <y ≦ 2, 0 <z ≦ 1.5), and an organic substance serving as a carbon source in a non-oxidizing atmosphere It is a conductive layer containing an electronic conductive material containing carbonaceous material produced by heat treatment.
この被覆層２２は、炭素質を含む電子導電性物質を炭素に換算した場合、炭素として３０質量％以上かつ９９質量％以下含有することが好ましく、５０質量％以上かつ９５質量％以下含有することがより好ましい。
この炭素質を含む電子導電性物質は、炭素質を炭素換算値で３０質量％以上かつ９９質量％以下含有することで、電極活物質２１に所望の電子伝導性を付与することができる。
This coating layer 22 preferably contains 30% by mass or more and 99% by mass or less as carbon, and contains 50% by mass or more and 95% by mass or less as carbon when an electronically conductive substance containing carbon is converted to carbon. Is more preferable.
The electron conductive material containing carbonaceous material can impart desired electronic conductivity to the electrode active material 21 by containing the carbonaceous material in a carbon conversion value of 30% by mass or more and 99% by mass or less.
被覆層２２の厚みは０．１ｎｍ以上かつ２５ｎｍ以下が好ましく、より好ましくは２ｎｍ以上かつ１０ｎｍ以下である。
その理由は、厚みが０．１ｎｍより薄いと、被覆層２２自体の電子導電性が不十分となり、その結果、電極活物質２１としての電子導電性が大きく低下するからであり、また、厚みが２５ｎｍより厚いと、電極活物質２１中の活物質の割合が減少し、活物質が有効に利用され難くなるからである。
The thickness of the coating layer 22 is preferably 0.1 nm or more and 25 nm or less, more preferably 2 nm or more and 10 nm or less.
The reason is that if the thickness is less than 0.1 nm, the electronic conductivity of the coating layer 22 itself is insufficient, and as a result, the electronic conductivity as the electrode active material 21 is greatly reduced. This is because if the thickness is larger than 25 nm, the ratio of the active material in the electrode active material 21 is reduced, and the active material is hardly used effectively.
このように、粒子２の平均粒径及び被覆層２２の厚みを勘案すると、この電極活物質２１の平均粒径は５ｎｍ以上かつ５５０ｎｍ以下、好ましくは２０ｎｍ以上かつ３００ｎｍ以下となる。
この電極活物質２１は、平均粒径の範囲がシャープで単分散性に優れているので、この電極活物質２１をリチウムイオン電池の正電極に用いた場合、この正電極の電気的特性が極めて均一なものとなり、特性のバラツキも極めて小さなものとなる。したがって、得られたリチウムイオン電池は、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたものとなる。
Thus, taking into consideration the average particle diameter of the particles 2 and the thickness of the coating layer 22, the average particle diameter of the electrode active material 21 is 5 nm to 550 nm, preferably 20 nm to 300 nm.
Since this electrode active material 21 has a sharp average particle diameter range and excellent monodispersibility, when this electrode active material 21 is used for the positive electrode of a lithium ion battery, the electrical characteristics of this positive electrode are extremely high. It becomes uniform and the variation in characteristics becomes extremely small. Therefore, the obtained lithium ion battery has high voltage, high energy density, high load characteristics, and excellent long-term cycle stability and safety.
（電極活物質の製造方法）
本実施形態の電極活物質の製造方法は、ＬｉｗＡｘＤＯ４粒子を、Ｌｉ源、Ｅ源及びＧ源をモル比（Ｌｉ源：Ｅ源：Ｇ源）でｙ：ｚ：１の割合で含むとともに炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体を得、この粉体を非酸化性雰囲気下にて熱処理する方法である。
(Method for producing electrode active material)
In the method for producing an electrode active material according to the present embodiment, Li w A x DO 4 particles are mixed in a molar ratio of Li source, E source and G source (Li source: E source: G source) and a ratio of y: z: 1. And is stirred into a slurry, dried to obtain a powder, and the powder is heat-treated in a non-oxidizing atmosphere.
Ｌｉ源としては、例えば、水酸化リチウム（ＬｉＯＨ）、炭酸リチウム（Ｌｉ２ＣＯ３）、塩化リチウム（ＬｉＣｌ）、リン酸リチウム(Ｌｉ３ＰＯ４）等のリチウム無機酸塩、酢酸リチウム（ＬｉＣＨ３ＣＯＯ）、蓚酸リチウム（（ＣＯＯＬｉ）２）等のリチウム有機酸塩、及びこれらの水和物の群から選択された１種または２種以上が好適に用いられる。
Ｅ源としては、Ｆｅ、Ｎｉの群から選択される１種または２種を含む化合物、例えば、塩化鉄（II）（ＦｅＣｌ２）、硫酸鉄（II）（ＦｅＳＯ４）、酢酸鉄（II）（Ｆｅ（ＣＨ３ＣＯＯ）２）、塩化ニッケル（II）（ＮｉＣｌ２）、硫酸ニッケル（II）（ＮｉＳＯ４）、酢酸ニッケル（II）（Ｎｉ（ＣＨ３ＣＯＯ）２）、及びこれらの水和物、の群から選択された１種または２種以上が好適に用いられる。
Examples of the Li source include lithium inorganic acid salts such as lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium chloride (LiCl), and lithium phosphate (Li 3 PO 4 ), lithium acetate (LiCH 3). One or more selected from the group of lithium organic acid salts such as (COO) and lithium oxalate ((COOLi) 2 ), and hydrates thereof are preferably used.
As the E source, a compound containing one or two selected from the group of Fe and Ni, for example, iron (II) chloride (FeCl 2 ), iron (II) sulfate (FeSO 4 ), iron (II) acetate (Fe (CH 3 COO) 2 ), nickel chloride (II) (NiCl 2 ), nickel sulfate (II) (NiSO 4 ), nickel acetate (II) (Ni (CH 3 COO) 2 ), and their hydration One or two or more selected from the group of products are preferably used.
Ｇ源としては、オルトリン酸（Ｈ３ＰＯ４）、メタリン酸（ＨＰＯ３）等のリン酸、リン酸二水素アンモニウム（ＮＨ４Ｈ２ＰＯ４）、リン酸水素二アンモニウム（（ＮＨ４）２ＨＰＯ４）、リン酸アンモニウム（（ＮＨ４）３ＰＯ４）、及びこれらの水和物等のリン酸源、酸化ケイ素（ＳｉＯ２）、シリコンテトラメトキシド（Ｓｉ（ＯＣＨ３）４）等のＳｉ源、硫酸二アンモニウム（（ＮＨ４）２ＳＯ４）、硫酸（Ｈ２ＳＯ４）等のＳ源、の群から選択された１種または２種以上が好適に用いられる。
この炭素源となる有機物、及び炭素源となる有機物を溶解させる溶媒については、第３の実施形態の炭素源となる有機物、及び炭素源となる有機物を溶解させる溶媒と全く同様である。
Examples of the G source include phosphoric acid such as orthophosphoric acid (H 3 PO 4 ) and metaphosphoric acid (HPO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), and diammonium hydrogen phosphate ((NH 4 ) 2. HPO 4 ), ammonium phosphate ((NH 4 ) 3 PO 4 ), and phosphate sources such as hydrates thereof, silicon oxide (SiO 2 ), silicon tetramethoxide (Si (OCH 3 ) 4 ), etc. One or more selected from the group of Si sources, S sources such as diammonium sulfate ((NH 4 ) 2 SO 4 ) and sulfuric acid (H 2 SO 4 ) are preferably used.
The organic substance that becomes the carbon source and the solvent that dissolves the organic substance that becomes the carbon source are exactly the same as the organic substance that becomes the carbon source and the solvent that dissolves the organic substance that becomes the carbon source in the third embodiment.
粉体を窒素雰囲気等の非酸化性雰囲気下にて熱処理する際の条件は、ＬｉｙＥｚＧＯ４が生成するとともに炭素源となる有機物から炭素が生成する温度及び時間の範囲であればよく、例えば、温度は５００℃以上かつ１０００℃以下、時間は、熱処理時の温度にもよるが、１時間以上かつ２４時間以下が好ましい。 The conditions for heat-treating the powder in a non-oxidizing atmosphere such as a nitrogen atmosphere may be in the temperature and time range in which Li y E z GO 4 is generated and carbon is generated from an organic substance that is a carbon source. For example, the temperature is preferably 500 ° C. or more and 1000 ° C. or less, and the time is preferably 1 hour or more and 24 hours or less, although it depends on the temperature during the heat treatment.
以上により、ＬｉｗＡｘＤＯ４粒子２の表面が、ＬｉｙＥｚＧＯ４と炭素質の電子伝導性物質との複合体からなる被覆層２２により被覆され、平均粒径が５ｎｍ以上かつ５５０ｎｍ以下、好ましくは２０ｎｍ以上かつ３００ｎｍ以下の電極活物質２１を、容易に作製することができる。 As described above, the surface of the Li w A x DO 4 particle 2 is covered with the coating layer 22 made of the composite of Li y E z GO 4 and the carbonaceous electron conductive material, and the average particle diameter is 5 nm or more and 550 nm. Hereinafter, the electrode active material 21 preferably having a thickness of 20 nm or more and 300 nm or less can be easily produced.
以上説明したように、本実施形態の電極活物質２１によれば、ＬｉｗＡｘＤＯ４粒子２の表面を、ＬｉｙＥｚＧＯ４と炭素質の電子伝導性物質との複合体からなる被覆層２２により被覆したので、オリビン構造を有するＬｉｗＡｘＤＯ４の表面を、必要最少限の電子導電性を有するＬｉｙＥｚＧＯ４及び導電性に優れた炭素質の電子伝導性物質を含む被覆層２２により被覆することとなり、したがって、電圧、エネルギー密度、負荷特性を大幅に向上させることができ、さらには、長期のサイクル安定性及び安全性を大幅に向上させることができる。 As described above, according to the electrode active material 21 of the present embodiment, the surface of the Li w A x DO 4 particle 2 is made of a composite of Li y E z GO 4 and a carbonaceous electron conductive material. Since the surface of Li w A x DO 4 having an olivine structure is covered with the covering layer 22, Li y E z GO 4 having the minimum necessary electronic conductivity and a carbonaceous electron conductive material having excellent conductivity Therefore, the voltage, energy density, and load characteristics can be greatly improved, and long-term cycle stability and safety can be greatly improved.
本実施形態の電極活物質の製造方法によれば、ＬｉｗＡｘＤＯ４粒子を、Ｌｉ源、Ｅ源、Ｇ源及び炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体を得、この粉体を非酸化性雰囲気下にて熱処理するので、電圧、エネルギー密度、負荷特性が大幅に向上した電極活物質を容易に作製することができる。したがって、長期のサイクル安定性及び安全性が大幅に向上した電極活物質を、安定的に供給することができる。 According to the method for producing an electrode active material of the present embodiment, Li w A x DO 4 particles are put into a solution containing an organic substance serving as a Li source, an E source, a G source, and a carbon source, and stirred to form a slurry. The slurry is dried to obtain a powder, and the powder is heat-treated in a non-oxidizing atmosphere, so that an electrode active material with greatly improved voltage, energy density, and load characteristics can be easily produced. . Therefore, it is possible to stably supply an electrode active material with greatly improved long-term cycle stability and safety.
本実施形態のリチウムイオン電池によれば、本実施形態の電極活物質２１をリチウムイオン電池の正電極に用いたので、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたリチウムイオン電池を提供することができる。 According to the lithium ion battery of this embodiment, since the electrode active material 21 of this embodiment is used for the positive electrode of the lithium ion battery, it has high voltage, high energy density, high load characteristics, and long-term cycle stability. In addition, a lithium ion battery excellent in safety can be provided.
［第４の実施形態］
（電極活物質）
図４は、本発明の第４の実施形態の電極活物質を示す断面図であり、この電極活物質３１が第１の実施形態の電極活物質１と異なる点は、第１の実施形態の電極活物質１では、ＬｉｗＡｘＤＯ４粒子２の表面をＬｉｙＥｚＧＯ４を含む被覆層３により被覆したのに対し、本実施形態の電極活物質３１では、ＬｉｗＡｘＤＯ４粒子２の表面を、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の電子伝導性物質及びＦｅ及びＮｉのいずれか１種または２種を含む物質を含有するとともに、この有機系炭素質の電子伝導性物質がＦｅ及びＮｉのいずれか１種または２種を含む物質と接触してなる被覆層３２により被覆した点であり、この点以外の構成については、第１の実施形態の電極活物質１と全く同様であるから、説明を省略する。
[Fourth Embodiment]
(Electrode active material)
FIG. 4 is a cross-sectional view showing an electrode active material according to a fourth embodiment of the present invention. The difference between the electrode active material 31 and the electrode active material 1 according to the first embodiment is that of the first embodiment. In the electrode active material 1, the surface of the Li w A x DO 4 particles 2 was coated with the coating layer 3 containing Li y E z GO 4 , whereas in the electrode active material 31 of the present embodiment, Li w A x DO The surface of the four particles 2 contains an organic carbonaceous electron conductive substance obtained by heat-treating an organic substance in a non-oxidizing atmosphere and carbonized, and a substance containing one or two of Fe and Ni. The organic carbonaceous electron conductive material is coated with a coating layer 32 formed in contact with a material containing either one or two of Fe and Ni. Since it is completely the same as the electrode active material 1 of 1 embodiment Description thereof will be omitted.
この被覆層３２は、炭素源となる有機物を非酸化性雰囲気下にて熱処理することにより生成した炭素質を含む電子導電性物質と、Ｆｅ及びＮｉのいずれか１種または２種を含む物質とを含有したものである。 The coating layer 32 includes an electronically conductive material containing carbon produced by heat-treating an organic substance serving as a carbon source in a non-oxidizing atmosphere, and a material containing any one or two of Fe and Ni. Is contained.
この被覆層３２は、炭素質を含む電子導電性物質を炭素に換算した場合、炭素として３０質量％以上かつ９９質量％以下含有することが好ましく、５０質量％以上かつ９５質量％以下含有することがより好ましい。
この炭素質を含む電子導電性物質は、炭素質を炭素換算値で３０質量％以上かつ９９質量％以下含有することで、電極活物質３１に所望の電子伝導性を付与することができる。
また、Ｆｅ及びＮｉのいずれか１種または２種を含む物質としては、例えば、酸化鉄（II）（ＦｅＯ）、塩化鉄（II）（ＦｅＣｌ２）、硫酸鉄（II）（ＦｅＳＯ４）、酢酸鉄（II）（Ｆｅ（ＣＨ３ＣＯＯ）２）、酸化ニッケル（II）（ＮｉＯ）、塩化ニッケル（II）（ＮｉＣｌ２）、硫酸ニッケル（II）（ＮｉＳＯ４）、酢酸ニッケル（II）（Ｎｉ（ＣＨ３ＣＯＯ）２等が挙げられる。
The coating layer 32 preferably contains 30% by mass or more and 99% by mass or less as carbon, and contains 50% by mass or more and 95% by mass or less as carbon when the carbon-containing electronic conductive material is converted to carbon. Is more preferable.
The electron conductive material containing carbonaceous material can impart desired electronic conductivity to the electrode active material 31 by containing the carbonaceous material in a carbon equivalent value of 30% by mass or more and 99% by mass or less.
Examples of the substance containing one or two of Fe and Ni include, for example, iron oxide (II) (FeO), iron chloride (II) (FeCl 2 ), iron sulfate (II) (FeSO 4 ), Iron (II) acetate (Fe (CH 3 COO) 2 ), nickel (II) oxide (NiO), nickel chloride (II) (NiCl 2 ), nickel sulfate (II) (NiSO 4 ), nickel acetate (II) ( Ni (CH 3 COO) 2 and the like.
被覆層３２の厚みは０．１ｎｍ以上かつ３０ｎｍ以下が好ましく、より好ましくは１ｎｍ以上かつ５ｎｍ以下である。
その理由は、厚みが０．１ｎｍより薄いと、被覆層３２自体の電子導電性が不十分となり、その結果、電極活物質３１としての電子導電性が大きく低下するからであり、また、厚みが３０ｎｍより厚いと、電極活物質３１中の活物質の割合が減少し、活物質が有効に利用され難くなるからである。
The thickness of the coating layer 32 is preferably 0.1 nm or more and 30 nm or less, more preferably 1 nm or more and 5 nm or less.
The reason is that if the thickness is less than 0.1 nm, the electronic conductivity of the coating layer 32 itself is insufficient, and as a result, the electronic conductivity as the electrode active material 31 is greatly reduced. This is because if the thickness is larger than 30 nm, the ratio of the active material in the electrode active material 31 is reduced, and the active material is hardly used effectively.
このように、ＬｉｗＡｘＤＯ４粒子２の平均粒径及び被覆層３２の厚みを勘案すると、この電極活物質３１の平均粒径は５ｎｍ以上かつ６００ｎｍ以下、好ましくは２０ｎｍ以上かつ４００ｎｍ以下となる。
この電極活物質３１は、平均粒径の範囲がシャープで単分散性に優れているので、この電極活物質３１をリチウムイオン電池の正電極に用いた場合、この正電極の電気的特性が極めて均一なものとなり、特性のバラツキも極めて小さなものとなる。したがって、得られたリチウムイオン電池は、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたものとなる。
Thus, taking into consideration the average particle diameter of Li w A x DO 4 particles 2 and the thickness of the coating layer 32, the average particle diameter of the electrode active material 31 is 5 nm or more and 600 nm or less, preferably 20 nm or more and 400 nm or less. Become.
Since this electrode active material 31 has a sharp average particle size range and excellent monodispersibility, when this electrode active material 31 is used as a positive electrode of a lithium ion battery, the electrical characteristics of this positive electrode are extremely high. It becomes uniform and the variation in characteristics becomes extremely small. Therefore, the obtained lithium ion battery has high voltage, high energy density, high load characteristics, and excellent long-term cycle stability and safety.
（電極活物質の製造方法）
本実施形態の電極活物質の製造方法は、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液を乾燥後、熱処理して、表面処理ＬｉｗＡｘＤＯ４粒子とし、この表面処理ＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体とし、この粉体を非酸化性雰囲気下にて熱処理する方法である。
(Method for producing electrode active material)
In the method for producing an electrode active material of the present embodiment, Li w A x DO 4 particles are put into a solution in which an E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension. The suspension is dried and then heat-treated to form surface-treated Li w A x DO 4 particles. The surface-treated Li w A x DO 4 particles are put into a solution containing an organic substance as a carbon source and stirred. In this method, a slurry is formed, the slurry is dried to obtain a powder, and the powder is heat-treated in a non-oxidizing atmosphere.
まず、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して、懸濁液とする。
Ｅ源としては、Ｆｅ、Ｎｉの群から選択される１種または２種を含む化合物、例えば、塩化鉄（II）（ＦｅＣｌ２）、硫酸鉄（II）（ＦｅＳＯ４）、酢酸鉄（II）（Ｆｅ（ＣＨ３ＣＯＯ）２）、塩化ニッケル（II）（ＮｉＣｌ２）、硫酸ニッケル（II）（ＮｉＳＯ４）、酢酸ニッケル（II）（Ｎｉ（ＣＨ３ＣＯＯ）２）、及びこれらの水和物、の群から選択された１種または２種以上が好適に用いられる。
この水を主成分とする溶媒としては、例えば、水の他、アルコール類、ケトン類、エーテル類等を含む水溶液等を用いることができるが、使い易さ、安全性の点から水が好ましい。
First, Li w A x DO 4 particles are put into a solution obtained by dissolving E source in a solvent containing water as a main component, and stirred to obtain a suspension.
As the E source, a compound containing one or two selected from the group of Fe and Ni, for example, iron (II) chloride (FeCl 2 ), iron (II) sulfate (FeSO 4 ), iron (II) acetate (Fe (CH 3 COO) 2 ), nickel chloride (II) (NiCl 2 ), nickel sulfate (II) (NiSO 4 ), nickel acetate (II) (Ni (CH 3 COO) 2 ), and their hydration One or two or more selected from the group of products are preferably used.
As the solvent containing water as a main component, for example, an aqueous solution containing alcohols, ketones, ethers and the like can be used in addition to water, but water is preferable from the viewpoint of ease of use and safety.
この懸濁液中のＥ源の濃度は、特に限定されるものではないが、ＬｉｗＡｘＤＯ４粒子の表面を処理するために十分な濃度である必要があり、１質量％以上かつ１０質量％以下が好ましい。 The concentration of E source in this suspension is not particularly limited, but it needs to be a concentration sufficient to treat the surface of Li w A x DO 4 particles. The mass% or less is preferable.
次いで、この懸濁液を乾燥後、熱処理する。
熱処理する際の条件は、ＬｉｗＡｘＤＯ４粒子の表面を処理するのに十分な温度及び時間の範囲であればよく、例えば、温度は４００℃以上かつ９００℃以下、時間は、熱処理時の温度にもよるが、１時間以上かつ４８時間以下が好ましい。
このようにして、ＬｉｗＡｘＤＯ４粒子２に表面処理が施された表面処理ＬｉｗＡｘＤＯ４粒子が得られる。
The suspension is then heat treated after drying.
Conditions for the heat treatment may be in a range of temperature and time sufficient to treat the surface of Li w A x DO 4 particles. For example, the temperature is 400 ° C. or more and 900 ° C. or less, and the time is the time of heat treatment Depending on the temperature, it is preferably 1 hour or more and 48 hours or less.
In this way, Li w A x DO 4 particles 2 surface treatment surface-treated in Li w A x DO 4 particles.
次いで、この表面処理ＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとする。
この炭素源となる有機物としては、非酸化性雰囲気下にて熱処理することにより炭素を生成する有機物であればよく、特に制限はされないが、例えば、ヘキサノール、オクタノール等の高級一価アルコール、アリルアルコール、プロピノール（プロパルギルアルコール）、テルピネオール等の不飽和一価アルコール、ポリビニルアルコール（ＰＶＡ）等が挙げられる。
Next, the surface-treated Li w A x DO 4 particles are put into a solution containing an organic substance serving as a carbon source, and stirred to obtain a slurry.
The organic substance serving as the carbon source is not particularly limited as long as it is an organic substance that generates carbon by heat treatment in a non-oxidizing atmosphere. For example, higher monohydric alcohols such as hexanol and octanol, allyl alcohol , Unsaturated monohydric alcohols such as propynol (propargyl alcohol) and terpineol, polyvinyl alcohol (PVA), and the like.
このスラリー中の炭素源となる有機物の濃度は、特に限定されるものではないが、表面処理ＬｉｗＡｘＤＯ４粒子の表面に、有機系炭素質の電子伝導性物質及びＦｅ及びＮｉのいずれか１種または２種を含む物質を含有する被覆層３２を均一に形成するためには、１質量％以上かつ２５質量％以下が好ましい。
この炭素源となる有機物を溶解させる溶媒は、第２の実施形態の炭素源となる有機物を溶解させる溶媒と全く同様である。
The concentration of the organic substance serving as a carbon source in the slurry is not particularly limited, and any of organic carbonaceous electron conductive material and Fe and Ni is formed on the surface of the surface-treated Li w A x DO 4 particles. In order to uniformly form the coating layer 32 containing a substance containing one or two kinds, the content is preferably 1% by mass or more and 25% by mass or less.
The solvent for dissolving the organic substance serving as the carbon source is exactly the same as the solvent for dissolving the organic substance serving as the carbon source in the second embodiment.
次いで、このスラリーを乾燥して粉体を得、この粉体を窒素雰囲気等の非酸化性雰囲気下にて熱処理する。
この熱処理の条件は、炭素源となる有機物から炭素が生成する温度及び時間の範囲であればよく、例えば、温度は５００℃以上かつ１０００℃以下、時間は、熱処理時の温度にもよるが、１時間以上かつ２４時間以下が好ましい。
Next, the slurry is dried to obtain a powder, and the powder is heat-treated in a non-oxidizing atmosphere such as a nitrogen atmosphere.
The conditions for this heat treatment may be in the range of the temperature and time at which carbon is generated from the organic substance serving as the carbon source. For example, the temperature is 500 ° C. or more and 1000 ° C. or less, and the time depends on the temperature during the heat treatment, 1 hour or more and 24 hours or less are preferable.
この熱処理により、炭素源となる有機物から炭素が生成し、この炭素が表面処理ＬｉｗＡｘＤＯ４粒子の表面を覆うこととなる。この際、生成した炭素は、ＬｉｗＡｘＤＯ４粒子の表面処理された部分に存在するＦｅ及びＮｉのいずれか１種または２種を含む物質と接触することとなる。
これにより、ＬｉｗＡｘＤＯ４粒子の表面には、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の電子伝導性物質、すなわち炭素と、Ｆｅ及びＮｉのいずれか１種または２種を含む物質、すなわちＦｅ化合物あるいはＮｉ化合物と、を含む被覆層３２が形成されることとなる。
By this heat treatment, carbon is generated from an organic substance serving as a carbon source, and this carbon covers the surface of the surface-treated Li w A x DO 4 particles. At this time, the produced carbon comes into contact with a substance containing any one or two of Fe and Ni present in the surface-treated portion of the Li w A x DO 4 particles.
Thereby, on the surface of Li w A x DO 4 particles, an organic carbonaceous electron conductive material obtained by heat-treating and carbonizing an organic substance in a non-oxidizing atmosphere, that is, any of carbon, Fe, and Ni The covering layer 32 containing the substance containing one or two kinds, that is, the Fe compound or the Ni compound is formed.
以上により、ＬｉｗＡｘＤＯ４粒子２の表面に、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の電子伝導性物質及びＦｅ及びＮｉのいずれか１種または２種を含む物質を含有するとともに、この有機系炭素質の電子伝導性物質がＦｅ及びＮｉのいずれか１種または２種を含む物質と接触してなる被覆層３２を形成することができる。 As described above, on the surface of Li w A x DO 4 particles 2, an organic carbonaceous electron conductive material obtained by heat-treating and carbonizing an organic substance in a non-oxidizing atmosphere, and any one or two of Fe and Ni It is possible to form a coating layer 32 that contains a substance containing a seed and is brought into contact with a substance containing any one or two of Fe and Ni.
以上説明したように、本実施形態の電極活物質３１によれば、ＬｉｗＡｘＤＯ４粒子２の表面を、有機物を非酸化性雰囲気下にて熱処理し炭化してなる有機系炭素質の電子伝導性物質及びＦｅ及びＮｉのいずれか１種または２種を含む物質を含有するとともに、この有機系炭素質の電子伝導性物質がＦｅ及びＮｉのいずれか１種または２種を含む物質と接触してなる被覆層３２により被覆したので、電圧、エネルギー密度、負荷特性を大幅に向上させることができ、さらには、長期のサイクル安定性及び安全性を大幅に向上させることができる。 As described above, according to the electrode active material 31 of the present embodiment, the surface of the Li w A x DO 4 particles 2 is an organic carbonaceous material obtained by heat-treating and carbonizing an organic substance in a non-oxidizing atmosphere. An organic conductive substance and a substance containing one or two of Fe and Ni, and the organic carbonaceous electronic conductive substance contains one or two of Fe and Ni; Since it coat | covered with the coating layer 32 formed in contact, a voltage, an energy density, and a load characteristic can be improved significantly, Furthermore, long-term cycle stability and safety | security can be improved significantly.
本実施形態の電極活物質の製造方法によれば、ＬｉｗＡｘＤＯ４粒子を、Ｅ源を水を主成分とする溶媒中に溶解した溶液中に投入し、撹拌して懸濁液とし、この懸濁液を乾燥後、熱処理して、表面処理ＬｉｗＡｘＤＯ４粒子とし、この表面処理ＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体とし、この粉体を非酸化性雰囲気下にて熱処理するので、電圧、エネルギー密度、負荷特性が大幅に向上した電極活物質を容易に作製することができる。したがって、長期のサイクル安定性及び安全性が大幅に向上した電極活物質を、安定的に供給することができる。 According to the method for producing an electrode active material of this embodiment, Li w A x DO 4 particles are put into a solution in which an E source is dissolved in a solvent containing water as a main component, and stirred to obtain a suspension. The suspension is dried and then heat-treated to form surface-treated Li w A x DO 4 particles. The surface-treated Li w A x DO 4 particles are put into a solution containing an organic substance serving as a carbon source and stirred. This slurry is dried to form a powder, and this powder is heat-treated in a non-oxidizing atmosphere, so that an electrode active material with greatly improved voltage, energy density, and load characteristics can be easily produced. be able to. Therefore, it is possible to stably supply an electrode active material with greatly improved long-term cycle stability and safety.
本実施形態のリチウムイオン電池によれば、本実施形態の電極活物質３１をリチウムイオン電池の正電極に用いたので、高電圧、高エネルギー密度、高負荷特性を有するとともに、長期のサイクル安定性及び安全性に優れたリチウムイオン電池を提供することができる。 According to the lithium ion battery of this embodiment, since the electrode active material 31 of this embodiment is used for the positive electrode of the lithium ion battery, it has high voltage, high energy density, high load characteristics, and long-term cycle stability. In addition, a lithium ion battery excellent in safety can be provided.
以下、実施例１〜９及び比較例１、２により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely by Examples 1-9 and Comparative Examples 1 and 2, this invention is not limited by these Examples.
（ＬｉＭｎＰＯ４粒子の合成）
実施例１〜３、９及び比較例１共通のＬｉＭｎＰＯ４を、以下のようにして作製した。
Ｌｉ源及びＰ源としてＬｉ３ＰＯ４を、Ｍｎ源としてＭｎＳＯ４・５Ｈ２Ｏを用い、これらをモル比でＬｉ：Ｍｎ：Ｐ＝３：１：１となるように純水に溶解して前駆体溶液２００ｍＬを作製した。
(Synthesis of LiMnPO 4 particles)
LiMnPO 4 common to Examples 1 to 3 and 9 and Comparative Example 1 was produced as follows.
Li 3 PO 4 was used as the Li source and P source, MnSO 4 .5H 2 O was used as the Mn source, and these were dissolved in pure water so that the molar ratio was Li: Mn: P = 3: 1: 1. 200 mL of the precursor solution was prepared.
次いで、この前駆体溶液を耐圧容器に入れ、１７０℃にて２４時間、水熱合成を行った。この反応後に室温になるまで冷却し、沈殿しているケーキ状の反応生成物を得た。
次いで、この沈殿物を蒸留水にて５回水洗して不純物を洗い流し、その後、乾燥しないように含水率３０％に保持し、ケーキ状のＬｉＭｎＰＯ４とした。
このケーキ状のＬｉＭｎＰＯ４から若干量の試料を採取し、７０℃にて２時間真空乾燥させて得られた粉体をＸ線回折法にて同定したところ、単相のＬｉＭｎＰＯ４が生成していることが確認された。
Subsequently, this precursor solution was put into a pressure vessel and hydrothermal synthesis was performed at 170 ° C. for 24 hours. After this reaction, the reaction mixture was cooled to room temperature to obtain a precipitated cake-like reaction product.
Next, the precipitate was washed with distilled water 5 times to wash away impurities, and then kept at a water content of 30% so as not to be dried, to obtain cake-like LiMnPO 4 .
A small amount of sample was taken from this cake-like LiMnPO 4 and vacuum-dried at 70 ° C. for 2 hours, and the powder obtained was identified by X-ray diffraction. As a result, single-phase LiMnPO 4 was produced. It was confirmed that
（ＬｉＣｏＰＯ４粒子の合成）
実施例４〜６及び比較例２共通のＬｉＣｏＰＯ４を、以下のようにして作製した。
Ｌｉ源及びＰ源としてＬｉ３ＰＯ４を、Ｃｏ源としてＣｏＳＯ４・７Ｈ２Ｏを用い、これらをモル比でＬｉ：Ｃｏ：Ｐ＝３：１：１となるように純水に溶解して前駆体溶液２００ｍＬを作製した。
(Synthesis of LiCoPO 4 particles)
LiCoPO 4 common to Examples 4 to 6 and Comparative Example 2 was produced as follows.
Li 3 PO 4 was used as the Li source and P source, CoSO 4 .7H 2 O was used as the Co source, and these were dissolved in pure water so that the molar ratio was Li: Co: P = 3: 1: 1. 200 mL of the precursor solution was prepared.
次いで、この前駆体溶液を耐圧容器に入れ、１７０℃にて２４時間、水熱合成を行った。この反応後に室温になるまで冷却し、沈殿しているケーキ状の反応生成物を得た。
次いで、この沈殿物を蒸留水にて５回水洗して不純物を洗い流し、その後、乾燥しないように含水率３０％に保持し、ケーキ状のＬｉＣｏＰＯ４とした。
このケーキ状のＬｉＣｏＰＯ４から若干量の試料を採取し、７０℃にて２時間真空乾燥させて得られた粉体をＸ線回折法にて同定したところ、単相のＬｉＣｏＰＯ４が生成していることが確認された。
Subsequently, this precursor solution was put into a pressure vessel and hydrothermal synthesis was performed at 170 ° C. for 24 hours. After this reaction, the reaction mixture was cooled to room temperature to obtain a precipitated cake-like reaction product.
Next, the precipitate was washed with distilled water 5 times to wash away impurities, and then kept at a moisture content of 30% so as not to be dried, to obtain cake-like LiCoPO 4 .
A small amount of sample was taken from the cake-like LiCoPO 4 and vacuum-dried at 70 ° C. for 2 hours. The powder obtained was identified by X-ray diffraction. As a result, single-phase LiCoPO 4 was produced. It was confirmed that
（実施例１）
ＬｉＭｎＰＯ４９５質量％に対し、Ｌｉ源としてＬｉＣＨ３ＣＯＯを、Ｆｅ源としてＦｅ（ＣＨ３ＣＯＯ）２を、リン酸源として（ＮＨ４）２ＨＰＯ４を、ＬｉＦｅＰＯ４に換算して５質量％含むように、これらの各質量を調整して純水中に投入し、撹拌して懸濁させ、得られたスラリーを乾燥後、６００℃にて６時間、熱処理を行い、粉体を得た。
次いで、この粉体９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図２に示す構造の実施例１の電極活物質を得た。
Example 1
LiMnPO 4 95% by mass, LiCH 3 COO as the Li source, Fe (CH 3 COO) 2 as the Fe source, (NH 4 ) 2 HPO 4 as the phosphoric acid source, and 5% by mass in terms of LiFePO 4 Each of these masses was adjusted so as to be contained, poured into pure water, stirred and suspended, and the obtained slurry was dried and then heat-treated at 600 ° C. for 6 hours to obtain a powder. .
Next, a 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of the powder so that the solid content of polyvinyl alcohol is 5% by mass to obtain a suspended slurry. Heat treatment was performed for a time, and the electrode active material of Example 1 having the structure shown in FIG. 2 was obtained.
（実施例２）
ＬｉＭｎＰＯ４９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、さらに、Ｌｉ源としてＬｉＣＨ３ＣＯＯを、Ｆｅ源としてＦｅ（ＣＨ３ＣＯＯ）２を、リン酸源として（ＮＨ４）２ＨＰＯ４を、ＬｉＦｅＰＯ４に換算して４質量％含むように、これらの各質量を調整して投入し、撹拌して懸濁させ、得られたスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図３に示す構造の実施例２の電極活物質を得た。
(Example 2)
LiMnPO 4 to 95 wt%, polyvinyl alcohol 10% aqueous solution, was added in an amount of 5 wt% polyvinyl alcohol solids, addition, LiCH 3 COO as Li source, as Fe source Fe (CH 3 COO) 2 And (NH 4 ) 2 HPO 4 as a phosphoric acid source, each of these masses is adjusted so as to be contained in an amount of 4% by mass in terms of LiFePO 4 , and the resulting slurry is stirred and suspended. After drying, heat treatment was performed at 600 ° C. for 1 hour to obtain an electrode active material of Example 2 having the structure shown in FIG.
（実施例３）
ＬｉＭｎＰＯ４９５質量％に対し、Ｆｅ源として塩化鉄（II）（ＦｅＣｌ２）を５質量％含むように、これらＬｉＭｎＰＯ４及び塩化鉄（II）（ＦｅＣｌ２）の各質量を調整して純水中に投入し、撹拌して懸濁させ、この懸濁液を乾燥後、６００℃にて６時間、熱処理を行い、粉体を得た。
次いで、この粉体９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図４に示す構造の実施例３の電極活物質を得た。
Example 3
Pure water is prepared by adjusting each mass of LiMnPO 4 and iron chloride (II) (FeCl 2 ) so that 95 mass% of LiMnPO 4 contains 5 mass% of iron chloride (II) (FeCl 2 ) as an Fe source. The suspension was stirred and suspended, and the suspension was dried and then heat-treated at 600 ° C. for 6 hours to obtain a powder.
Next, a 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of the powder so that the solid content of polyvinyl alcohol is 5% by mass to obtain a suspended slurry. Heat treatment was performed for a time, and an electrode active material of Example 3 having the structure shown in FIG. 4 was obtained.
（実施例４）
ＬｉＣｏＰＯ４９５質量％に対し、Ｌｉ源としてＬｉＣＨ３ＣＯＯを、Ｆｅ源としてＦｅ（ＣＨ３ＣＯＯ）２を、リン酸源として（ＮＨ４）２ＨＰＯ４を、ＬｉＦｅＰＯ４に換算して５質量％含むように、これらの各質量を調整して純水中に投入し、撹拌して懸濁させ、得られたスラリーを乾燥後、６００℃にて６時間、熱処理を行い、粉体を得た。
次いで、この粉体９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図２に示す構造の実施例４の電極活物質を得た。
Example 4
5% by mass in terms of LiCoPO 4 95% by mass in terms of LiCH 3 COO as the Li source, Fe (CH 3 COO) 2 as the Fe source, (NH 4 ) 2 HPO 4 as the phosphoric acid source, and LiFePO 4 Each of these masses was adjusted so as to be contained, poured into pure water, stirred and suspended, and the obtained slurry was dried and then heat-treated at 600 ° C. for 6 hours to obtain a powder. .
Next, a 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of the powder so that the solid content of polyvinyl alcohol is 5% by mass to obtain a suspended slurry. Heat treatment was performed for a time, and an electrode active material of Example 4 having the structure shown in FIG. 2 was obtained.
（実施例５）
ＬｉＣｏＰＯ４９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、さらに、Ｌｉ源としてＬｉＣＨ３ＣＯＯを、Ｆｅ源としてＦｅ（ＣＨ３ＣＯＯ）２を、リン酸源として（ＮＨ４）２ＨＰＯ４を、ＬｉＦｅＰＯ４に換算して４質量％含むように、これらの各質量を調整して投入し、撹拌して懸濁させ、得られたスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図３に示す構造の実施例５の電極活物質を得た。
(Example 5)
With respect to 95% by mass of LiCoPO 4, a 10% aqueous solution of polyvinyl alcohol is added so that the solid content of polyvinyl alcohol is 5% by mass. Further, LiCH 3 COO as a Li source and Fe (CH 3 COO) 2 as an Fe source And (NH 4 ) 2 HPO 4 as a phosphoric acid source, each of these masses is adjusted so as to be contained in an amount of 4% by mass in terms of LiFePO 4 , and the resulting slurry is stirred and suspended. After drying, heat treatment was performed at 600 ° C. for 1 hour to obtain an electrode active material of Example 5 having the structure shown in FIG.
（実施例６）
ＬｉＣｏＰＯ４９５質量％に対し、Ｆｅ源として塩化鉄（II）（ＦｅＣｌ２）を５質量％含むように、これらＬｉＣｏＰＯ４及び塩化鉄（II）（ＦｅＣｌ２）の各質量を調整して純水中に投入し、撹拌して懸濁させ、この懸濁液を乾燥後、６００℃にて６時間、熱処理を行い、粉体を得た。
次いで、この粉体９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で５質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、図４に示す構造の実施例６の電極活物質を得た。
(Example 6)
Pure water is prepared by adjusting each mass of LiCoPO 4 and iron chloride (II) (FeCl 2 ) so that 95 mass% of LiCoPO 4 contains 5 mass% of iron (II) chloride (FeCl 2 ) as an Fe source. The suspension was stirred and suspended, and the suspension was dried and then heat-treated at 600 ° C. for 6 hours to obtain a powder.
Next, a 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of the powder so that the solid content of polyvinyl alcohol is 5% by mass to obtain a suspended slurry. Heat treatment was performed for a time, and an electrode active material of Example 6 having the structure shown in FIG. 4 was obtained.
（実施例７）
実施例３のＬｉＭｎＰＯ４をＬｉＭｎ０．５Ｃｏ０．５ＰＯ４に替えた他は、実施例３に準じて、図４に示す構造の実施例７の電極活物質を得た。
(Example 7)
The electrode active material of Example 7 having the structure shown in FIG. 4 was obtained according to Example 3, except that LiMnPO 4 of Example 3 was replaced with LiMn 0.5 Co 0.5 PO 4 .
（実施例８）
実施例３のＬｉＭｎＰＯ４をＬｉ２ＭｎＳｉＯ４に替えた他は、実施例３に準じて、図４に示す構造の実施例７の電極活物質を得た。
(Example 8)
The electrode active material of Example 7 having the structure shown in FIG. 4 was obtained according to Example 3 except that LiMnPO 4 of Example 3 was replaced with Li 2 MnSiO 4 .
（実施例９）
実施例３のＦｅ源である塩化鉄（II）（ＦｅＣｌ２）をＮｉ源である塩化ニッケル（ＮｉＣｌ２）に替えた他は、実施例３に準じて、図４に示す構造の実施例９の電極活物質を得た。
Example 9
Example 9 of the structure shown in FIG. 4 is the same as Example 3 except that iron chloride (II) (FeCl 2 ) as the Fe source in Example 3 is replaced with nickel chloride (NiCl 2 ) as the Ni source. An electrode active material was obtained.
（比較例１）
ＬｉＭｎＰＯ４９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で７質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、比較例１の電極活物質を得た。
(Comparative Example 1)
A 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of LiMnPO 4 so that the solid content of polyvinyl alcohol is 7% by mass to obtain a suspended slurry. The slurry is dried and then heat treated at 600 ° C. for 1 hour. The electrode active material of Comparative Example 1 was obtained.
（比較例２）
ＬｉＣｏＰＯ４９５質量％に対し、ポリビニルアルコール１０％水溶液を、ポリビニルアルコール固形分で７質量％となるように添加し、懸濁したスラリーとし、このスラリーを乾燥後、６００℃にて１時間、熱処理を行い、比較例２の電極活物質を得た。
(Comparative Example 2)
A 10% aqueous solution of polyvinyl alcohol is added to 95% by mass of LiCoPO 4 so that the solid content of polyvinyl alcohol is 7% by mass to obtain a suspended slurry. The slurry is dried and then heat treated at 600 ° C. for 1 hour. The electrode active material of Comparative Example 2 was obtained.
「リチウムイオン電池の作製」
実施例１〜９及び比較例１、２各々の正電極を作製した。
ここでは、実施例１〜９及び比較例１、２各々にて得られた各電極活物質、導電助剤としてアセチレンブラック（ＡＢ）、バインダーとしてポリフッ化ビニリデン（ＰＶｄＦ）、溶媒としてＮ−メチル−２−ピロリジノン（ＮＭＰ）を用い、これらを混合し、実施例１〜９及び比較例１、２各々のペーストを作製した。なお、ペースト中の質量比、ＬｉＭｎＰＯ４またはＬｉＣｏＰＯ４：ＡＢ：ＰＶｄＦは８５：１０：５であった。
次いで、これらのペーストを厚み３０μｍのアルミニウム（Ａｌ）箔上に塗布し、乾燥した。その後、４０ＭＰａの圧力にて圧密し、正電極とした。
“Production of lithium-ion batteries”
The positive electrodes of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared.
Here, each electrode active material obtained in each of Examples 1 to 9 and Comparative Examples 1 and 2, acetylene black (AB) as a conductive assistant, polyvinylidene fluoride (PVdF) as a binder, and N-methyl- as a solvent Using 2-pyrrolidinone (NMP), these were mixed to prepare pastes of Examples 1 to 9 and Comparative Examples 1 and 2, respectively. The mass ratio in the paste, LiMnPO 4 or LiCoPO 4 : AB: PVdF, was 85: 10: 5.
Next, these pastes were applied onto an aluminum (Al) foil having a thickness of 30 μm and dried. Then, it compacted with the pressure of 40 Mpa, and set it as the positive electrode.
次いで、この正電極を成形機を用いて面積が２ｃｍ２の円板状に打ち抜き、真空乾燥後、乾燥Ａｒ雰囲気下にてステンレススチール（ＳＵＳ）製の２０１６コイン型セルを用いて、実施例１〜９及び比較例１、２各々のリチウムイオン電池を作製した。なお、負極には金属Ｌｉを、セパレーターには多孔質ボリプロピレン膜を、電解質溶液には１ＭのＬｉＰＦ６溶液を、それぞれ用いた。このＬｉＰＦ６溶液の溶媒としては、炭酸エチレンと炭酸ジエチルとの比が１：１のものを用いた。 Next, this positive electrode was punched into a disk shape having an area of 2 cm 2 using a molding machine, vacuum dried, and then subjected to a stainless steel (SUS) 2016 coin cell in a dry Ar atmosphere. To 9 and Comparative Examples 1 and 2 were prepared. Metal Li was used for the negative electrode, a porous polypropylene film was used for the separator, and a 1M LiPF 6 solution was used for the electrolyte solution. As a solvent for this LiPF 6 solution, a solvent having a ratio of ethylene carbonate to diethyl carbonate of 1: 1 was used.
「電池特性試験」
実施例１〜９及び比較例１、２各々のリチウムイオン電池の電池特性試験を、環境温度６０℃、充電電流０．１ＣＡで、試験極の電位がＬｉの平衡電位に対して所定の充電電圧になるまで充電し、１分間休止の後、０．１ＣＡ及び１ＣＡの放電電流で２．０Ｖになるまで放電させて行った。
充電電圧は、実施例１〜３、８、９及び比較例１のＭｎ系のリチウムイオン電池については４．５Ｖ、実施例４〜７及び比較例２のＣｏ系のリチウムイオン電池については４．９Ｖとした。
実施例１〜９及び比較例１、２各々の環境温度６０℃における放電容量（１Ｃ）を表１に示す。また、図５〜７に実施例１〜３の０．１ＣＡの充放電曲線を示す。
"Battery characteristics test"
The battery characteristics test of each of the lithium ion batteries of Examples 1 to 9 and Comparative Examples 1 and 2 was performed at an environmental temperature of 60 ° C., a charging current of 0.1 CA, and a predetermined charging voltage with respect to the equilibrium potential of the test electrode being Li The battery was charged until the battery was discharged, and after a pause of 1 minute, the battery was discharged at a discharge current of 0.1 CA and 1 CA to 2.0 V.
The charging voltage is 4.5 V for the Mn-based lithium ion batteries of Examples 1 to 3, 8, and 9 and Comparative Example 1, and 4 for the Co-based lithium ion batteries of Examples 4 to 7 and Comparative Example 2. It was set to 9V.
Table 1 shows the discharge capacities (1C) of Examples 1 to 9 and Comparative Examples 1 and 2 at an environmental temperature of 60 ° C. Moreover, the charging / discharging curve of 0.1CA of Examples 1-3 is shown in FIGS.
なお、実施例１〜９では、電極材料自体の挙動をデータに反映させるために、負極に金属リチウムを用いたが、金属リチウムの代わりに天然黒鉛、人造黒鉛、コークス等の炭素材料、リチウム合金、Ｌｉ４Ｔｉ５Ｏ１２等の負極材料を用いてもよい。
また、実施例１〜９では、導電助剤としてアセチレンブラックを用いているが、カーボンブラック、グラファイト、ケッチェンブラック、天然黒鉛、人造黒鉛等の炭素材料を用いてもよい。
In Examples 1 to 9, in order to reflect the behavior of the electrode material itself in the data, metallic lithium was used for the negative electrode, but instead of metallic lithium, carbon materials such as natural graphite, artificial graphite and coke, lithium alloys A negative electrode material such as Li 4 Ti 5 O 12 may be used.
Moreover, in Examples 1-9, although acetylene black is used as a conductive support agent, you may use carbon materials, such as carbon black, graphite, ketjen black, natural graphite, and artificial graphite.
また、電解質溶液にＬｉＰＦ６溶液を、このＬｉＰＦ６溶液の溶媒として炭酸エチレンと炭酸ジエチルとの比が１：１のものを、それぞれ用いたが、ＬｉＰＦ６の代わりにＬｉＢＦ４やＬｉＣｌＯ４溶液を用いてもよく、炭酸エチレンの代わりにプロピレンカーボネートやジエチルカーボネートを用いてもよい。
また、電解液とセパレーターの代わりに固体電解質を用いてもよい。
Further, a LiPF 6 solution was used as the electrolyte solution, and a 1: 1 ratio of ethylene carbonate and diethyl carbonate was used as a solvent for this LiPF 6 solution. However, instead of LiPF 6 , LiBF 4 or LiClO 4 solution was used. Propylene carbonate or diethyl carbonate may be used instead of ethylene carbonate.
Moreover, you may use a solid electrolyte instead of electrolyte solution and a separator.
１ 電極活物質
２ ＬｉｗＡｘＤＯ４粒子
３ 被覆層
１１ 電極活物質
１２ （第２の）被覆層
２１ 電極活物質
２２ 被覆層
３１ 電極活物質
３２ 被覆層
1 the electrode active material 2 Li w A x DO 4 particles 3 covering layer 11 electrode active material 12 (second) coating layer 21 electrode active material 22 coating layer 31 electrode active material 32 coating layer
Claims (3)
前記被覆層が１ｎｍ以上かつ５ｎｍ以下であり、
前記被覆層は、前記ＬｉｗＡｘＤＯ４粒子を表面処理する前記Ｆｅ及びＮｉのいずれか１種または２種を含む化合物と、
前記ＬｉｗＡｘＤＯ４粒子の表面処理された部分に存在する前記Ｆｅ及びＮｉのいずれか１種または２種を含む化合物と接触する有機系炭素質の電子伝導性物質と、を有する電極活物質。 Li w A x DO 4 (where A is one or two selected from the group of Mn and Co, D is one or two selected from the group of P, Si and S) The surface of particles consisting of 0 <w ≦ 4, 0 <x ≦ 1.5) is coated with a coating layer,
The coating layer is 1 nm or more and 5 nm or less,
The coating layer includes a compound containing any one or two of Fe and Ni that surface-treats the Li w A x DO 4 particles;
An organic carbonaceous electron conductive material in contact with a compound containing either one or two of Fe and Ni present in the surface-treated portion of the Li w A x DO 4 particles. material.
水を主成分とする溶媒中にＦｅ、Ｎｉの群から選択される１種または２種を含む化合物を溶解した溶液中に、前記Ｌｉ ｗ Ａ ｘ ＤＯ ４ 粒子を投入し、撹拌して懸濁液とし、この懸濁液を乾燥後、熱処理して、表面処理ＬｉｗＡｘＤＯ４粒子とし、この表面処理ＬｉｗＡｘＤＯ４粒子を、炭素源となる有機物を含む溶液中に投入し、撹拌してスラリーとし、このスラリーを乾燥して粉体とし、この粉体を非酸化性雰囲気下にて熱処理することを特徴とする電極活物質の製造方法。 It is a manufacturing method of the electrode active material according to claim 1,
The Li w A x DO 4 particles are put into a solution in which a compound containing one or two selected from the group of Fe and Ni is dissolved in a solvent containing water as a main component, and suspended by stirring. After the suspension is dried and heat-treated to obtain surface-treated Li w A x DO 4 particles, the surface-treated Li w A x DO 4 particles are put into a solution containing an organic substance serving as a carbon source. A method for producing an electrode active material, comprising stirring to form a slurry, drying the slurry to form a powder, and heat-treating the powder in a non-oxidizing atmosphere.
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| WO2013047510A1 (en) * | 2011-09-29 | 2013-04-04 | 昭和電工株式会社 | Positive electrode active material used in lithium secondary batteries and production method therefor |
| JP5967101B2 (en) * | 2011-12-02 | 2016-08-10 | 昭栄化学工業株式会社 | Positive electrode material for lithium ion secondary battery, positive electrode member for lithium ion secondary battery, and lithium ion secondary battery |
| KR20130066326A (en) * | 2011-12-12 | 2013-06-20 | 어플라이드 머티어리얼스, 인코포레이티드 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
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