CN101065322A - Method of producing electrode active material - Google Patents
Method of producing electrode active material Download PDFInfo
- Publication number
- CN101065322A CN101065322A CNA2005800404644A CN200580040464A CN101065322A CN 101065322 A CN101065322 A CN 101065322A CN A2005800404644 A CNA2005800404644 A CN A2005800404644A CN 200580040464 A CN200580040464 A CN 200580040464A CN 101065322 A CN101065322 A CN 101065322A
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- China
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- source material
- general formula
- active material
- electrode active
- compound
- Prior art date
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000007772 electrode material Substances 0.000 title abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 100
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- -1 phosphate compound Chemical class 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 110
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 61
- 238000002360 preparation method Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 230000002829 reductive effect Effects 0.000 claims description 27
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011343 solid material Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 10
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 229910000319 transition metal phosphate Inorganic materials 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 33
- 238000012360 testing method Methods 0.000 description 32
- 239000000155 melt Substances 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 239000006230 acetylene black Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 18
- 239000013078 crystal Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000010583 slow cooling Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 150000003016 phosphoric acids Chemical class 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- CQTRUFMMCCOKTA-UHFFFAOYSA-N diacetoneamine hydrogen oxalate Natural products CC(=O)CC(C)(C)N CQTRUFMMCCOKTA-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical class CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical class [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
An object of the present invention is to provide a method of more efficiently producing an electrode active material whose main component is a transition metal phosphate compound. According to the present invention, a method of producing an electrode active material is provided in which the main component thereof is a phosphate compound represented by the general formula: AxM(PO4) y (here, 0 = x = 2, 0 < y = 2, A is an alkali metal, and M is a transition metal). This method comprises preparing a composition in the melted state that contains a source of M and a source of phosphorus (and also a source of A when 0 < x). This method is suitable as a method of producing an electrode active material whose main component is, for example, an olivine-type lithium iron phosphate compound.
Description
The present invention relates to be used as the electrode active material of store battery, by general formula A
xM (PO
4)
yThe preparation method of the phosphate compounds that (0≤x≤2,0＜y≤2 wherein, A is one or both or multiplely is selected from alkali-metal element, M is one or both or the multiple element that is selected from transition metal) are represented.In addition, the invention still further relates to the non-aqueous electrolyte battery that utilizes this electrode active material.
Technical background
Known store battery charges by moving between electrode pair such as positively charged ion such as lithium ions and discharges.The exemplary of this class store battery has lithium battery (being typically lithium ion battery).Can store/discharge the electrode active material that cationic material can be used as store battery.Electrode active material in this specification sheets and claims refers to the material that is used to make battery terminal.Except electrode active material, electrode can comprise electro-conductive material and tackiness agent.Usually, electrode active material uses together with the tinsel that is connected to battery terminal.In general, it is Powdered that electrode active material is, and the paste that comprises the electrode activity powder is coated onto on the tinsel.Except the electrode activity powder, paste can comprise conductive powder and tackiness agent.The electrode activity powder can be pressed into electrode.
Studying active material of positive electrode and the active material of cathode of various materials as this store battery.For example, Japanese Laid-Open Patent Application bulletin H9-134724 discloses and has contained by LiFePO
4The represented olivine-type tertiary iron phosphate compound of formula is as the non-aqueous electrolyte battery of active material of positive electrode.In addition, Japanese Laid-Open Patent Application bulletin 2000-509193 discloses by Li
3Fe
2(PO
4)
3The electrode active material that the represented Nasicon type tertiary iron phosphate compound of formula is constituted.Other prior art reference that relate to electrode active material comprise Japanese Laid-Open Patent Application bulletin H9-134725,2001-250555,2002-15735 and H8-83606.
Through intensive research, confirm by general formula A
xM (PO
4)
y(0≤x≤2 wherein, 0＜y≤2, A is one or both or multiplely is selected from alkali-metal element, and M is one or both or the multiple element that is selected from transition metal) represented phosphate compounds (compound of transition metal and phosphoric acid or basic metal, transition metal and phosphatic compound) can be used as the electrode active material of store battery.Below, when being suitable for above-mentioned definition, re-defining of x, y, A and M will be omitted.
Summary of the invention
In the prior art, prepare the phosphate compounds that is suitable for use as electrode active material by solid state reaction (curing).This class solid state reaction generally needs the long relatively time.If it will be useful that the more high-efficiency method of preparation phosphate compounds can be provided.
Thus, a target of the present invention be to provide preparation can be used as electrode active material by general formula A
xM (PO
4)
yRepresented phosphate compounds biology is high-efficiency method more.
Another target of the present invention is that the store battery that contains this class electrode active material will be provided.
The inventor finds, by the melt composition from molten state (liquid state) to solid-state slow cooling raw material, can prepare general formula A more efficiently
xM (PO
4)
yRepresented phosphate compounds.
Relate to by general formula A in this disclosed invention
xM (PO
4)
y(0≤x≤2 wherein, 0＜y≤2, A is one or both or multiplely is selected from alkali-metal element, and M is one or both or the multiple element that is selected from transition metal) preparation method of represented phosphate compounds (transition metal and phosphatic compound or basic metal, transition metal and phosphatic compound).This preparation method comprises the preparation process of molten feedstock composition.Work as A
xM (PO
4)
yIn x when not being 0 (x ≠ 0), just (during 0＜x, raw material contains at A greater than 0 as x
xM (PO
4)
yIn contain A source material, at A
xM (PO
4)
yIn contain M source material and phosphorus (P) source material.Work as A
xM (PO
4)
yIn x when being 0 (x=0), raw material is at A
xM (PO
4)
yIn contain M source material and phosphorus (P) source material.Can pass through, for example, mix the solid material contain M source material and the solid material that contains phosphorus source material, and, subsequently raw material is fused into molten state and prepare this melt composition when the solid material that contains A source material of x greater than 0 time.The preparation method further comprises the step of slow cooling melt composition.Here, " slowly cooling " is the notion opposite with quenching, and the meaning is to reduce temperature relatively lentamente.Slowly can there be boundary clearly between cooling and the quenching.Can distinguish slow cooling and quenching like this, that is, what obtain when melting compound is cooled off fast is noncrystalline phosphoric acid salt, and on the other hand, what obtain when melting compound is slowly cooled off is crystallization phosphoric acid salt.Just, the predetermined speed of speed of cooling ratio is cooled off (quenching) noncrystalline phosphoric acid salt of growth and the speed of cooling slow cooling generation crystallization phosphoric acid salt slower than predetermined speed faster fast.
Can distinguish noncrystalline phosphoric acid salt and crystallization phosphoric acid salt by x-ray diffraction pattern.Noncrystalline phosphoric acid salt does not show the peak in x-ray diffraction pattern, and on the other hand, in x-ray diffraction pattern, crystallization phosphoric acid salt demonstrates the peak corresponding to crystallization phosphate crystal structure.
According to production method of the present invention, can more efficiently prepare the compound that shows as the useful property of electrode active material (for example, in the shorter time).
Of present method preferred aspect, it is 1: 1: 1 A, M and phosphorus substantially that melt composition and/or the composition that constitutes fused raw material contain atomic ratio.Melt composition with this atomic ratio is suitable for preparing phosphate compounds, wherein at formula A
xM (PO
4)
yMiddle x and y are 1 substantially.In other words, the melt composition with this atomic ratio is suitable for preparation formula AMPO
4The phosphate compounds corresponding to olivine-type of representative.The AMPO of olivine-type
4Has outstanding characteristic as electrode active material.
Another preferred aspect, the composition of melt composition and/or fused raw material does not contain A.It is 1: 1 M and phosphorus substantially that melt composition and/or raw material contain atomic ratio.Melt composition with this atomic ratio is fit to be used for preparing phosphate compounds, wherein at formula A
xM (PO
4)
yIn, x is 0 and at formula A
xM (PO
4)
yIn, y is 1 substantially.In other words, the melt composition with this atomic ratio is suitable for preparation formula MPO
4The phosphate compounds corresponding to olivine-type of representative.The MPO of olivine-type
4Has outstanding characteristic equally as electrode active material.
M source material can be that the compound (hereinafter be also referred to as " M compound ") of M as the composition element arranged.The valency that the M compound can be selected from M is higher than A
xM (PO
4)
yValent compound of middle M.In addition, the M compound valency that can be selected from M equals A
xM (PO
4)
yValent compound of middle M.In addition, the valency of M wherein can be higher than A
xM (PO
4)
yIn M valent M compound and wherein the valency of M equal A
xM (PO
4)
yValent M compound of middle M uses together.According in this disclosed preparation method, the selection of M source material can be widened the low activity oxide compound that can not be used in the conventional solid phase baking process(of sulfonation).Particularly, the advantage of oxide raw material be they usually cheaply than more active raw material such as ammonium salt, acetate, oxalate etc.In addition, oxide raw material seldom produces stench or toxic active by-product gas.Therefore, this disclosed preparation method to shorten the production time, to cut down finished cost, reduce raw materials cost etc. very effective.
When the valency of M wherein is higher than A
xM (PO
4)
yIn valent M compound of M when being used as part or all of M source material, the composition of preferred molten attitude (melt composition) contains reductive agent.So just can prepare desirable A efficiently
xM (PO
4)
yPhosphate compounds.For example, can use carbon dust as reductive agent.In addition, replace using reductive agent, or except reductive agent, the top temperature (hereinafter, top temperature refers to the top temperature of melt composition in the preparation process) that improves melt composition also is favourable.
Can be used to prepare the electrode active material that main component is phosphate compounds (wherein M mainly is iron (Fe)) in this disclosed invention.For example, the present invention is suitable for preparing the tertiary iron phosphate compd A
xFe
II(PO
4)
y, wherein x and y are 1 (olivine-type tertiary iron phosphate compound are by AFe usually
II(PO
4) represent).The present invention also is suitable for preparing the tertiary iron phosphate compd A
xFe
III(PO
4)
y, wherein x be 0 and y be 1 (olivine-type tertiary iron phosphate compound be by Fe usually
III(PO
4) represent).Particularly preferred application is the tertiary iron phosphate compound, wherein at A
xM (PO
4)
yIn, x and y substantially are 1.According in this disclosed method, not only contain ferrous iron and can be selected as preparation as the compound (for example FeO) of composition element and have the above-mentioned raw material (source of iron material) that ferrous phosphate of olivine type compound is arranged, and contain ferric iron as the compound of composition element (Fe for example
2O
3) also can be selected as raw material.As ferric oxide (Fe
2O
3Deng) when being used as part or all of source of iron material, preferably add reductive agent (carbon dust) in melt composition, and/or improve the top temperature of melt composition relatively.Can prepare the electrode active material that main component is desirable tertiary iron phosphate compound efficiently like this.
All be suitable for use as the composition material of store battery (being generally lithium-ions battery) by any above-mentioned electrode active material that method obtained.Above-mentioned store battery contains, for example, have first electrode (male or female) of any above-mentioned electrode active material, can store/discharge the second electrode (electrode opposite of cationic material with first electrode, for example negative electrode or anode), and non-aqueous electrolyte or solid state electrolyte.
Also relate to store battery in this disclosed another invention, this store battery has the anode that contains by the resulting electrode active material of any aforesaid method.In addition, store battery has the negative electrode that contains the material that can store/discharge alkalimetal ion.For example, if battery of the present invention is a lithium battery, it will have the negative electrode that contains the material that can store/discharge lithium ion.In addition, store battery has non-aqueous solution type ionogen or solid electrolyte.According to the present invention, can prepare store battery efficiently with said structure.
In this disclosed invention is the active material of positive electrode that is used for the store battery produced by above-mentioned any method on the other hand.The exemplary of active material of the present invention is that to be used for its main component be by A substantially
xM (PO
4)
yThe active material of positive electrode of the store battery of the crystallization phosphate compounds of representative.
Brief description of drawings
Fig. 1 is the X-ray diagram of sample 1.
Fig. 2 is the X-ray diagram of sample 2.
Fig. 3 is the X-ray diagram of sample 3.
Fig. 4 is the X-ray diagram of sample 4.
Fig. 5 is the X-ray diagram of sample 5.
Fig. 6 is the X-ray diagram of sample 6.
Fig. 7 is the X-ray diagram of sample 7.
Fig. 8 is the charge/discharge graph of sample 1.
Fig. 9 is the cycle characteristics chart of sample 1.
Figure 10 is the multiplying power property chart of sample 1.
Figure 11 is the charge/discharge graph of sample 2.
Figure 12 is the cycle characteristics chart of sample 2.
Figure 13 is the multiplying power property chart of sample 2.
Figure 14 is the charge/discharge graph of sample 3.
Figure 15 is the cycle characteristics chart of sample 3.
Figure 16 is the multiplying power property chart of sample 3.
Figure 17 is the charge/discharge graph of sample 5.
Figure 18 is the cycle characteristics chart of sample 5.
Figure 19 is a cross sectional representation of measuring battery structure.
Implement best mode of the present invention
To narrate preferred implementation of the present invention below.Should be noted in the discussion above that for a person skilled in the art, except those particularly point out in this manual,, should be understood as that the content of design implementing those contents of necessity of the present invention.Just can realize the present invention based on the common technical knowledge of the disclosed content of this specification sheets and this area.
It is by general formula A that preparation method of the present invention can be applied to its main component
xM (PO
4)
yIn the preparation of the electrode active material of the transition metal phosphate compound of representative.A
xM (PO
4)
yIn M be one or both or the multiple element that is selected from transition metal.The object lesson of M comprises iron (Fe), vanadium (V), titanium (Ti) etc.A
xM (PO
4)
yIn A be the element that one or both or multiple (normally a kind of) are selected from basic metal such as lithium (Li), sodium (Na), potassium (K) etc." x " is the numerical value that satisfies 0≤x≤2 (normally 0＜x≤2, but x can be 0).In addition, " y " is the numerical value that satisfies 0＜y≤2 (y can not be 0).Because A
xM (PO
4)
yThe electrochemical equivalent of the compound of representative is relatively little, therefore just can obtain bigger theoretical capacity.Preparation in accordance with the present invention can be prepared the useful electrode active material of this class efficiently.
Can comprise that main component is A wherein by the electrode active material that the disclosed method of this specification sheets prepares
xM (PO
4)
yIn M mainly be the electrode active material of the composition of iron.Preferably at A
xM (PO
4)
yIn about 75% or more M be Fe.Preferably at A
xM (PO
4)
yIn about 90% or more M be Fe.Even more preferably at A
xM (PO
4)
yIn basic all M all be Fe.Preferred its main component of electrode active material of being used to the store battery that its charge/discharge finishes by lithium ion moving between electrode pair is A wherein
xM (PO
4)
yIn x greater than 0 and formula in A be the compound of lithium (Li).In addition, preferred its main component of electrode active material of being used to the store battery that its charge/discharge finishes by sodium ion moving between electrode pair is A wherein
xM (PO
4)
yIn x greater than 0 and formula in A be the compound of sodium (Na).
Can be applied to preparing electrode active material in this disclosed method, its main component is an olivine compounds, wherein A
xM (PO
4)
yIn x and y be that x=y=1 is (by AM substantially
II(PO
4) compound of representative, for example LiFe
II(PO
4)).Perhaps, can be applied to preparing electrode active material in this disclosed method, its main component is an olivine compounds, wherein A
xM (PO
4)
yIn x and y be x=0 substantially, y=1 is (by M
III(PO
4) compound of representative, for example Fe
III(PO
4)).In the preparation of above-mentioned olivine-type material (especially wherein M is the olivine-type material of divalence), adopt method of the present invention especially can embody good effect.
In addition, also can be applied to preparing electrode active material in this disclosed method, its main component is Nasicon type compound, wherein A
xM (PO
4)
yIn x and y be x=y=1.5 (A substantially
3M
III 2(PO
4)
3).By A
3M
III 2(PO
4)
3The compound of representative comprises, for example Li
3Fe
III 2(PO
4)
3Owing to adopt method of the present invention, even effect also has corresponding embodiment in above-mentioned Nasicon section bar material preparation.
When be applied to preparing its main component in this disclosed method is A wherein
xM (PO
4)
yIn x (just during the electrode active material of the compound of 0＜x, can make the melted state composition (melts) that contains M source material, P (phosphorus) source material and A source material greater than 0.Usually, in melts, the atomic ratio of M, P and A (mol ratio) is corresponding to the electrode active material (A that will be produced out
xM (PO
4)
y) atomic ratio of (objective composition).For example, can prepare the solids composition of such raw material, it contains M, P and A with the atomic ratio corresponding to target compound, and can be with the fusion of raw material combination thing.In general, for the atomic ratio of M, P and A, it can be considered to roughly the same between melts and/or raw material combination thing and target compound.
Any one compound as component with M, P and A can be used as M source material respectively, P source material and A source material.In other words, contain M and can be used as M source material as the compound (M compound) of component.The compound (carbonate of M, supercarbonate, acetate, oxalate, halogenide or oxyhydroxide etc.) that the oxide compound of M or the method by heating prepare the M oxide compound can be used as the M compound.Contain phosphorus and can be used as P source material as the phosphide of component.For example, can use the oxide compound of phosphorus or can generate compound (oxide compound such as the P of oxide compound of phosphorus by heating
2O
5Deng, and ammonium salt such as NH
4H
2PO
4, (NH
4)
2HPO
4Deng).Contain A and can be used as A source material as the A compound (A compound) of component.For example, can use the salt (carbonate, supercarbonate, acetate, oxalate, halogenide, oxyhydroxide etc.) of A.Every provenance material by a kind of compound two or multiple compound formed.When A was Li, lithium source substance can be by one or both or the multiple for example compound of the lithium salts of Quilonum Retard, lithium hydroxide etc. that is selected from.
Be noted that by selecting and can be used as fusing assistant (Li for example simultaneously as A source material
2CO
3) compound, can reduce the fusing point of melts.
Perhaps, can be used as M source material, P source material and A source material with any two or more elements among M, P and the A as the compound of component.For example, have P and A and can be used as P source material and A source material, can be used as M source material as the compound of component and have M as the compound of component.In addition, has M, P and A can be used as M, P and A as the compound of component common source material.For example by A
xM (PO
4)
yOne or both of representative or multiple phosphorus compound also can be used as the source material of M, P and A.Note, be used as the A of source material
xM (PO
4)
yCan be crystal or noncrystal, or crystal and non-crystal mixture.Owing to can be easy to adjust the atomic ratio of various elements (M, P and A), at least three kinds of compounds of general preferred use, every kind of compound contains a kind of among M, P and the A respectively, with raw material and/or the melts (being in the feedstock composition of molten state) of preparing compound.
Wherein the valency of M equals desirable A in the compound
xM (PO
4)
yValent compound of middle M can be selected as M source material.For example, in order to prepare AM
II(PO
4) the olivine-type electrode active material of representative, can select M is the compound of divalence.In order to prepare A
3M
III 2(PO
4)
3The Nasicon type electrode active material of representative, can select M is tervalent compound.When M is the element (as iron) with three valence states tendency more stable than divalent state, and target material is A wherein
xM (PO
4)
yIn the valency of M when mainly being 2 electrode active material, in order to prevent the oxidized trivalent that becomes of divalence M source material (for example FeO), can under reductive condition, carry out the preparation of electrode active material.
In addition, the valency of M is higher than that valent compound of M can be selected as M source material in the target material in the material of source.According in this disclosed method, have the three valence states tendency more stable even work as M, and the valency of M is in target material at 2 o'clock than divalent state, it still is possible selecting trivalent M source material.For example, when target material be by LiFe
II(PO
4) the olivine-type material that contains divalence Fe of representative, contain the Fe of trivalent Fe
2O
3Can be used as Fe source material.In other words, the method according to this invention, trivalent M source material can be used to prepare contain divalence M as the material of component (for example, by AM
II(PO
4) represented olivine-type electrode active material).This substantially from the olivine-type material (wherein, for example at A
xM (PO
4)
yIn, the valency of M mainly is ferrous iron (Fe)) very important in the preparation of the electrode active material that constituted.This is because obviously use Fe
2O
3As source of iron material cheap than FeO.Even the FeO that works as part is by Fe
2O
3When substituting, adopt effect of the present invention (reducing the effect of material cost) also will obtain suitable embodiment as the source of iron material.
On the other hand, be A wherein when preparing its main component
xM (PO
4)
yIn x be 0 compound (M (PO substantially
4)
y) electrode active material the time, the molten state composition (melts) that contains aforesaid M source material and phosphorus (P) source material should be produced out.Can suitably be selected with the compound that above-mentioned illustrated compound is the same when 0＜x as M source material and P source material.For example, when planning preparation by M
III(PO
4) during the olivine-type material (being y=1) of representative, can selecting wherein, M is tervalent compound.
Usually by raw material that will have M source material and raw material, adding as x that the raw material with A source material is mixed together greater than 0 the time and the blended composition of raw material heated and preparing aforesaid melts with P source material.For example, can be with the powder of M source material, the powder mixes of the powder of P source material and A source material gets up to prepare the raw material combination thing.Particle diameter and particle diameter distribution to each provenance material are not particularly limited.This is because feedstock composition is melted, so the influence of the character pair the finished product of feedstock composition will be restricted.The mixed state of preferred these raw materials each (being generally powder) is even relatively.More preferably mixed state is basic fully evenly.Yet,,, still can prepare and for the use in practice have enough inhomogeneity electrode active material even the homogeneity of raw material does not reach such height because feedstock composition is melted.Thereby the management of present method preparation parameter with ratio as solid phase reaction method easier.For example, the proterties of the manageable raw material that will use (every kind of element source material etc.) and the uniformity coefficient of feedstock composition (mixed state of every kind of raw material).This is useful to enhancing productivity.
Fusing (heating) method to feedstock composition is not particularly limited.Can adopt known heating means such as induction heating, microwave heating etc.
Rate of heating (heat-up rate) to the melt raw material composition is not particularly limited.Wait according to the ability of heating unit and to adopt suitable rate of heating.Yet when rate of heating is too low, production efficiency will descend.Consider from this respect,, be preferably about 60 ℃/h or higher usually for rate of heating, and 150 ℃/h or higher more preferably.
Top temperature to molten state composition (melts) is not particularly limited, as long as can obtain the molten state of composition.For example, it is about 800 to 2000 ℃ (preferred about 850 to 1800 ℃, more preferably from about 900 to 1600 ℃), and for obtaining the temperature of molten state.The minimum temperature that can obtain molten state is along with raw material combination thing (for example the kind of A and M, the value of x and y etc.) and different.For example, when A mainly is a lithium, when M mainly was Fe, top temperature was preferably about 850 to 1800 ℃, and more preferably from about 900 to 1600 ℃.
When M has three valence states than at the element of the more stable trend of divalent state, and to want to prepare wherein M mainly be that (usually, the main component of electrode active material is A wherein to divalence
xM (PO
4)
yIn x and y all be 1 compound substantially) the olivine-type material time, preferred above-mentioned top temperature will improve relatively.For example, preferably selected preparation parameter so that top temperature than the minimum temperature that can obtain molten state high at least about 400 ℃ (about 400 to 800 ℃ usually), and more preferably high at least about 600 ℃ temperature (common about 600 to 800 ℃).
The time (fusing time) that feedstock composition is maintained at molten state is not particularly limited.Consider that from the angle of production efficiency, energy consumption etc. general suitable fusing time is about 24 hours or still less (usually, about 5 minutes to 24 hours), and preferred about 6 hours or still less (about 5 minutes to 6 hours usually).In addition, the time (time length) that melts is maintained at aforesaid top temperature also is not particularly limited.Consider that from the homogeneity equal angles that increases target material the suitable time length was generally about 30 seconds or bigger (for example about 30 seconds to 2 hours) and be preferably 1 minute or bigger (for example about 1 minute to 1 hour).Perhaps can allow temperature descend (cooling or slowly cooling) after the top temperature immediately at heating combination.
Notice that molten state preparation of compositions method is not limited to aforesaid method, the composition of wherein pre-mixing (preparing) solid material is melted.For example, each solid material can prepare separately, can be melted and will melt separately good raw material then separately and mix, to form the melt composition of raw material.More specifically, every kind of raw material can be melted separately, and the source material of molten is mixed.Perhaps, material fusing in solid M source can be added to solid A source material in the material of fused M source then, and solid P source material can be added to wherein.
In aforesaid melt composition, can contain reductive agent.Especially, be higher than A when the valency of M wherein
xM (PO
4)
yWhen the M compound (for example, wherein M is tervalent M compound) of the valency (for example divalence) of middle M is used as part or whole M source material, preferably reductive agent is added in the melt composition.In addition, as wherein valency and the A of M
xM (PO
4)
yWhen the M compound (for example, wherein M is the M compound of divalence) that the valency (for example divalence) of middle M is the same is used as part or whole M source material, preferably reductive agent is added in the melt composition.Particularly, when M is when the three valence states element more stable than divalent state (for example iron), preferably reductive agent is added in the melt composition.Reductive agent can prevent better that the divalence M in the M compound is oxidized to the phenomenon of trivalent M.
Can preferably use carbonaceous material (carbon dust such as acetylene black, ketjen black, graphite precursor etc. for instance).Other reductive agent examples that can be used in this disclosed method comprise carbohydrate, polypropylene etc.
Adding this class reductive agent is not particularly limited to the mode of melt composition.For example, every kind of powder source material can mix with the preparation feedstock composition with powder reduction agent (carbon dust etc.), then can be with the mixture melt of raw material.Perhaps, can after every provenance material fusing, add reductive agent again.The amount that is added to the reductive agent in the melt composition is not particularly limited, but when the amount of adding very little the time, the effect of use reductive agent is not enough to show.On the other hand, if use too many reductive agent, the performance that may produce beyond thought influence and battery to the characteristic of target material may worsen.In every 100g melt composition, the amount of reductive agent is about 2g.
To obtain target material by the slow cooling and the aforesaid melt composition of hardening.Slowly cool off cooling simultaneously slowly so that obtain predetermined temperature curve, or allow the melt composition naturally cooling.Aforementioned predetermined temperature curve can be the wherein temperature curve that descends gradually with fixed speed of temperature, the temperature curve that descends step by step of temperature wherein, perhaps these combination.In general, reduce temperature with fixed speed (temperature lowering speed) and realize easily, thus preferably it.In this case, the temperature lowering speed can be, for example, and about 600 ℃/h or littler, preferred about 450 ℃/h or littler, and 300 ℃/h or littler more preferably from about.For target material, it has become high crystalline megatrend when the temperature lowering speed is slow.On the other hand, low excessively temperature lowering speed can cause the decline of production efficiency.From this point of view, in general Shi Yi temperature lowering speed is about 6 ℃/h or bigger, preferred about 30 ℃/h or bigger, and 60 ℃/h or bigger more preferably from about.Even when temperature progressively descends, the medial temperature lowering speed that the slow cool down of postponing begins to finish to slow cooling is preferably in above-mentioned scope.
Aspect of this disclosed method, melt composition slowly is cooled to composition by the hardened temperature from the temperature (normally from top temperature) that foregoing is in molten state.Usually slowly cooling off temperature up to composition is reduced at least about 300 ℃ or lower (preferred about 100 ℃ or lower).Preferably slowly cool off temperature up to composition and almost be room temperature (for example, about 60 ℃ or lower, preferred about 40 ℃ or lower).
Work as A
xM (PO
4)
yIn M have such character, promptly have the A of ratio as M
xM (PO
4)
yIn valency (A for example
xM (PO
4)
yIn M mainly be that divalence and M are when being iron) more stable relatively during higher valency, can in non-oxidizable atmosphere, carry out (normally inert atmosphere such as argon gas or contain reducing gas such as hydrogen (H to the aforesaid preparation process of small part
2) atmosphere that waits).Usually slow cool down (temperature decline) melt composition of preferably postponing begins to finish this process to its slow cooling and carries out under non-oxidizable atmosphere.More preferably finish this process and under non-oxidizable atmosphere, carry out, and even more preferably finish this process and under non-oxidizable atmosphere, carry out from the slow cooling of being prepared into of raw material from the slow cooling of being melted to of solid material.
By any one above-mentioned electrode active material that the preparation method obtained generally all is crystal.For example, the electrode active material for preparing like this is a crystallization transition metal phosphate compound as mentioned above.One preferred aspect, electrode active material can be that main component is the material that has the crystallization transition metal phosphate compound of olivine-type structure or have the crystallization transition metal phosphate compound of Nasicon type structure.Perhaps, electrode active material also can be mainly to be crystal but to contain the material of noncrystal part.Electrode active material is that the fact of crystal (at least mainly being crystal) and the fact that electrode active material has specific crystalline structure (olivine-type, Nasicon type etc.) can be determined by for example x-ray diffraction pattern.Generally be to obtain x-ray diffraction pattern by X-ray diffraction equipment.
According in this disclosed method, can prepare the material of being formed by the single-phase transition metal phosphate compound of peridotites substantially (or being to make electrode active material substantially) from this material.Here, " peridotites is single-phase " refers to, when, for example, want preparation by AM
II(PO
4) during the olivine-type material of representative, material does not contain trivalent M (for example, trivalent Fe) substantially.Just mean to have obtained " peridotites is single-phase " when having trivalent Fe when can not determine in the x-ray diffraction pattern at material.According to preferred aspect, can prepare the single-phase basic metal of above-mentioned peridotites, transition metal and phosphate compounds (being generally lithium tertiary iron phosphate compound etc.) efficiently.Not only can be from divalence source of iron material (for example FeO), and can be from ferric iron source material (Fe for example
2O
3) prepare iron lithium phosphate compound etc.
Can be used as by the various cationic storages/method of release by the electrode active material that makes in this disclosed method and can produce the electrode active material of the store battery of voltage.Can be comprised alkalimetal ion such as lithium ion, sodium ion, potassium ion, caesium example etc. by the positively charged ion of this active material storage/release; Alkaline-earth metal ions such as calcium ion, barium ion etc.; Magnesium ion; Aluminum ion; Silver ions; Zine ion; Ammonium ion such as TBuA ion, tetraethyl ammonium ion, tetramethyl ammonium, triethyl ammonium methyl ion, triethyl ammonium ion etc.; Imidazoles ion is imidazoles ion, ethyl-methyl imidazoles ion etc. for example; Pyridine ion; Hydrogen ion; The tetraenium ion; Tetramethyl- ion; Tetraphenyl ion, the triphenylsulfonium ion; Triethyl sulfonium cation etc.In the middle of these, preferred as alkali ion, and preferred lithium ion especially.
When being used in the anode of store battery by the electrode active material for preparing in this disclosed method, the active material that cationic carbonaceous material can be used as negative electrode maybe can be stored/be discharged to metal such as lithium, sodium, magnesium, aluminium etc. or its alloy.
Electrode with above-mentioned electrode active material can be by suitably as the electrode of different shape such as coin, cylindric, square etc. store battery.For example, electrode active material can be pressed the electrode that moulding becomes tabular grade.In addition, by above-mentioned electrode active material is adhered on the collector of being made up of electro-conductive material such as metal sheet etc., just can make tabular or sheet electrode.As required, except electrode active material of the present invention, this class electrode also can contain same a kind of two or multiple electrode with standard electrode active material in material.The representative example of this class material comprises electro-conductive material and tackiness agent.Carbonaceous material such as acetylene black (AB) etc. can be used as electro-conductive material.Organic polymer such as polyvinylidene difluoride (PVDF) (PVDF), polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer (PVDF-HFP) etc. can be used as tackiness agent.
For the nonaqueous electrolyte that is used for store battery, can use the ionogen that contains non-aqueous solvent and have the cationic compound that to store/to discharge by electrode active material (supporting electrolyte).
Non-proton (aprotonic) solvent with carbonate, ester, ether, nitryl, sulfone, lactone etc. can be used as the non-aqueous solvent that forms nonaqueous electrolyte, but is not limited to these.For example Texacar PC, ethylene carbonate, diethyl carbonate, methylcarbonate, ethylmethyl carbonate, 1,2-glycol dimethyl ether, 1,2-diethoxyethane, acetonitrile, propionitrile, tetrahydrofuran (THF), 2-methyltetrahydrofuran, diox, 1,3-dioxoran, Nitromethane 99Min., N, dinethylformamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, gamma-butyrolactone etc.Only can use and to use a kind of of the non-aqueous solvent that is selected from these, or two or more mixture.
In addition, for the supporting electrolyte that forms nonaqueous electrolyte, when using lithium-ions battery, can use one or both or multiple being selected to contain the cationic compound that can be stored by electrode active material/discharge, for example, lithium compound (lithium salts) is as LiPF
6, LiBF
4, LiN (CF
3SO
2)
2, LiCF
3SO
3, LiC
4F
9SO
3, LiC (CF
3SO
2)
3, LiClO
4Deng.
Below explanation is related to several embodiments of the present invention, still, the present invention never is subject to these embodiment.
(EXPERIMENTAL EXAMPLE 1)
This EXPERIMENTAL EXAMPLE is that to prepare main component be the electrode active material with ferrous phosphate compounds for Fe source material (FeO) that a use has a divalence Fe.
Be in molar ratio 1: 0.5: 1 with FeO, P
2O
5Mix with LiOH.In the Ar atmosphere, this mixture (feedstock composition) is heated to 1100 ℃ top temperature and is melted with the heat-up rate of 200 ℃/h, and with this temperature maintenance 15 minutes.Then, with the cooling rate of 200 ℃/h with the molten state slow cool to room temperature of this melt composition (melts) from 1100 ℃.By standard method resulting product is pulverized, obtained a kind of sample (hereinafter resulting product and milling product thereof being called " sample 1 "), and analyze through powder x-ray diffraction (XRD).Use is from the resulting X-ray diffraction equipment of Rigaku Corporation (model: Rigaku RINT2100HLR/PC) analyze.The result as shown in Figure 1.As can be seen from Figure 1, only observe x-ray diffraction pattern with olivine-type feature.Confirm thus, be crystal substantially by the sample 1 that this EXPERIMENTAL EXAMPLE obtained, and be peridotites (LiFePO
4) single-phase.
(EXPERIMENTAL EXAMPLE 2)
This EXPERIMENTAL EXAMPLE is that to prepare main component be the embodiment with electrode active material of ferrous phosphate compounds for Fe source material (FeO) that another use has a divalence Fe.
Be in molar ratio 1: 0.5: 0.5 with FeO, P
2O
5And Li
2CO
3Mix.Except with this mixture as feedstock composition and under 1100 ℃ of top temperatures, keeping 30 minutes, all the other prepare sample 2 by the method identical with EXPERIMENTAL EXAMPLE 1.By the method identical, sample 2 is carried out XRD measure with EXPERIMENTAL EXAMPLE 1.Resulting result as shown in Figure 2.As can be seen from Figure 2, only observe x-ray diffraction pattern, thereby confirmatory sample 2 is crystal substantially, and is peridotites (LiFePO with olivine-type feature
4) single-phase.Confirm that thus sample 2 is crystal substantially, and is peridotites (LiFePO
4) single-phase.
(EXPERIMENTAL EXAMPLE 3)
This EXPERIMENTAL EXAMPLE is that a use has trivalent Fe (Fe
2O
3) Fe source material to prepare main component be the embodiment with electrode active material of ferrous phosphate compounds.
Be in molar ratio 1: 1: 1 with Fe
2O
3, P
2O
5And Li
2CO
3Mix, and toward wherein sneaking into carbon dust (acetylene black is also referred to as " AB " hereinafter) as reductive agent.Toward the amount of wherein sneaking into AB is the Fe of per 100 mass parts of 2 mass parts
2O
3, P
2O
5And Li
2CO
3Gross weight.And, this mixture heating up to 1100 ℃ of top temperatures and make its fusing, and was kept under top temperature 30 minutes as EXPERIMENTAL EXAMPLE 1.Then, this melts (containing AB as reductive agent) is slowly cooled off from 1100 ℃ molten state, almost arrive room temperature with the cooling rate of 200 ℃/h.By standard method resulting product is pulverized, obtained sample 3,, sample 3 is carried out XRD detect by the method identical with EXPERIMENTAL EXAMPLE 1.Resulting result as shown in Figure 3.As can be seen from Figure 3, only observe x-ray diffraction pattern, thereby confirmatory sample 3 is crystal substantially, and is peridotites (LiFePO with olivine-type feature
4) single-phase.
(EXPERIMENTAL EXAMPLE 4)
This EXPERIMENTAL EXAMPLE is that another use has trivalent Fe (Fe
2O
3) Fe source material to prepare main component be the electrode active material with ferrous phosphate compounds.
Except not using AB, prepare feedstock composition by the method the same with EXPERIMENTAL EXAMPLE 3 as the reductive agent.Use this feedstock composition, and heat (200 ℃/h of heat-up rate, 1000 ℃ of top temperatures were held time 30 minutes) by the method identical with EXPERIMENTAL EXAMPLE 3, (200 ℃ of cooling rates/h) and pulverizing are to obtain sample 4 in cooling.By the method identical, sample 4 is carried out XRD detect with EXPERIMENTAL EXAMPLE 1.Resulting result as shown in Figure 4.As can be seen from Figure 4, the sample that method obtained 4 of the preparation parameter by this EXPERIMENTAL EXAMPLE contains trivalent Fe compound, and is not peridotites (LiFePO
4) single-phase.
(EXPERIMENTAL EXAMPLE 5)
This EXPERIMENTAL EXAMPLE is another embodiment, and wherein using the Fe source material with divalence Fe (FeO) to prepare main component is the electrode active material with ferrous phosphate compounds.
Be in molar ratio 1: 0.5: 1 with FeO, P
2O
5Mix with LiOH.In argon atmosphere, this mixture (feedstock composition) is heated to 1500 ℃ (top temperatures) with fusing with the heat-up rate of 200 ℃/h, and with this temperature maintenance 5 minutes.Then, with the cooling rate of 200 ℃/h this melts is cooled off almost to room temperature from 1500 ℃ molten state.By standard method resulting product is pulverized, obtained sample 5, and carry out powder x-ray diffraction (XRD) and detect.The result as shown in Figure 5.As can be seen from Figure 5, only observe x-ray diffraction pattern, and confirmatory sample 5 is crystal substantially, and is peridotites (LiFePO with olivine-type feature
4) single-phase.Therefore, even be raised to 1500 ℃ from 1100 ℃ when top temperature, also can obtain as experiment embodiment 1 by the single-phase sample of forming of peridotites.
(EXPERIMENTAL EXAMPLE 6)
This EXPERIMENTAL EXAMPLE is that another use has trivalent Fe
2O
3Fe source material to prepare main component be the embodiment with electrode active material of ferrous phosphate compounds.
Except not using AB, prepare feedstock composition by the method the same with EXPERIMENTAL EXAMPLE 3 as the reductive agent.Use this mixture (feedstock composition), and heat (200 ℃/h of heat-up rate, 1500 ℃ of top temperatures were held time 5 minutes) by the method identical with EXPERIMENTAL EXAMPLE 5, (200 ℃ of cooling rates/h) and pulverizing are to obtain sample 6 in slowly cooling.By the method identical, sample 6 is carried out XRD detect with EXPERIMENTAL EXAMPLE 1.Resulting result as shown in Figure 6.As can be seen from Figure 6, only observe x-ray diffraction pattern, and can determine that sample 6 is crystal substantially, and be peridotites (LiFePO with olivine-type feature
4) single-phase.Therefore, do not use reductive agent, by melt temperature (top temperature) is raised to 1500 ℃ from 1100 ℃, even when using Fe
2O
3As Fe source material, also can obtain by the single-phase sample of forming of peridotites.
(EXPERIMENTAL EXAMPLE 7)
This EXPERIMENTAL EXAMPLE is that another use has trivalent Fe
2O
3Fe source material to prepare main component be the electrode active material with ferric phosphate compounds.
Be in molar ratio 1: 1 with Fe
2O
3And P
2O
5Mix.Use this mixture (feedstock composition), and heat (200 ℃/h of heat-up rate, 1500 ℃ of top temperatures were held time 5 minutes) by the method identical with EXPERIMENTAL EXAMPLE 6, (200 ℃ of cooling rates/h) and pulverizing are to obtain sample 7 in cooling.By the method identical, sample 7 is carried out XRD detect with EXPERIMENTAL EXAMPLE 1.Resulting result as shown in Figure 7.As shown in Figure 7, only observe X-ray diagram, and can determine that sample 7 is crystal substantially, and be peridotites (LiPO with olivine-type feature
4) single-phase.
(property test of sample 1)
The sample 1 that uses EXPERIMENTAL EXAMPLE 1 to be obtained is made a test battery.
In other words, sample 1 is pulverized up to not feeling the degree of granular sensation at finger tip, preparation electrode active material (for convenience, hereinafter the product that crushes being also referred to as " sample 1 ").With the electrode active material of about 0.25g and about 0.089g as the acetylene black (AB) of electro-conductive material mix (mass ratio: about 70: 25).Come mixed electrods active material and AB with planetary ball mill.In this mixture (mixture of electrode active material and AB), add and mix the polytetrafluoroethylene (PTFE) of about 0.018g as tackiness agent (mass ratio of electrode active material: AB: PTFE: about 70: 25: 5).Become diameter to be about 1.0cm mixture compression moulding, thickness is about the discoid of 0.5mm, has just prepared test electrode.
With diameter is that 1.5mm and thickness are that 0.15 lithium paper tinsel is as counter electrode.Diameter is that 22mm and thickness are that the porous polyethylene plate of 0.02mm is used as dividing plate.In addition, use nonaqueous electrolyte, wherein LiPF
6Be dissolved in volume ratio and be in the mixed solvent of 1: 1 ethylene carbonate (EC) and diethyl carbonate (DEC), concentration is about 1 mol.These elements are incorporated in the stainless steel vessel, and as shown in Figure 19, thickness is 2mm, and diameter is that the coin battery (2032 type) of 32mm has just been carried out.In Figure 19, numerical markings 1 refers to positive pole (test electrode), and numerical markings 2 refers to negative pole (counter electrode), numerical markings 3 refers to dividing plate and ionogen (nonaqueous electrolyte), numerical markings 4 refers to packing ring, and numerical markings 5 refers to anodal container, and numerical markings 6 refers to negative cover.Wherein sample 1 is used as electrode active material, and adopts the above-mentioned electrode active material of planetary type ball-milling machining blended and AB and the above-mentioned battery made, is known as " battery 1-B " hereinafter.
In addition, prepare test electrode and make battery, but be to use stoning machine to replace planetary ball mill that electrode active material, AB and PTFE are mixed by the method the same with battery with above-mentioned test electrode.Wherein sample 1 is used as electrode active material, and stoning machine is used to mix the above-mentioned battery of above-mentioned electrode active material and AB, is known as " battery 1-S " hereinafter.
Above-mentioned battery 1-B that will prepare then and battery 1-S (i.e. completing from battery) placed about 12 hours, finished constant current charge/discharge test afterwards on these batteries.Test parameter is: voltage control is 4.5 to 2.5V (cell voltage), and current density is 0.2mA/cm
2Be displayed on the top of Fig. 8 by the resulting charge/discharge curve of the charge first time.The result shows, wherein planetary ball mill is used to performance (lithium ion rate of utilization) that blended battery 1-B (thick line among the figure) represents and is better than wherein that stoning machine is used to blended battery 1-S (fine rule among the figure).Therefore, have only the result of battery 1-B to be displayed on the bottom of Fig. 8 in the circulation in the second time.
Notice that the original charge capacity is because the loss of lithium a shade below the reason of loading capacity, this is owing to the volatilization of Li in the melting process.But this is not the loss in site, and the charging capacity that reduces corresponding to the loss of Li is circulating for the second time and after this is being resumed.
Finish the loop test of battery 1-B.In other words, (voltage control is 4.5 to 2.5V, and current density is 0.2mA/cm at above-mentioned test parameter
2) under battery 1-B is repeated charge, and measured each round-robin specific storage.The result who is obtained (cycle characteristics) is displayed among Fig. 9.
In addition, the loading capacity of battery 1-B is at 0.1mA/cm in circulation for the first time
2, 0.2mA/cm
2, 0.5mA/cm
2And 1.0mA/cm
2Discharge-rate down measure.The result who is obtained (multiplying power property) is displayed among Figure 10.
(property test of sample 2)
Except replacing sample 1 as the electrode active material with sample 2, all the other prepare test battery (being the mixing that planetary ball mill is used to electrode active material and AB) by the method identical with battery 1-B.This test battery is known as " battery 2-B " hereinafter.
By finishing constant current charge/discharge test and the loop test of battery 2-B with the same test parameter of above-mentioned test 1.The result who is obtained is presented at respectively among Figure 11 and Figure 12.In addition, the loading capacity of battery 2-B is at 0.1mA/cm in circulation for the first time
2, 0.2mA/cm
2, 0.5mA/cm
2And 1.0mA/cm
2Discharge-rate down measure.The result who is obtained is displayed among Figure 13.
(property test of sample 3)
Except replacing sample 1 as the electrode active material with sample 3, all the other prepare test battery (being the mixing that planetary ball mill is used to electrode active material and AB) by the method identical with battery 1-B.This test battery is known as " battery 3-B " hereinafter.
By finishing constant current charge/discharge test and the loop test of battery 3-B with the same test parameter of above-mentioned test 1.The result who is obtained is presented at respectively among Figure 14 and Figure 15.In addition, the loading capacity of battery 3-B is at 0.1mA/cm in circulation for the first time
2, 0.2mA/cm
2And 0.5mA/cm
2Discharge-rate down measure.The result who is obtained is displayed among Figure 16.
(property test of sample 5)
Except replacing sample 1 as the electrode active material with sample 5, all the other prepare test battery (being the mixing that stoning machine is used to electrode active material and AB) by the method identical with battery 1-S.This test battery is known as " battery 5-S " hereinafter.
By finishing constant current charge/discharge test and the loop test of battery 5-S with the same test parameter of above-mentioned test 1.The result who is obtained is presented at respectively among Figure 17 and Figure 18.
By these tests, can determine, by the above-mentioned all samples that EXPERIMENTAL EXAMPLE obtained 1,2,3 and 5, all show various useful property as lithium battery (normally lithium-ions battery) electrode active material.
At length illustrated preferred implementation of the present invention above.But this is a simple embodiment, can not limit the scope of Patent right requirement.The various modifications and the change of all respects that disclosed technology is illustrated above comprising in the scope of Patent right requirement.In addition, the technology essential factor of being narrated in this specification sheets or accompanying drawing demonstrates technology alone or various combinations and uses, and is not subjected to the restriction of disclosed combination in the claims when application.In addition, technology case illustrated in this specification sheets or accompanying drawing reaches many purposes simultaneously, reaches the application that promptly possesses skills of a kind of purpose in the middle of these.
Claims (12)
1. the preparation method of phosphate compounds, described phosphate compounds is by general formula A
xM (PO
4)
yExpression, 0≤x≤2 wherein, 0＜y≤2, A is one or both or multiplely is selected from alkali-metal element, and M is one or both or the multiple element that is selected from transition metal, and described method comprises: preparation is in the step of the composition of molten state, melt composition contains, when the x in the general formula greater than 0 the time, the source material of the A in the general formula and the source material of the M in the general formula and the source material of phosphorus; With composition slowly is cooled to solid-state step from molten state.
2. the process of claim 1 wherein that the step for preparing melt composition comprises the step of the composition for preparing molten state, melt composition contains, when the x in the general formula equals 0, and the source material of the M in the general formula and the source material of phosphorus.
3. the method for claim 1, the step that wherein prepares melt composition comprises, when the x in the general formula greater than 0 the time, will contain the solid material of the source material of A in the general formula, the solid material of source material that contains the M in the general formula and the solid material blended step of phosphorated source material; With with the mixture heating up of solid material step to molten state.
4. the method for claim 3, the method that wherein prepares melt composition comprise, when the x in the general formula equals 0, mixes the step of the solid material of the solid material of the source material that contains the M in the general formula and phosphorated source material.
5. claim 1 or 3 method, wherein to contain be A, M and the P of 1: 1: 1 atomic ratio to melt composition substantially.
6. claim 2 or 4 method, wherein to contain be the M and the P of 1: 1 atomic ratio to melt composition substantially.
7. any one method in the claim 1 to 6, wherein the source material of M contain with M be component and wherein in compound the valency of M be higher than the valent compound of M in the described general formula; And melt composition contains reductive agent.
8. any one method in the claim 1 to 7, wherein the phosphate compounds by described general formula representative is an olivine-type tertiary iron phosphate compound, the M in its formula of mainly is a ferrous iron.
9. the method for claim 8, wherein melt composition contains the Fe as the source material of M
2O
3And reductive agent.
10. claim 7 or 9 method, wherein carbon dust is used as reductive agent.
11. store battery, comprising: anode had by the phosphate compounds of an any method that is limited preparation in the claim 1 to 10;
Negative electrode with material of storage/release alkalimetal ion; And
Nonaqueous electrolyte or solid electrolyte.
12. the store battery of claim 11, wherein alkalimetal ion is a lithium ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004340979A JP2006155941A (en) | 2004-11-25 | 2004-11-25 | Method of manufacture for electrode active material |
| JP340979/2004 | 2004-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101065322A true CN101065322A (en) | 2007-10-31 |
Family
ID=35530821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800404644A Pending CN101065322A (en) | 2004-11-25 | 2005-10-31 | Method of producing electrode active material |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1812341A2 (en) |
| JP (1) | JP2006155941A (en) |
| KR (1) | KR20070086541A (en) |
| CN (1) | CN101065322A (en) |
| CA (1) | CA2583391A1 (en) |
| WO (1) | WO2006057146A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101964413A (en) * | 2010-10-13 | 2011-02-02 | 临沂杰能新能源材料有限公司 | Nanoscale lithium iron phosphate electrode material and preparation method thereof |
| CN102186770A (en) * | 2008-10-20 | 2011-09-14 | 古河电池株式会社 | Multi-element lithium phosphate compound particles having olivine structure, method for producing same, and lithium secondary battery using same in positive electrode material |
| CN102378738A (en) * | 2009-04-03 | 2012-03-14 | 旭硝子株式会社 | Process for production of lithium iron phosphate particles and process for production of secondary battery |
| CN102491303A (en) * | 2011-11-14 | 2012-06-13 | 日照华轩新能源有限公司 | Method for preparing lithium ion phosphate, cathode material of lithium ion battery |
| CN102668193A (en) * | 2009-11-16 | 2012-09-12 | 日本电气硝子株式会社 | Method for producing positive electrode material for lithium ion secondary battery |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5164246B2 (en) * | 2007-03-30 | 2013-03-21 | 国立大学法人九州大学 | Electrode active material and lithium secondary battery |
| JP2009146773A (en) * | 2007-12-14 | 2009-07-02 | Agc Seimi Chemical Co Ltd | Olivine type lithium iron phosphorus composite oxide and its manufacturing method |
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| TW201010944A (en) * | 2008-04-17 | 2010-03-16 | Basf Se | Process for the preparation of crystalline lithium-, iron-and phosphate-comprising materials |
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| TWI474970B (en) | 2008-12-29 | 2015-03-01 | Basf Se | Synthesis of lithium-metal-phosphates under hydrothermal conditions |
| EP2408712B1 (en) | 2009-03-17 | 2015-05-13 | Basf Se | Synthesis of lithium-iron-phosphates under hydrothermal conditions |
| CN102803133B (en) | 2009-06-24 | 2016-01-06 | 巴斯夫欧洲公司 | Preparation LiFePO 4the method of-carbon composite |
| KR101748406B1 (en) * | 2009-08-07 | 2017-06-16 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Manufacturing method for positive electrode active material |
| FR2978137A1 (en) * | 2011-07-21 | 2013-01-25 | Saint Gobain Ct Recherches | MELT PRODUCT BASED ON LITHIUM |
| KR101895902B1 (en) * | 2012-08-03 | 2018-09-07 | 삼성에스디아이 주식회사 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| JP5770239B2 (en) * | 2012-09-28 | 2015-08-26 | アマゾン電池株式会社 | Vanadium phosphate complex secondary battery |
| JP6639801B2 (en) * | 2015-04-28 | 2020-02-05 | 株式会社クオルテック | Metal phosphate complex secondary battery |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3484003B2 (en) * | 1995-11-07 | 2004-01-06 | 日本電信電話株式会社 | Non-aqueous electrolyte secondary battery |
| JP3523397B2 (en) * | 1995-11-07 | 2004-04-26 | 日本電信電話株式会社 | Non-aqueous electrolyte secondary battery |
| US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
| US6528033B1 (en) * | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
| US7001690B2 (en) * | 2000-01-18 | 2006-02-21 | Valence Technology, Inc. | Lithium-based active materials and preparation thereof |
| JP4769995B2 (en) * | 2000-03-06 | 2011-09-07 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte battery |
| JP4963330B2 (en) * | 2000-06-29 | 2012-06-27 | 株式会社豊田中央研究所 | Lithium iron composite oxide for positive electrode active material of lithium secondary battery, method for producing the same, and lithium secondary battery using the same |
| US7189475B2 (en) * | 2000-07-27 | 2007-03-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Lithium secondary battery |
| JP3988374B2 (en) * | 2000-10-06 | 2007-10-10 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| EP1553647B1 (en) * | 2002-10-18 | 2016-12-07 | Japan as represented by President of the University of Kyusyu | Method for preparing positive electrode material for secondary cell, and secondary cell |
| CA2791156C (en) * | 2003-12-23 | 2015-12-15 | Universite De Montreal | Process for preparing electroactive insertion compounds and electrode materials obtained therefrom |
-
2004
- 2004-11-25 JP JP2004340979A patent/JP2006155941A/en not_active Withdrawn
-
2005
- 2005-10-31 CA CA002583391A patent/CA2583391A1/en not_active Abandoned
- 2005-10-31 CN CNA2005800404644A patent/CN101065322A/en active Pending
- 2005-10-31 KR KR1020077014188A patent/KR20070086541A/en not_active Application Discontinuation
- 2005-10-31 EP EP05800528A patent/EP1812341A2/en not_active Withdrawn
- 2005-10-31 WO PCT/JP2005/020324 patent/WO2006057146A2/en not_active Application Discontinuation
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| US8841023B2 (en) | 2008-10-20 | 2014-09-23 | The Furukawa Battery Co., Ltd. | Multi-component-system lithium phosphate compound particle having an olivine structure and lithium secondary battery employing the lithium phosphate compound particle as a positive electrode material |
| US9337488B2 (en) | 2008-10-20 | 2016-05-10 | The Furukawa Battery Co., Ltd. | Method of manufacturing a multicomponent system lithium phosphate compound particle having an olivine structure |
| CN102378738A (en) * | 2009-04-03 | 2012-03-14 | 旭硝子株式会社 | Process for production of lithium iron phosphate particles and process for production of secondary battery |
| CN102668193A (en) * | 2009-11-16 | 2012-09-12 | 日本电气硝子株式会社 | Method for producing positive electrode material for lithium ion secondary battery |
| CN101964413A (en) * | 2010-10-13 | 2011-02-02 | 临沂杰能新能源材料有限公司 | Nanoscale lithium iron phosphate electrode material and preparation method thereof |
| CN101964413B (en) * | 2010-10-13 | 2013-05-15 | 临沂杰能新能源材料有限公司 | Nanoscale lithium iron phosphate electrode material and preparation method thereof |
| CN102491303A (en) * | 2011-11-14 | 2012-06-13 | 日照华轩新能源有限公司 | Method for preparing lithium ion phosphate, cathode material of lithium ion battery |
| CN105152154A (en) * | 2015-07-09 | 2015-12-16 | 上海电力学院 | Olivine type NaFePO4 sodium ion battery positive electrode material preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006057146A2 (en) | 2006-06-01 |
| KR20070086541A (en) | 2007-08-27 |
| CA2583391A1 (en) | 2006-06-01 |
| JP2006155941A (en) | 2006-06-15 |
| EP1812341A2 (en) | 2007-08-01 |
| WO2006057146A3 (en) | 2007-03-08 |
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