CN100448071C - Lithium battery positive electrode material and preparation method thereof - Google Patents
Lithium battery positive electrode material and preparation method thereof Download PDFInfo
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- CN100448071C CN100448071C CNB031139345A CN03113934A CN100448071C CN 100448071 C CN100448071 C CN 100448071C CN B031139345 A CNB031139345 A CN B031139345A CN 03113934 A CN03113934 A CN 03113934A CN 100448071 C CN100448071 C CN 100448071C
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- lithium
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- iron phosphate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 title description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000013078 crystal Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002019 doping agent Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 229910010710 LiFePO Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 51
- 239000011777 magnesium Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- JVLRGEATDIWSHH-UHFFFAOYSA-K lithium;magnesium;iron(2+);phosphate Chemical compound [Li+].[Mg+2].[Fe+2].[O-]P([O-])([O-])=O JVLRGEATDIWSHH-UHFFFAOYSA-K 0.000 claims description 16
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 12
- 229940062993 ferrous oxalate Drugs 0.000 claims description 11
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- QWWVBNODQCWBAZ-WHFBIAKZSA-N (2r)-2-amino-3-[(2r)-2-carboxy-2-(methylamino)ethyl]sulfanylpropanoic acid Chemical compound CN[C@H](C(O)=O)CSC[C@H](N)C(O)=O QWWVBNODQCWBAZ-WHFBIAKZSA-N 0.000 claims description 6
- 229910016876 Fe(NH4)2(SO4)2 Inorganic materials 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- HDCVHVAWSPSEET-UHFFFAOYSA-K lithium;magnesium;manganese(2+);phosphate Chemical compound [Li+].[Mg+2].[Mn+2].[O-]P([O-])([O-])=O HDCVHVAWSPSEET-UHFFFAOYSA-K 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001722 carbon compounds Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 238000004544 sputter deposition Methods 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 229910016953 Fe0.5Mn0.5PO4 Inorganic materials 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940029985 mineral supplement Drugs 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a positive electrode material for a lithium battery, which is represented by a chemical general formula LixM 1-xFePO 4, wherein M is selected from Mg < 2+ >, Ca < 2+ >, Sr < 2+ >, Ti < 3+ >, Al < 3+ >, B < 3+ >, Si < 4+ >, Ge < 4+ >, P < 5+ >. The material is prepared by adding a conductive dopant, and heating to 500-900 ℃ to react for 10 hours by adopting metal oxide, carbonate, sulfide, phosphate, fluoride and unsaturated lithium iron phosphate crystal. The lithium iron phosphate crystal with high conductivity can be prepared by a non-stoichiometric method, and the material of the lithium iron phosphate crystal is represented by a chemical general formula LiFePO 4-y. For preparing the anode material of the lithium battery by the supercharged replacement ions, the chemical general formula is Li < x > M < 1-x > Fe < z > M '1-z > PO 4, M' is selected from Ti < 3+ >, V < 3+ >, Co < 3+ >, Ni < 3+ >, Mn < 3+ >, Cr < 3+ >, Cu < 3+ > and Mo < 3+ >, solid powder of magnesium-doped lithium iron manganese phosphate LixMg 1-xFezMn 1-zPO 4 is prepared through solid phase reaction. The cathode material with the nano structure has a chemical general formula of LixFePO 4-y, and is prepared by vacuum sputtering deposition, the conductivity of the material can reach 10< -2 > S/cm, and the actual discharge capacity can reach 240 mAh/g. The novel anode material has the characteristics of low price, high energy and safety, and is not only suitable for medium and small polymer, colloid and liquid lithium ion batteries, but also particularly suitable for high-power batteries.
Description
Technical field
The present invention relates to a kind of lithium ion battery positive electrode material and preparation method, be used for polymer, colloid and liquid lithium ion battery, be particularly useful for the high-power drive pond.
Background technology
At present, positive electrode commonly used in lithium battery is three kinds of embedding lithium oxides, and they are cobalt acid lithium (LiCoO
2), lithium nickel cobalt dioxide (LiNi
xCo
1-xO
2) and LiMn2O4 (LiMn
2O
4).LiCoO
2And LiNi
xCo
1-xO
2Be the oxide of hexagonal layered rock salt structure, lithium ion Li moves in the octahedral layer gap that O-Co-O constitutes, and has higher electric conductivity and lithium ion and takes off embedding/embedding invertibity.LiMn
2O
4Be the oxide of spinelle three-dimensional structure, lithium ion Li moves in the octahedra stereo channel that O-Mn-O constitutes, and also has higher electric conductivity and lithium ion and takes off embedding/embedding invertibity.They all are a large amount of positive electrodes that use in the present lithium ion battery industry.But metallic cobalt is one of less element of resource on the earth, and these two kinds of oxides over-charging of battery and when overheated can with electrolyte generation vigorous reaction, emit a large amount of heats and cause battery to catch fire even explode.Therefore, cobalt acid lithium (LiCoO
2), lithium nickel cobalt dioxide (LiNi
xCo
1-xO
2) manufacturing cost all very high, and security performance is relatively poor.LiMn2O4 (LiMn
2O
4Though) comparatively cheap and safety, but not only discharge capacity is less for it, and the cycle life of (for example more than 55 ℃) is relatively poor under hot conditions, and although mix and chemical surface treatment through composition, its cycle life still can't satisfy the requirement of actual use.Therefore, lithium battery industry, particularly high-power dynamic lithium battery needs that a kind of cost is lower, capacity more greatly and safer positive electrode.
In order to solve the problem that exists in the above-mentioned anode material of lithium battery, (A.K.Padhi such as texas,U.S college professor J.B.Goodenough, K.S.Najundaswamy, C.Masqueslier, S.Okada and J.B.Goodenough, J.Electrochem.Soc.144,1609-1613 (1997)) on U.S.'s electrochemistry magazine, delivered academic article in 1997, a kind of new lithium intercalation compound is disclosed: lithium iron phosphate LiFePO
4Polycrystal.Lithium ion in this crystal can be at FeO
6Octahedron and PO
4Move freely in the tetrahedral structure, have lithium ion and take off embedding/embedding invertibity.When 1 mole lithium ion takes off embedding when coming out, lithium iron phosphate LiFePO from structure
4Multicrystal theoretical discharge capacity can reach 170mAh/g.Because lithium, iron and P elements all are the abundant elements of reserves on the earth, therefore, lithium iron phosphate LiFePO
4Multicrystal production cost is very low.This article prediction is because lithium iron phosphate LiFePO
4Polycrystal has the characteristic of low price, high energy and safety, and it may have broad application prospects in lithium battery industry.
The positive electrode lithium iron phosphate LiFePO that J.B.Goodenough mentions in academic article
4Though have broad application prospects, because its room-temperature conductivity is very low, have only 10
-9S/cm.At regular picture electric current (for example 10
-1MA/cm
2) under the condition, lithium iron phosphate LiFePO
4The actual discharge capacity is 10% of theoretical discharge capacity 170mAh/g.Therefore, lithium iron phosphate LiFePO
4Can not directly in lithium ion battery, use.In order to improve lithium iron phosphate LiFePO
4Conductivity has academic article report (Sung-YoonChung, Jason T.Bloking and Yet-Ming Chiang, Nature, October 123-128 (2002)) abroad in the recent period, adds trace mineral supplement in its structure, for example Mg, Ti, Nb and Zr.Add after these trace elements lithium iron phosphate LiFePO
4The conductivity at room temperature rate be enhanced.But the adding method of the trace element of mentioning in this article is comparatively complicated, and micro-price is more expensive, the incompatibility large-scale industrial production.In addition, lithium iron phosphate LiFePO
4The conductivity at room temperature rate also have the space of further improving; Lithium iron phosphate LiFePO
4Discharge voltage all lower than three kinds of embedding lithium oxides commonly used in the present lithium battery, thereby influenced the energy density of this material.
Summary of the invention
Technical problem to be solved by this invention is further to increase lithium iron phosphate LiFePO
4Conductivity, and improve discharge voltage and improve discharge capacity.For this reason, this patent has proposed a kind of new anode material of lithium battery and preparation method thereof, substitutes the cobalt acid lithium (LiCoO that generally uses at present
2), lithium nickel cobalt dioxide (LiNi
xCo
1-xO
2) and LiMn2O4 (LiMn
2O
4).The lithium battery that this new material not only can be applied to low capacity is mobile phone, personal digital assistant and laptop computer for example, and more valuable in the big capacity more than 10 ampere-hours, high-power drive pond, because electrokinetic cell is higher to the requirement of cost and security performance.Three kinds of embedding lithium oxide costs that generally use in lithium battery industry are higher at present, safe performance indexes is relatively poor, it is overheated that battery overcharges easily, and the danger of blast on fire is arranged in actual applications, therefore can't compete mutually with existing fuel-engined vehicle power product in market.
In order to realize the purpose of foregoing invention, the technical solution used in the present invention is: use the novel conductive additive to improve lithium iron phosphate LiFePO
4Conductivity, utilize the method for non-stoichiometric compound to prepare the lithium iron phosphate polycrystal of high conductivity, take chemical solid solution method to improve the discharge voltage of lithium iron phosphate series material and use method for making Nano to improve the discharge capacity of lithium iron phosphate series material.
Technology contents of the present invention has four aspects:
First aspect is by at lithium iron phosphate LiFePO
4Add novel dopant in the crystal and improve its conductance.This material is expressed as Li with chemical general formula
xM
1-xFePO
4, x=0.95～0.999.
The present invention proposes new conductiving doping agent and their working mechanism.The conductiving doping agent can be selected in following multiple cation, and they are bivalent positive ion Mg
2+, Ca
2+, Sr
2+, trivalent cation Ti
3+, Al
3+, B
3+And multivalence cation Si
4+, Ge
4+, P
5+Or the like.Lithium iron phosphate LiFePO
4Crystal is an olivine structural, by polybasic anionic PO
4Tetrahedron constitutes the foundation stone of this crystal structure.The Fe ion is by PO
4Tetrahedron is around the stable phase FePO that forms this crystal structure
4The Li ion can be at FePO
4In freely insert and take off embedding.The trace high price cation that adds partly replaces the monovalence lithium ion and is in LiO as conductive additive
6Octahedral lattice position when doped crystal promptly forms n-N-type semiconductor N or p-N-type semiconductor N through structural adjustment after keeping the electricity price balance, makes lithium iron phosphate LiFePO
4Charge carrier in the crystal (electronics or hole) concentration increases greatly, thereby becomes semiconductor by insulator.Doping lithium iron phosphate Li
xM
1-xFePO
4Conductivity is than the lithium iron phosphate LiFePO that do not mix
4High 1,000,000 times, can under big current condition, discharge and recharge, its actual discharge capacity can reach 95% of theoretical capacity, that is to say 160mAh.Compare doping lithium iron phosphate Li with the actual discharge capacity 140mAh of cobalt acid lithium
xM
1-xFePO
4Discharge capacity surpass cobalt acid lithium 14%, wherein the nominal price ion of M for mixing.
The doping lithium iron phosphate Li that the present invention relates to
xM
1-xFePO
4Preparation technology's method can in following three kinds of methods, select according to different composition of raw materials.
(1) solid reaction process
After lithium nitrate, ferrous oxalate, ammonium di-hydrogen phosphate and conductiving doping agent mixed by proper proportion, put into the stainless steel ball grinding machine and mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible under inert gases such as nitrogen, prior to heating under 200～400 ℃ of temperature 2 hours, the gas componant in the powder is discharged, and then be warmed up to 500-900 ℃ of reaction 10 hours, cool to room temperature can use after grinding.For example conduction is mixed agent and is selected magnesium nitrate for use, obtains to mix magnesium lithium iron phosphate Li at last
xM
1-xFePO
4Pressed powder.
(2) liquid-solid phase reaction method
Amorphous state FePO
4Be by methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O and phosphorus hydracid ammonia NH
4H
2PO
4Carrying out reactant aqueous solution in oxidizing atmosphere is prepared from.The process lithium ion is at semi-finished product FePO
4In chemical diffusion after and form the Li of unsaturated state
xFePO
4Metal oxide, carbonate, sulfide, phosphate and fluoride are adopted in the conductiving doping agent, the lithium iron phosphate crystal Li of it and unsaturated state
xFePO
4Form Li by the solid state heat chemical reaction
xM
1-xFePO
4, M is Mg
2+, Ca
2+, Sr
2+, Ti
3+, Al
3+, B
3+, Si
4+, Ge
4+, P
5+In any one; Promptly be warmed up to 500-900 ℃ of reaction 10 hours, obtain to mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4Pressed powder.Cool to room temperature cleans residual reactant through water, vacuumize and grind after can use.
(3) thermal diffusion ion-exchange
The first step after lithium nitrate, ferrous oxalate and ammonium di-hydrogen phosphate mixed by proper proportion, is put into the stainless steel ball grinding machine and was mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible under inert gases such as nitrogen, prior to heating under the 200-400 ℃ of temperature 2 hours, gas componant in the powder is discharged, and then be warmed up to 600-900 ℃ of reaction 10 hours, obtain unsaturation lithium iron phosphate Li
xFePO
4Polycrystal powder, behind the cool to room temperature, standby through grinding.
Second step is the unsaturation lithium iron phosphate Li that obtains by first step method
xFePO
4Polycrystal powder and the material powders such as carbon compound, nitrate, sulfate or phosphate of conductiving doping agent in 2: 1 ratios grind mix after, use the oil pressure forcing press to be pressed into thin slice, thin slice is put into rustless steel container, be warmed up to 500 ℃ then, and under this temperature, kept 5 hours, because unsaturation lithium iron phosphate Li
xFePO
4Polycrystal powder particle and magnesium nitrate polycrystal powder particle quilt are closely compacted together, and at unsaturation lithium iron phosphate Li
xFePO
4There is the lithium ion room to exist in the crystal, therefore the magnesium ion thermal diffusion reaction takes place, make unsaturation lithium iron phosphate Li
xFePO
4Lithium ion room in the crystal is replaced by magnesium ion, mixes magnesium lithium iron phosphate Li and generate
xM
1-xFePO
4Pressed powder.After ions diffusion reaction is finished, cool to room temperature, the product pressed powder behind the water cleaning reaction washes wherein magnesium nitrate.After vacuumize, mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4Pressed powder can use.。
The conductiving doping agent that the present invention relates to and their concentration ranges in the lithium iron phosphate crystal structure are listed in the table 1.
Table 1 lithium iron phosphate crystal doping ion M is at Li
xM
1-xFePO
4In concentration range
| Dopant ion M | Mg 2+ | Ca 2+ | Sr 2+ | Ti 3+ | Al 3+ | Si 4+ | Ge 4+ | P 5+ |
| Doping content scope 1-x (%) | 0.1-5.0 | 0.1-4.2 | 0.1-3.1 | 0.1-2.4 | 0.1-2.6 | 0.1-1.9 | 0.1-1.8 | 0.1-0.9 |
Second aspect, preparation non-chemical measured lithium iron phosphate LiFePO
4-yPolycrystal improves its conductance.
According to lithium iron phosphate LiFePO
4The architectural characteristic of olivine crystal is analyzed, and the physical insulation of material is because the stoichiometry and the structural intergrity of its crystal structure cause.If at lithium iron phosphate LiFePO
4Introduce fault of construction in the olivine crystal, for example the oxygen room that is to say and make nonstoichiometric composition artificially in polycrystalline compounds, destroys its structural intergrity, then can improve its conductive characteristic widely.Prepare non-chemical measured lithium iron phosphate LiFePO by chemical method
4-yPolycrystal not only can increase stable phase FePO
4The carrier concentration that body is interior mutually, and can increase the polycrystal surface activity, the both can improve conductivity of electrolyte materials widely.
The non-chemical measured lithium iron phosphate LiFePO that the present invention proposes
4-yMulticrystal preparation technology's method is a sol-gal process, and its concrete steps are described below:
The first step, with ferrous oxalate, ammonium di-hydrogen phosphate and carbon gel by the proper proportion scale good after, under agitation successively join in the ethanol formation emulsion.
Second step under agitation was dissolved into lithium hydroxide in the deionized water, formed limpid solution.
The 3rd step, above-mentioned two kinds of liquid are under agitation mixed, form sol solutions, transfer to then in the aluminium oxide ceramics crucible, in Sealing furnace, under 150 ℃ of temperature, heated 2 hours, then, 10
-2Under the torr low vacuum, slowly be heated under 500 ℃ of temperature and kept 5 hours, the partial oxygen element generates CO and CO with the carbon gel reaction under vacuum heating conditions
2Discharge, under atmospheric conditions, be warmed up to 700 ℃ and kept 5 hours, product is removed the residual hydrogen lithia after cleaning through water, after non-chemical measured lithium iron phosphate LiFePO is made in vacuumize
4-yMulticrystal pressed powder.
The non-chemical measured lithium iron phosphate LiFePO that the present invention proposes
4-yThe quantitative range in oxygen room is y=0.01-1.50 in the polycrystal.
The 3rd aspect carried out active ion and replaced the discharge operating voltage that improves material in crystalline framework.
Lithium iron phosphate LiFePO
4Discharge voltage plateau have only 3.4V, than the discharge voltage plateau 3.7V low 8% of cobalt acid lithium.The present invention is at doping lithium iron phosphate Li
xM
1-xFePO
4Carrying out active ion in the crystalline framework replaces and improves its discharge voltage.Because energy density is that discharge capacity multiply by discharge voltage, therefore, increase the energy density that discharge voltage can improve battery effectively.In the octahedra lattice of iron ion, add other active ions, for example most of transition metal ions Ti
3+, V
3+, Co
3+, Ni
3+, Mn
3+, Cr
3+, Cu
3+And Mo
3+Or the like have the function that improves discharge voltage, can be with doping lithium iron phosphate Li
xM
1-xFePO
4Discharge voltage bring up to 3.9V by 3.4V, the phosphatic energy density of boosting type elements doped lithium iron increases widely because of the raising of its discharge voltage.Ion is replaced in the supercharging that the present invention relates to and they are at Li
xM
1-xFePO
4Concentration range in the structure is listed in the table 2.
Table 2 supercharging displacement ion M ' is at elements doped lithium iron phosphate crystal Li
xM
1-xFe
zM '
1-zPO
4In concentration range
| Supercharging displacement ion M ' | Ti 3+ | V 3+ | Co 3+ | Ni 3+ | Mn 3+ | Cr 3+ | Cu 3+ | Mo 3+ |
| Displacement ion concentration scope 1-z (%) | 1-50 | 1-80 | 1-45 | 1-45 | 1-49 | 1-35 | 1-60 | 1-60 |
Can prepare boosting type doping lithium iron phosphate with following two kinds of processes according to different composition of raw materials:
(1) solid reaction process:
The first step: after lithium nitrate, ferrous oxalate, ammonium di-hydrogen phosphate and conductiving doping agent mixed by proper proportion, put into the stainless steel ball grinding machine and mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible under inert gases such as nitrogen, prior to heating under the 200-400 ℃ of temperature 2 hours, the gas componant in the powder is discharged, and then be warmed up to 500-900 ℃ of reaction 10 hours, cool to room temperature, standby after grinding.For example, magnesium nitrate is adopted in the conductiving doping agent, then obtains to mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4Pressed powder.
Second goes on foot: after lithium nitrate, the inferior manganese of oxalic acid, ammonium di-hydrogen phosphate and conductiving doping agent are mixed by proper proportion, put into the stainless steel ball grinding machine and mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible under inert gases such as nitrogen, prior to heating under the 200-400 ℃ of temperature 2 hours, the gas componant in the powder is discharged, and then be warmed up to 600-1000 ℃ of reaction 10 hours, cool to room temperature, standby after grinding; For example, conduction is mixed agent and is selected magnesium nitrate for use, then can obtain to mix magnesium lithium manganese phosphate Li
xMg
1-xMnPO
4Pressed powder.The 3rd step: mixing magnesium lithium iron phosphate Li by first step acquisition
xMg
1-xEPO
4Pressed powder and mix magnesium lithium manganese phosphate Li by the acquisition that second step obtained
xMg
1-xMnPO
4Pressed powder mix by proper proportion after, put into the stainless steel ball grinding machine and mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible under inert gases such as nitrogen, and heating can obtain to mix magnesium ithium iron manganese phosphate Li in 5 hours under 600-1000 ℃ of temperature
xMg
1-xFe
zMn
1-zPO
4Pressed powder, cool to room temperature can use after grinding.
(2) sol-gal process:
The first step, with lithium carbonate, ferrous oxalate and ammonium di-hydrogen phosphate by the proper proportion scale good after, under agitation the priority join in the ethanol, form limpid solution.
Second step, with the inferior manganese of lithium carbonate, oxalic acid and ammonium di-hydrogen phosphate by the proper proportion scale good after, under agitation priority joins in the ethanol, forms limpid solution.
The 3rd step after above-mentioned two kinds of solution mixed on demand, under agitation added carbon gel and conductiving doping agent, formed emulsion.
In the 4th step, emulsion is transferred in the aluminium oxide ceramics crucible 10
-1Under the torr low vacuum,, the solvent composition in the raw material is discharged, and then be warmed up to 500-900 ℃ of reaction 10 hours under sealing condition, obtain elements doped lithium ferrimanganic phosphate Li prior to heating under 100 ℃ of temperature 1 hour
xM
1-xFe
zMn
1-zPO
4Polycrystal powder.Behind the cool to room temperature, after grinding, can use.
The 4th aspect, the preparation nano structural material improves lithium iron phosphate LiFePO
4The actual discharge capacity:
Lithium iron phosphate LiFePO
4Theoretical discharge capacity be 170mAh/g, this discharge capacity also has the leeway of further improving.The present invention reaches 240mAh/g by making the method for doping lithium iron phosphate polycrystal nanometer above its original theoretical discharge capacity.
Elements doped lithium iron processes for producing phosphates with nanostructure can be realized with following two kinds of processes:
(1) vacuum sputtering deposition (PVD)
With lithium iron phosphate LiFePO
4Potsherd sticks on the metal target surface with the silver slurry, and a flake aluminum is placed on LiFePO
4About 6 centimeters in target surface below are as substrate.This aluminium flake passes through pickling processes in advance, and surface oxide layer is disposed.When the vacuum degree of vacuum chamber reaches 10
-3Behind the torr, feed argon/nitrogen mixture gas, and aluminium substrate is heated to 150 ℃.Under the vacuum sputtering energy, a kind of polycrystal film of nanostructure is deposited on the aluminium flake surface, the about 30nm of crystal grain average-size.But, since the effect of vacuum sputtering, target material lithium iron phosphate LiFePO
4In light element, for example Li and O can have trace loss in sputter deposition process, thereby make the chemical composition of polycrystal film depart from target material lithium iron phosphate LiFePO
4, and formed non-metering compound L i
xFePO
4-yNanostructure.At this non-stoichiometric compound Li
xFePO
4-yThere are a large amount of defectives (for example oxygen vacancies) to exist in the polycrystal film, therefore, charge carrier dense, the conductivity of nanostructure polycrystal film can reach 10
-2S/cm.In addition, with lithium iron phosphate LiFePO
4The architectural characteristic difference, the nanostructure of polycrystal film makes Li
xFePO
4-yMany activation points have been produced to the core place by superficial layer, these activation point and LiO
6Octahedral lattice position equally has makes the Li ion embed and take off the function of embedding.Use Li
xFePO
4-yThe half-cell of forming as negative electrode as positive electrode and lithium sheet metal, through after several charge and discharge cycles, nanostructure polycrystal film Li
xFePO
4-yThe actual discharge capacity surpass its theoretical discharge capacity and reach 240mAh/g.
(2) sol-gal process:
The first step, with ferrous oxalate, ammonium di-hydrogen phosphate and carbon gel by the proper proportion scale good after, under agitation successively join in the ethanol formation coagulant liquid;
Second step, with lithium carbonate and conductiving doping agent (for example magnesium nitrate) by the proper proportion scale good after, under agitation priority joins in the ethanol, forms limpid solution;
The 3rd step, above-mentioned two kinds of solution ratio is on demand under agitation mixed, form emulsion;
In the 4th step, emulsion is transferred in the aluminium oxide ceramics crucible 10
-1Under the torr low vacuum,, obtain elements doped lithium ferrimanganic phosphate Li with nanostructure prior to heating under 100 ℃ of temperature 1 hour
xMg
1-xFePO
4Polycrystal powder; Behind the cool to room temperature, after grinding, can use.
The beneficial effect that the present invention produces is:
(1) agent improves lithium iron phosphate crystal Li as conductiving doping to have used less and the nominal price ion that polarizability is higher of atomic weight
xM
1-xFePO
4Conductance, the higher nominal price ion of these new polarizabilities is M=Mg
2+, Ca
2+, Sr
2+, Ti
3+, Al
3+, B
3+, Si
4+, Ge
4+, P
5+They are to improving lithium iron phosphate crystal Li
xM
1-xFePO
4Conductivity obviously effect is arranged more.
The conductiving doping agent joins lithium iron phosphate crystal Li
xM
1-xFePO
4List in the table 3 for the part measurement result of room temperature (25 ℃) conductivity afterwards, their doping is 0.1-4%.
Lithium iron phosphate crystal Li under the table 325 ℃ condition
xM
1-xFePO
4Conductivity
| Dopant ion M | Do not mix | Mg 2+ | Ca 2+ | Ti 3+ | Al 3+ | Si 4+ | Ge 4+ | P 5+ |
| Dopant ion concentration 1-x (%) | 0 | 1.6 | 1.2 | 0.8 | 0.9 | 0.5 | 0.6 | 0.4 |
| Conductivity (S/cm) | 3·10 -9 | 6·10 -2 | 2·10 -3 | 4·10 -2 | 1·10 -2 | 3·10 -3 | 1·10 -3 | 2·10 -3 |
As seen from the above table, behind the micro-multivalence cation that mixed, lithium iron phosphate crystal Li
xM
1-xFePO
4Room-temperature conductivity improved 10
6Doubly.
(2) the present invention proposes and use nonstoichiometric composition LiFePO
4-y(y=0.01-1.50) improve lithium iron phosphate crystal conduction rate with relevant preparation technology's method, compare with the method that adds the conductiving doping agent at the lithium iron phosphate crystal, the non-stoichiometry method is to improving the conductivity of lithium iron phosphate crystal, more simple and effect remarkable (seeing Table 4).
Table 4 nonstoichiometric composition LiFePO
4-yConductivity
| Oxygen vacancy concentration y | 0.0 | 0.1 | 0.3 | 0.6 | 0.8 | 1.1 |
| Conductivity (S/cm) | 3·10 -9 | 1·10 -5 | 1·10 -3 | 2·10 -3 | 7·10 -3 | 2·10 -2 |
(3) the present invention proposes the notion of supercharging additive, and change Li with the method for ion exchange
xM
1-xFe
yM '
1-yPO
4Thereby chemical potential energy reaches the purpose that improves the material discharging operating voltage in the crystal structure.Boosting type doping lithium iron phosphate Li
xM
1-xFe
yM '
1-yPO
4Multicrystal discharge operating voltage is than lithium iron phosphate LiFePO
4Multicrystal discharge operating voltage is high by 15%.
(4) the present invention proposes to prepare nano structural material and improves lithium iron phosphate LiFePO
4Discharge capacity, novel nano structural material Li
xFePO
4-yAnd Li
xM
1-xFePO
4Actual discharge Capacity Ratio lithium iron phosphate crystal LiFePO
4Improve 40%.
(5) the used raw material of preparation anode material of lithium battery of the present invention's proposition has rich in natural resources at home, and preparation technology's flow process is reasonable, and production cost is lower.The a large amount of uses of this novel anode material in lithium battery industry will be reversed the outlet of China lithium battery industrial products and the situation of raw material dependence on import, for various high-tech electronics communication apparatus and electric automobile provide more safe and reliable novel energy.
Description of drawings
Fig. 1 is that embodiment 3 is at Li
xMg
1-xFePO
4Add Mn in (1-x ≈ 0.02) crystal structure as the discharge voltage variation diagram before and after the supercharging additive.Dotted line is for mixing magnesium lithium iron phosphate Li
xMg
1-xFePO
4The discharge voltage variation diagram, solid line is for mixing magnesium lithium iron phosphate Li
xMg
1-xFe
0.5Mn
0.5PO
4The discharge voltage variation diagram.
Concrete execution mode
Embodiment 1: the preparation high conductivity mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4The polycrystalline pressed powder
The first step is with 356 gram methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O and 115 gram phosphorus hydracid ammonia NH
4H
2PO
4In stirring, be dissolved in the 2000 gram deionized waters.Aerating oxygen in the aqueous solution, and be warmed up to 95 ℃ of temperature maintenances 10 hours.In the oxidizing atmosphere and the aqueous solution, methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O and phosphorus hydracid ammonia NH
4H
2PO
4React and the generation sediment amorphous phase FePO
4
Second step is at above-mentioned semi-finished product FePO
4Add 24 gram lithium hydroxides in the aqueous solution, under 95 ℃ of temperature, kept 3 hours.After aqueous chemical diffusion and the Li of formation unsaturated state
xFePO
4Product is removed residual reactant after cleaning through water, after unsaturated state lithium iron phosphate Li is made in vacuumize
xFePO
4The amorphous solid powder.
The 3rd step, 150 gram lithium iron phosphate Li
xFePO
4Amorphous solid powder and 100 gram magnesium chlorides through grinding evenly mixes after, be pressed into the thin slice of 3 millimeters of diameter 20 millimeters thick with hydraulic press, be warmed up under 500 ℃ of temperature and kept 5 hours, be warmed up under 700 ℃ of temperature maintenance again 5 hours.Lithium iron phosphate Li
xFePO
4The pressed powder crystallization is by the noncrystal polycrystal that changes into; Meanwhile, under the effect of thermal diffusion, magnesium ion enters into lithium iron phosphate Li
xFePO
4In the crystal structure, form and mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4(1-x ≈ 0.02) polycrystalline pressed powder.Behind the cool to room temperature, product is removed residual reactant after cleaning through water, after vacuumize can use.
Mix magnesium lithium iron phosphate Li with what above method obtained
xMg
1-xFePO
4(x ≈ 0.02) polycrystalline pressed powder is pressed into the disk of 0.5 millimeter of diameter 12 millimeters thick with hydraulic press, surface vacuum gold evaporation film, and the room-temperature conductivity of using four-point probe method to measure is 2.5 * 10
-3S/cm.
Embodiment 2: the non-chemical measured lithium iron phosphate LiFePO of preparation high conductivity
4-yThe polycrystalline pressed powder
The first step is with 174 gram ferric acetate (CH
3COO)
2Fe, 115 gram phosphorus hydracid ammonia NH
4H
2PO
4With 20 gram carbon gels, under agitation successively join in the 1000 gram ethanol, form the colloidal sol emulsion.
Second step is with 66 gram lithium acetate CH
3COOLi under agitation is dissolved in the above-mentioned colloidal sol emulsion.
The 3rd step, sol solutions is transferred in the aluminium oxide ceramics crucible, in Sealing furnace, under 150 ℃ of temperature, heated 2 hours.Then, 10
-2Under the torr low vacuum, slowly be heated under 500 ℃ of temperature and kept 5 hours.The partial oxygen element generates CO and CO with the carbon gel reaction under vacuum heating conditions
2Discharge.At last, under atmospheric conditions, be warmed up to 700 ℃ and kept 5 hours, finish the polycrystallization reaction of product, make non-chemical measured lithium iron phosphate LiFePO
4-yMulticrystal pressed powder.
Non-chemical measured lithium iron phosphate LiFePO with above method acquisition
4-yThe polycrystalline pressed powder be pressed into the disk of 0.5 millimeter of diameter 12 millimeters thick with hydraulic press, surface vacuum gold evaporation film, the room-temperature conductivity of using four-point probe method to measure is 9.5 * 10
-4S/cm.
Embodiment 3: the preparation boosting type is mixed magnesium ithium iron manganese phosphate Li
xMg
1-xFe
zMn
1-zPO
4
The first step: with 180 gram methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O, 178 gram Mn (NH
4)
2(SO
4)
26H
2O and 115 gram phosphorus hydracid ammonia NH
4H
2PO
4In stirring, be dissolved in the 2000 gram deionized waters.Aerating oxygen in the aqueous solution, and be warmed up to 95 ℃ of temperature maintenances 10 hours.In the oxidizing atmosphere and the aqueous solution, methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O, Mn (NH
4)
2(SO
4)
26H
2O and phosphorus hydracid ammonia NH
4H
2PO
4React and the generation sediment amorphous phase Fe
0.5Mn
0.5PO
4
Second step is at above-mentioned semi-finished product Fe
0.5Mn
0.5PO
4The middle 24 gram lithium hydroxides that add kept 3 hours under 95 ℃ of temperature.After aqueous chemical diffusion and the Li of formation unsaturated state
xFePO
4Product is removed residual reactant after cleaning through water, after unsaturated state ithium iron manganese phosphate Li is made in vacuumize
xFe
0.5Mn
0.5PO
4The amorphous solid powder.
The 3rd step, 150 gram ithium iron manganese phosphate Li
xFe
0.5Mn
0.5PO
4Amorphous solid powder and 100 restrains magnesium chlorides through ground and mixed, is warmed up under 650 ℃ of temperature to keep 5 hours.Lithium iron phosphate Li
xFePO
4The pressed powder crystallization is by the noncrystal polycrystal that changes into; Meanwhile, under the effect of thermal diffusion, magnesium ion enters into ithium iron manganese phosphate Li
xFe
0.5Mn
0.5PO
4In the crystal structure, form and mix magnesium ithium iron manganese phosphate Li
xMg
1-xFe
0.5Mn
0.5PO
4(1-x ≈ 0.02) polycrystalline pressed powder.Behind the cool to room temperature, product is removed residual reactant after cleaning through water, after vacuumize can use.
At Li
xMg
1-xFePO
4Add Mn in (x ≈ 0.02) crystal structure as before and after the supercharging additive, accompanying drawing one is seen in the variation of discharge voltage.
Embodiment 4: preparation high-energy nanostructure is mixed magnesium lithium iron phosphate Li
xMg
1-xFePO
4
The first step is with 174 gram ferric acetate (CH
3COO)
2Fe, 115 gram phosphorus hydracid ammonia NH
4H
2PO
4With 20 gram carbon gels, under agitation successively join in the 1000 gram ethanol, form the colloidal sol emulsion.
Second step is with 75 gram lithium carbonate Li
2CO
3With 3 gram magnesium nitrate Mg (NO
3)
2Under agitation successively join above-mentioned colloidal sol emulsion.
In the 3rd step, emulsion is transferred in the aluminium oxide ceramics crucible 10
-1Under the torr low vacuum, prior to heating under 100 ℃ of temperature 1 hour, the solvent composition in the raw material is discharged, and then be warmed up to 200-400 ℃ of reaction 10 hours under sealing condition, under 500-900 ℃ of temperature, kept 1 hour at last, obtain elements doped lithium ferrimanganic phosphate Li with nanostructure
xMg
1-xFePO
4Polycrystal powder.Behind the cool to room temperature, after grinding, can use.
Claims (10)
1. positive electrode that is used for lithium battery is at lithium iron phosphate LiFePO
4Add the conductiving doping agent in the crystal, it is characterized in that: this material is expressed as Li with chemical general formula
xM
1-xFePO
4, x=0.95～0.999, dopant ion M is selected from Mg
2+, Ca
2+, Sr
2+, Ti
3+, Al
3+, B
3+, Si
4+, Ge
4+, or P
5+
2. one kind prepares the described method that is used for the positive electrode of lithium battery of claim 1 by solid phase reaction, and this method may further comprise the steps:
(1) with after lithium nitrate, ferrous oxalate, ammonium di-hydrogen phosphate and the conductiving doping agent mixing, puts into the stainless steel ball grinding machine and mixed 1 hour;
(2) powder that will mix back formation is transferred in the aluminium oxide ceramics crucible, under inert gas, prior to heating under 200～400 ℃ of temperature 2 hours, the gas componant in the powder is discharged;
(3) be warmed up to 500～900 ℃ of reactions 10 hours again, make Li
xMg
1-xFePO
4Solid powder material.
3. one kind by the described method that is used for the positive electrode of lithium battery of liquid-solid phase prepared in reaction claim 1, and this method may further comprise the steps:
(1) amorphous state FePO
4Be by methyllanthionine iron Fe (NH
4)
2(SO
4)
26H
2O and phosphorus hydracid ammonia NH
4H
2PO
4Carrying out reactant aqueous solution in oxidizing atmosphere is prepared from;
(2) the process lithium ion is at amorphous state FePO
4In chemical diffusion after form the Li of unsaturated state
xFePO
4
(3) the lithium iron phosphate crystal Li of conductiving doping agent and unsaturated state
xFePO
4Form Li by the solid state heat chemical reaction
xM
1-xFePO
4
(4) be warmed up to 500～900 ℃ of reactions 10 hours, make Li
xM
1-xFePO
4Pressed powder.
4. the method for preparing anode material of lithium battery according to claim 3 is characterized in that: any one in metal oxide, carbonate, sulfide, phosphate and the fluoride that contains the M ion adopted in the conductiving doping agent.
5. one kind prepares the described method that is used for the positive electrode of lithium battery of claim 1 by thermal diffusion ion-exchange, and this method may further comprise the steps:
(1) with lithium nitrate, ferrous oxalate and ammonium di-hydrogen phosphate by after mixing, put into the stainless steel ball grinding machine and mixed 1 hour.Transfer in the aluminium oxide ceramics crucible under inert gas mixing powder that the back forms, prior to heating under 200～400 ℃ of temperature 2 hours, gas componant in the powder is discharged, and then be warmed up to 600～900 ℃ of reactions 10 hours, obtain unsaturation lithium iron phosphate Li
xFePO
4Polycrystal powder, behind the cool to room temperature, standby through grinding;
(2) the unsaturation lithium iron phosphate Li that (1) method is set by step obtained
xFePO
4Polycrystal powder and carbon compound, nitrate, sulfate or the phosphatic raw materials powder of conductiving doping agent in 2: 1 ratios grind mix after, use the oil pressure forcing press to be pressed into thin slice, thin slice is put into rustless steel container, be warmed up to 500 ℃ then, and under this temperature, kept 5 hours, because unsaturation lithium iron phosphate Li
xFePO
4Polycrystal powder particle and magnesium nitrate polycrystal powder particle quilt are closely compacted together, and at unsaturation lithium iron phosphate Li
xFePO
4There is the lithium ion room to exist in the crystal, therefore the magnesium ion thermal diffusion reaction takes place, make unsaturation lithium iron phosphate Li
xFePO
4Lithium ion room in the crystal is replaced by magnesium ion, mixes magnesium lithium iron phosphate Li and generate
xMg
1-xFePO
4Pressed powder, after ions diffusion reaction is finished, cool to room temperature, the product pressed powder behind the water cleaning reaction washes wherein conductiving doping agent, after vacuumize, mixes magnesium lithium iron phosphate Li
xMg
1-xFePO
4Pressed powder can use.
6, a kind of positive electrode that is used for lithium battery, it is characterized in that: this material is expressed as LiFePO with the non-stoichiometry general formula
4-y, y=0.01～1.50.
7, a kind ofly prepare the described method that is used for anode material of lithium battery of claim 6 by collosol and gel, this method may further comprise the steps:
(1) with joining in the ethanol after ferrous oxalate, ammonium di-hydrogen phosphate and the carbon gel mixing stirring, forms emulsion;
(2) lithium hydroxide under agitation is dissolved in the ionized water, forms limpid solution;
(3) above-mentioned two kinds of liquid are under agitation mixed, form sol solutions, transfer to then in the aluminium oxide ceramics crucible, in Sealing furnace, under 150 ℃ of temperature, heated 2 hours, then, 10
-2Under the torr low vacuum, slowly be heated under 500 ℃ of temperature and kept 5 hours, the partial oxygen element generates CO and CO with the carbon gel reaction under vacuum heating conditions
2Discharge, under atmospheric conditions, be warmed up to 700 ℃ and kept 5 hours, product is removed the residual hydrogen lithia after cleaning through water, after LiFePO is made in vacuumize
4-yPressed powder.
8. positive electrode that is used for lithium battery, it is characterized in that: its chemical general formula is Li
xM
1-xFe
zM '
1-zPO
4, x=0.95～1.05, z=0.20～0.99, dopant ion M is selected from Mg
2+, Ca
2+, Sr
2+, Ti
3+, Al
3+, B
3+, Si
4+, Ge
4+, or P
5+, M ' is selected from Ti
3+, V
3+, Co
3+, Ni
3+, Mn
3+, Cr
3+, Cu
3+Or Mo
3+
9. one kind prepares the described method that is used for the positive electrode of lithium battery of claim 8 by solid phase reaction, and this method may further comprise the steps:
(1) with after lithium nitrate, ferrous oxalate, ammonium di-hydrogen phosphate and the conductiving doping agent mixing, puts into the stainless steel ball grinding machine and mixed 1 hour; The powder that mixes back formation is transferred in the aluminium oxide ceramics crucible, under the nitrogen inert gas,, the gas componant in the powder is discharged prior to heating under 200～400 ℃ of temperature 2 hours, and then be warmed up to 500～900 ℃ of reactions 10 hours, obtain to mix magnesium lithium iron phosphate Li
xMg
1-xFePO
4Pressed powder, cool to room temperature, standby after grinding;
(2) with after lithium nitrate, the inferior manganese of oxalic acid, ammonium di-hydrogen phosphate and the conductiving doping agent mixing, put into the stainless steel ball grinding machine and mixed 1 hour; The powder that mixes is transferred in the aluminium oxide ceramics crucible, under the nitrogen inert gas,, the gas componant in the powder is discharged prior to heating under 200～400 ℃ of temperature 2 hours, and then be warmed up to 600～1000 ℃ of reactions 10 hours, obtain to mix magnesium lithium manganese phosphate Li
xMg
1-xMnPO
4Pressed powder, cool to room temperature, standby after grinding;
(3) mix magnesium lithium iron phosphate Li to what step (1) made
xMg
1-xFePO
4Pressed powder and step (2) make mix magnesium lithium manganese phosphate Li
xMg
1-xFeMnPO
4Pressed powder mix after, put into the stainless steel ball grinding machine and mixed 1 hour.The powder that mixes is transferred in the aluminium oxide ceramics crucible, and under the nitrogen inert gas, heating is 5 hours under 600-1000 ℃ of temperature, makes and mixes magnesium ithium iron manganese phosphate Li
xMg
1-xFe
zMn
1-zPO
4Pressed powder.
10. one kind prepares the described method that is used for the positive electrode of lithium battery of claim 8 by solgel reaction, and this method may further comprise the steps:
(1) lithium carbonate, ferrous oxalate and ammonium di-hydrogen phosphate are stirred, join in the ethanol, form limpid solution;
(2) lithium carbonate, the inferior manganese of oxalic acid and ammonium di-hydrogen phosphate are stirred, join in the ethanol, form limpid solution;
(3) with after above-mentioned two kinds of solution mixing, under agitation add carbon gel and conductiving doping agent, form emulsion;
(4) emulsion is transferred in the aluminium oxide ceramics crucible 10
-1Under the torr low vacuum, prior to heating under 100 ℃ of temperature 1 hour, the solvent composition in the emulsion is discharged, and then be warmed up to 500～900 ℃, reaction is 10 hours under sealing condition, obtains elements doped lithium ferrimanganic phosphate Li
xM
1-xFe
zMn
1-zPO
4Polycrystal powder.
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