CN1772604A - Prepn process of oxygen place doped lithium ferric phosphate powder - Google Patents
Prepn process of oxygen place doped lithium ferric phosphate powder Download PDFInfo
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- CN1772604A CN1772604A CNA2005101125626A CN200510112562A CN1772604A CN 1772604 A CN1772604 A CN 1772604A CN A2005101125626 A CNA2005101125626 A CN A2005101125626A CN 200510112562 A CN200510112562 A CN 200510112562A CN 1772604 A CN1772604 A CN 1772604A
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- nitrogen
- ferric phosphate
- lithium
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- oxygen place
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 title claims abstract description 38
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 28
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 28
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title description 9
- 230000008569 process Effects 0.000 title description 4
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 229910010701 LiFeP Inorganic materials 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 78
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 239000012298 atmosphere Substances 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000005338 frosted glass Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical group O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229940116007 ferrous phosphate Drugs 0.000 claims description 6
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 6
- 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 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 33
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
- 229910010710 LiFePO Inorganic materials 0.000 description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 18
- 206010013786 Dry skin Diseases 0.000 description 16
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 238000009413 insulation Methods 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 16
- 238000007789 sealing Methods 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 10
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 10
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 10
- 229910013870 LiPF 6 Inorganic materials 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 230000004087 circulation Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 239000005030 aluminium foil Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000012876 topography Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000005518 electrochemistry Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention belongs to the field of electrochemical power source material preparing technology, and is especially preparation process of oxygen place doped lithium ferric phosphate powder. The oxygen place doped lithium ferric phosphate as positive pole material in lithium ion cell has the molecular expression LiFeP(MxO4-x), and is prepared through mixing the dopant and the mother body material and sintering the mixture, or through solid phase reaction of the dopant and the mother body material. The preparation process has effective doping in the oxygen place of mother body material and the prepared material can raise the capacity and the circular discharge performance of the cell effectively and thus can find its wide application as positive pole material in secondary lithium ion cell and power cell.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material.Be particularly related to as using secondary lithium battery or power source preparation method always with a kind of oxygen place doped lithium ferric phosphate powder of modification lithium-ion battery anode material.
Technical background
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, numerous advantages such as have that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile telephone, notebook computer, portable power tool, electronic instrument, weaponry etc., in electromobile, also have a good application prospect, become the emphasis that competitively research and develop countries in the world at present.Positive electrode material is an important component part of lithium ion battery, in the lithium ion battery charge and discharge process, not only to be provided in the positive and negative electrode lithium intercalation compound the needed lithium of back and forth embedding/take off, form the needed lithium of SEI film but also will bear the negative material surface, therefore, research and develop the key point that high performance positive electrode material has become the lithium ion battery development.Present research mainly concentrates on the lithium-containing transition metal oxide aspect, and transition metal is mainly cobalt, nickel, manganese.In recent years, based on Fe
3+/ Fe
2+The material of redox couple causes people's very big interest, particularly has the iron lithium phosphate (LiFePO of olivine crystal structure
4) become the most promising alternative positive electrode material of recent research.
LiFePO
4That material has is cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, multiple advantage such as capacity is higher, stability is fine.Goodenough[J.Electrochem.Soc., 144 (1997) 1188] research group has synthesized iron lithium phosphate (LiFePO at first
4), this material has high theoretical specific storage (170mAh/g) as anode material for lithium-ion batteries, greater than commercial LiCoO
2Actual discharge specific storage 140mAh/g, so cause investigator's very big concern.But the electronic conductivity of this material is relatively poor, has greatly limited the application of material under higher current density.The method about this material property of improvement raising of report mainly contains the surface and mixes or coated with conductive carbon material or conductive metal particle at present, improves the intergranular electronic conductivity of fertile material; Mix micro-high volence metal ion and partly replace Li
+Electronic conductivity in the precursor granule is improved in the position; Relatively large transition element replaces Fe
2+The position, the ionic conductivity of raising material.From existing result, the method that adds electro-conductive material can increase substantially the circulation volume of lithium iron phosphate positive material, particularly improve the rate capacities performance, and the doping effect of lithium position and iron position is limited.
In other positive electrode materials, as spinel lithium manganate LiMn
2O
4, use low valence metal ion doped and substituted manganese position usually, can improve tetravalence manganese Mn
4+Ratio in compound, thereby stable crystal structure, the occurrence degree of restriction Jahn-Teller effect be the comparison effective means aspect the raising normal-temperature circulating performance, but under high temperature (＞55 ℃) running status, the effect of this method is just not obvious.People study trial to spinel lithium manganate LiMn in recent years
2O
4The doped and substituted of oxygen position is as with sulphur part replace oxygen (United States Patent (USP) U.S.Patent No.5,674,645,1999; Materials chemistry journal J.Mater.Chem., 1999,9,3147; The electrochemistry journal, J.Electrochem.Soc., 147 (6) (2000) 2116; The electrochemistry collected works, Electrochim.Acta, 46 (2000) 541; The electrochemistry communication, Electrochem.Commun., 3 (2001) 199; The electrochemistry journal, J.Electrochem.Soc., 148 (2001) A994; ) and fluorine part replace oxygen (81-82 (1999) 627 for energy journal, J.Power Sources; The electrochemistry journal, J.Electrochem.Soc., 148 (2) (2001) A171-A182; Power technology, 28 (9) (2004) 542), can reduce the dissolving of manganese in electrolytic solution in the electrode, suppress material structure distortion takes place in working cycle, thereby limit the Jahn-Teller effect that takes place in its charge and discharge process to a great extent, improve normal temperature charge/discharge capacity 1/3, particularly significantly improved the high temperature volumetric properties.The LiNiO that also has laminate structure
2Positive electrode material is substituted by the part of fluorion by oxygen, also makes its cycle performance improve (energy and material J.PowerSources, 81-82 (1999) 599-603).
It is doped raw material that the present invention proposes with compound that contains oxygen family element and halogens and simple substance (being designated as M, down together), utilizes conventional solid-state method to prepare oxygen place doped iron lithium phosphate LiFeP (M
xO
4-x) (0≤x≤2), improved the basic electrical property of this material, make it have higher charge/discharge capacity and good cycle performance of battery.
Summary of the invention
The object of the present invention is to provide a kind ofly, significantly improve a kind of preparation method of oxygen place doped lithium ferric phosphate powder of the anode material for lithium ion battery of parent basis electrical property by oxygen family element and halogens doped and substituted oxygen position.It is characterized in that described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP (M
xO
4-x) expression, wherein M is a doped source, 0≤x≤2;
The preparation method's of described oxygen place doped lithium ferric phosphate powder concrete mode is as follows:
1) mixing method of hotchpotch and parent stock
By lithium salts, ferrous salt and phosphoric acid salt by Li: Fe: P=1: 1: 1 mixed in molar ratio becomes parent stock, parent stock is pressed parent again: batch mixing of the mol ratio of hotchpotch=1: 0.001～2, adding at least a in deionized water, industrial spirit and the dehydrated alcohol then mixes as blending agent, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder is at nitrogen, and heating is 400～550 ℃ under the argon gas, at least a inert atmosphere in the nitrogen and hydrogen mixture or reducing atmosphere, and being incubated 2～10 hours carries out precalcining; With the pre-imitation frosted glass secondary ball milling of parent 6～12 hours, 40～70 ℃ of oven dry down, then at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder;
2) the pre-imitation frosted glass batch mixing of hotchpotch and parent blended solid phase method synthesis mode
In mode 1) ratio mixes parent stock, adding blending agent mixes, 6～12 hours mixing and ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, heat 400～550 ℃, be incubated 2～10 hours and carry out precalcining; Again pre-imitation frosted glass of parent and hotchpotch are pressed parent: the mol ratio of hotchpotch=1: 0.001～2, adding medium mixes, 6～12 hours ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas is under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture then, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder.
Described blending agent is at least a in deionized water, industrial spirit and the dehydrated alcohol
Described hotchpotch is the sulfur doping source of nitrogen doped source, sulfurous organic compound or the simple substance of itrogenous organic substance, the chlorine doped source of chlorine-containing compound or the fluorine doped source of fluorochemicals.
Described fluorine doped source is at least a in Neutral ammonium fluoride, the lithium fluoride.
Described sulfur doping source is at least a in sulphur S simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
Described chlorine doped source is at least a in ammonium chloride, the sodium-chlor.
Described nitrogen doped source is a urea.
Described lithium salts is Li
2CO
3, LiOH, lithium oxalate, at least a in the Lithium Acetate.
Described ferrous salt is a Ferrox, and Iron diacetate is at least a in iron protochloride, ferrous sulfate, the ferrous phosphate.
Described phosphoric acid salt comprises ammonium phosphate, Secondary ammonium phosphate, and primary ammonium phosphate, at least a in the ferrous phosphate.
Described inert atmosphere or reducing atmosphere are nitrogen, argon gas, at least a in the nitrogen and hydrogen mixture.
The invention has the beneficial effects as follows and utilize the solid phase method that is easy to commercially produce, doping draw materials itrogenous organic substance, sulfurous organic compound or simple substance, chlorine-containing compound, fluorochemicals widely, through the simple stoving process that mixes, by control thermal treatment temp and time, it is good to prepare crystal property, composition is even, the anode material for lithium ion battery iron lithium phosphate LiFeP (M of oxygen place doped sulphur, nitrogen, chlorine, fluorine
xO
4-x) (0≤x≤2) powder, its median size 0.5～2 μ m, first discharge specific capacity can reach 90-110mAh/g under the room temperature.Compare with metallic cation doping route, the present invention utilizes wide material sources, cheap anionic compound or simple substance to be hotchpotch, be easy to be implemented in effective doping of parent oxygen position by traditional solid phase method, parent basis capacity and cycle electric performance have been significantly improved, has clear superiority, very with practical value, have wide application prospect at secondary lithium battery, particularly power source commonly used with the cell positive material field.
Description of drawings
Fig. 1 presses the crystal X-ray powder diffraction collection of illustrative plates of the prepared oxygen place doped lithium ferric phosphate powder of embodiment 1～8, adopts CuK
αRadiation, λ=0.5418nm.
Fig. 2 presses the prepared oxygen place doped lithium ferric phosphate powder stereoscan photograph of embodiment 1～8.
Fig. 3 presses the prepared lithium ion battery of embodiment 1～8 discharge curve first, voltage 2.5V-4.2V, and discharging current 10～40mgh/g, electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1, volume ratio) mixed solution, measure 25 ℃ ± 2 ℃ of temperature.
Fig. 4 presses the cycle performance of embodiment 1～8 prepared lithium ion battery, the same Fig. 3 of used condition.
Embodiment
The object of the present invention is to provide a kind ofly, significantly improve a kind of preparation method of oxygen place doped lithium ferric phosphate powder of the anode material for lithium ion battery of parent basis electrical property by oxygen family element and halogens doped and substituted oxygen position.Described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP (M
xO
4-x) expression, wherein M is a doped source, 0≤x≤2;
The concrete mode of the preparation method of described oxygen place doped lithium ferric phosphate powder is as follows:
1) mixing method of hotchpotch and parent stock
Press lithium salts, ferrous salt and phosphoric acid salt and press Li: Fe: P=1: 1: 1 mixed in molar ratio parent stock, again parent stock is pressed parent: batch mixing of the mol ratio of hotchpotch=1: 0.001～2, adding at least a in deionized water, industrial spirit and the dehydrated alcohol then mixes as blending agent, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder is at nitrogen, and heating is 400～550 ℃ under the argon gas, at least a inert atmosphere in the nitrogen and hydrogen mixture or reducing atmosphere, and being incubated 2～10 hours carries out precalcining; With the pre-imitation frosted glass secondary ball milling of parent 6～12 hours, 40～70 ℃ of oven dry down, then at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder;
2) the pre-imitation frosted glass batch mixing of hotchpotch and parent blended solid phase method synthesis mode
In mode 1) ratio mixes parent stock, adding blending agent mixes, 6～12 hours mixing and ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, heat 400～550 ℃, be incubated 2～10 hours and carry out precalcining; Again pre-imitation frosted glass of parent and hotchpotch are pressed parent: the mol ratio of hotchpotch=1: 0.001～2, adding medium mixes, 6～12 hours ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas is under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture then, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder.
Described hotchpotch is the sulfur doping source of nitrogen doped source, sulfurous organic compound or the simple substance of itrogenous organic substance, the chlorine doped source of chlorine-containing compound or the fluorine doped source of fluorochemicals.
Described fluorine doped source is at least a in Neutral ammonium fluoride, the lithium fluoride.
Described sulfur doping source is at least a in sulphur simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
Described chlorine doped source is at least a in ammonium chloride, the sodium-chlor.
Described nitrogen doped source is a urea.
Described lithium salts is Li
2CO
3, LiOH, lithium oxalate, at least a in the Lithium Acetate.
Described ferrous salt is a Ferrox, and Iron diacetate is at least a in iron protochloride, ferrous sulfate, the ferrous phosphate.
Described phosphoric acid salt comprises ammonium phosphate, Secondary ammonium phosphate, and primary ammonium phosphate, at least a in the ferrous phosphate.
With doped lithium ferric phosphate and conductive carbon black, polyvinylidene difluoride (PVDF), by 9～16: 0.875～2.2: 1 mass ratio is coated on the collector aluminium flake after grinding evenly, make electrode slice, with the metal lithium sheet is negative pole, to be dissolved in the 1.0mol/L LiPF in ethyl-carbonate+methylcarbonate (volume ratio 1: 1) mixed solvent
6Be electrolytic solution, polypropylene microporous film is a barrier film, is assembled into the simulation Li-Ion rechargeable battery.
The system of discharging and recharging of the respective battery of described assembling is: press the 0.05-0.2C multiplying power at 2.5V-4.2V constant current charge-discharge under voltage.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 10 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass of parent and add 0.04 mole of thiocarbamide in the polyester jar, add an amount of alcohol, sealing back ball milling 6 hours under 0.3 liter/minute nitrogen atmosphere, rises to 700 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 8 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePS
0.4O
3.6, be designated as sample A.A is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the sulphur.A is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is 0.5～4 micron a primary particle size.
The chemical property of gained sample is measured as follows: take by weighing the 0.9g positive powder, add the 0.19g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, A is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.35V, the reversible specific capacity first of sample A is about 110mAh/g as can be seen.A is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 20mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 110mAh/g.
Embodiment 2
With 0.05 Quilonum Retard and 0.1 mole of Ferrox, 0.1 mole of phosphoric acid ammonium dihydrogen and 0.062 mole of simple substance sublimed sulphur mix, add in the polyester jar, add the 30ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 430 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 7.5 hours, cool to room temperature with the furnace, taking out 0.1 mole of pre-imitation frosted glass of parent is incorporated in the polyester jar, add an amount of alcohol, sealing back ball milling 10 hours is then at 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio) under, rise to 720 ℃ with 4 ℃/minute temperature rise rates,, be cooled to room temperature with stove this temperature insulation 7 hours.The gained positive electrode material is LiFePS
0.62O
3.38, be designated as sample B.B is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiEePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the sulphur.B is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is 1～20 micron primary particle size and comparatively serious aggregate particle size of reuniting.
The chemical property of gained sample is measured as follows: take by weighing the 1.125g positive powder, add the 0.169g carbon black, the 0.12g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 10mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, B is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.35V, the reversible specific capacity first of sample A is about 98mAh/g as can be seen.B is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 10mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 100mAh/g.
Embodiment 3
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 450 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 9 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass of parent and add 0.05 mole of urea in the polyester jar, add an amount of alcohol, sealing back ball milling 10 hours under 0.3 liter/minute nitrogen atmosphere, rises to 700 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 8 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePN
0.5O
3.5, be designated as sample C.C is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the nitrogen.C is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is for less than 0.5 micron primary particle size and some offsprings of 2 microns that are gathered into.
The chemical property of gained sample is measured as follows: take by weighing the 1.02g positive powder, add the 0.084g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 34mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, C is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.33V, the reversible specific capacity first of sample A is about 90mAh/g as can be seen.C is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 34mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on about 90mAh/g.
Embodiment 4
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen and 0.15 mole of urea are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 11 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 480 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 5 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass of parent and be incorporated in the polyester jar, add an amount of alcohol, sealing back ball milling 6 hours under 0.3 liter/minute nitrogen atmosphere, rises to 680 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 11 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePN
1.5O
2.5, be designated as sample D.D is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the nitrogen.D is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is for less than 0.5 micron primary particle size and some offsprings of 2 microns that are gathered into.
The chemical property of gained sample is measured as follows: take by weighing the 0.9g positive powder, add the 0.204g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, D is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.38V, the reversible specific capacity first of sample A is about 100mAh/g as can be seen.D is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 20mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on about 100mAh/g.
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 6.5 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8.5 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass of parent and put into the polyester jar with 0.03 mole of Neutral ammonium fluoride, add an amount of alcohol, sealing back ball milling 6 hours under 0.3 liter/minute nitrogen atmosphere, rises to 700 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 8 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePF
0.3O
3.7, be designated as sample E.E is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the fluorine.E is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is for less than 0.5 micron primary particle size and some offsprings of 2 microns that are gathered into.
The chemical property of gained sample is measured as follows: take by weighing the 0.3375g positive powder, add the 0.0765g carbon black, the 0.036g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 34mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, E is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the discharge voltage plateau of the inclination of 3.3V, the reversible specific capacity first of sample A is about 90mAh/g as can be seen.E is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 34mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 80mAh/g.
Embodiment 6
With 0.035 mole of Quilonum Retard and 0.1 mole of Ferrox, 0.1 mole of phosphoric acid ammonium dihydrogen and 0.02 mole of lithium fluoride mix, add in the polyester jar, add the 30ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, cool to room temperature with the furnace, taking out 0.1 mole of pre-imitation frosted glass of parent is incorporated in the polyester jar, add an amount of alcohol, sealing back ball milling 8 hours is then at 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio) under, rise to 700 ℃ with 4 ℃/minute temperature rise rates,, be cooled to room temperature with stove this temperature insulation 8 hours.The gained positive electrode material is LiFePF
0.2O
3.8, be designated as sample F.F is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the fluorine.F is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is 0.5 micron a primary particle size, but more serious reunion is arranged.
The chemical property of gained sample is measured as follows: take by weighing the 1.125g positive powder, add the 0.255g carbon black, the 0.12g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 10mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, F is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the discharge voltage plateau of the inclination of 3.3V, the reversible specific capacity first of sample A is about 60mAh/g as can be seen.F is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 10mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 55mAh/g.
Embodiment 7
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass of parent and put into the polyester jar with 0.08 mole of ammonium chloride, add an amount of alcohol, sealing back ball milling 6 hours under 0.3 liter/minute nitrogen atmosphere, rises to 700 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 8 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePCl
0.8O
3.2, be designated as sample G.G is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the chlorine.G is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is for less than 0.5 micron primary particle size and some offsprings of 2 microns that are gathered into.
The chemical property of gained sample is measured as follows: take by weighing the 0.3g positive powder, add the 0.068g carbon black, the 0.032g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, G is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.35V, the reversible specific capacity first of sample A is about 100mAh/g as can be seen.G is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 20mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 95mAh/g.
Embodiment 8
0.05 mole of Quilonum Retard and 0.1 mole of Ferrox and 0.1 mole of phosphoric acid ammonium dihydrogen are mixed, add in the polyester jar, add the 25ml raw spirit, mixed 7 hours on planetary ball mill the sealing back, under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, take out 0.1 mole of pre-imitation frosted glass and put into the polyester jar with 0.025 mole of ammonium chloride, add an amount of alcohol, sealing back ball milling 6 hours under 0.3 liter/minute nitrogen atmosphere, rises to 700 ℃ with 4 ℃/minute temperature rise rates then, this temperature insulation 8 hours, be cooled to room temperature with stove.The gained positive electrode material is LiFePCl
0.25O
3.75, be designated as sample H.H is gained LiFePO among Fig. 1
4XRD figure, the adding of hotchpotch does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that mixes due to the chlorine.H is gained LiFePO among Fig. 2
4Stereoscan photograph, sample topography is more to reunite less than 0.5 micron primary particle size with than embodiment 8.
The chemical property of gained sample is measured as follows: take by weighing the 0.9g positive powder, add the 0.204g carbon black, the 0.096g polyvinylidene difluoride (PVDF) is made dispersion agent with dehydrated alcohol, ultra-sonic oscillation are mixed 30min, it is even to make it thorough mixing, after 80 ℃ of dryings, adds N-Methyl pyrrolidone furnishing slurry, be coated on equably on the collector aluminium foil, after 80 ℃ of dryings, on roll squeezer, flatten, make the anode thin film of the about 200 μ m of thickness.On anode thin film, go out 1cm
2The size disk, after weighing, with it more than 140 ℃ of vacuum-drying 12h, behind the vacuum chamber naturally cooling, as backup electrode.Electrolytic solution adopts 1mol/L LiPF
6Ethyl-carbonate EC: methylcarbonate DMC (1: 1) mixed solution; Polypropylene microporous film is a barrier film; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours, speed by 20mA/g (in positive pole) charges to 4.2 volts, be discharged to 2.5 volts, H is the discharge curve first of battery among Fig. 3, the discharge voltage plateau that shows the battery of surveying that the weak point of 3.3V is arranged and tilt, the reversible specific capacity first of sample A is about 95mAh/g as can be seen.H is the cyclic curve of respective battery among Fig. 4, and after 20 circulations, under the 20mA/g charge-discharge velocity, the specific discharge capacity that respective material shows remains on more than the 95mAh/g.
Claims (9)
1. the preparation method of an oxygen place doped lithium ferric phosphate powder is characterized in that, described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP (M
xO
4-x) expression, wherein M is a doped source, 0≤x≤2;
The preparation method's of described oxygen place doped lithium ferric phosphate powder concrete mode is as follows:
1) by lithium salts, ferrous salt and phosphoric acid salt by Li: Fe: P=1: 1: 1 mixed in molar ratio becomes parent stock, again parent stock is pressed parent: batch mixing of the mol ratio of hotchpotch=1: 0.001～2, adding at least a in deionized water, industrial spirit and the dehydrated alcohol then mixes as blending agent, 6～12 hours mixing and ball milling time is 40～70 ℃ of oven dry down; Oven dry back powder is at nitrogen, and heating is 400～550 ℃ under the argon gas, at least a inert atmosphere in the nitrogen and hydrogen mixture or reducing atmosphere, and being incubated 2～10 hours carries out precalcining; With the pre-imitation frosted glass secondary ball milling of parent 6～12 hours, 40～70 ℃ of oven dry down, then at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder;
2) the pre-imitation frosted glass batch mixing of hotchpotch and parent blended solid phase method synthesis mode
In mode 1) ratio mixes parent stock, adding blending agent mixes, 6～12 hours mixing and ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas, under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture, heat 400～550 ℃, be incubated 2～10 hours and carry out precalcining; Again pre-imitation frosted glass of parent and hotchpotch are pressed parent: the mol ratio of hotchpotch=1: 0.001～2, adding medium mixes, 6～12 hours ball milling time, 40～70 ℃ of oven dry down, at nitrogen, argon gas is under at least a inert atmosphere or reducing atmosphere in the nitrogen and hydrogen mixture then, 550～850 ℃ of secondary clacinings obtain oxygen place doped lithium ferric phosphate LiFeP (M
xO
4-x) powder.
2. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 1, it is characterized in that described hotchpotch is the sulfur doping source of nitrogen doped source, sulfurous organic compound or the simple substance of itrogenous organic substance, the chlorine doped source of chlorine-containing compound or the fluorine doped source of fluorochemicals.
3. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 3, it is characterized in that described fluorine doped source is at least a in Neutral ammonium fluoride, the lithium fluoride.
4. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 3, it is characterized in that described sulfur doping source is at least a in sulphur S simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
5. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 3, it is characterized in that described chlorine doped source is at least a in ammonium chloride, the sodium-chlor.
6. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 3, it is characterized in that described nitrogen doped source is a urea.
7. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 1, it is characterized in that described lithium salts is Li
2CO
3, LiOH, lithium oxalate, at least a in the Lithium Acetate.
8. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 1, it is characterized in that described ferrous salt is a Ferrox, Iron diacetate is at least a in iron protochloride, ferrous sulfate, the ferrous phosphate.
9. according to the preparation method of the described oxygen place doped lithium ferric phosphate powder of claim 1, it is characterized in that described phosphoric acid salt comprises ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, at least a in the ferrous phosphate.
Priority Applications (1)
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|---|---|---|---|
| CNB2005101125626A CN1332878C (en) | 2005-10-11 | 2005-10-11 | Prepn process of oxygen place doped lithium ferric phosphate powder |
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