CN1785823A - Preparation method of phosphorus position partly substituted iron lithium phosphate powder - Google Patents
Preparation method of phosphorus position partly substituted iron lithium phosphate powder Download PDFInfo
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- CN1785823A CN1785823A CNA200510132430XA CN200510132430A CN1785823A CN 1785823 A CN1785823 A CN 1785823A CN A200510132430X A CNA200510132430X A CN A200510132430XA CN 200510132430 A CN200510132430 A CN 200510132430A CN 1785823 A CN1785823 A CN 1785823A
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- Prior art keywords
- lithium
- preparation
- phosphate powder
- replacement source
- hours
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- 239000000843 powder Substances 0.000 title claims abstract description 34
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000011574 phosphorus Substances 0.000 title claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000005955 Ferric phosphate Substances 0.000 claims description 9
- 229910010701 LiFeP Inorganic materials 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229940032958 ferric phosphate Drugs 0.000 claims description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical group O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- -1 tetraethoxy Chemical compound 0.000 claims description 7
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 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
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 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
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000007599 discharging Methods 0.000 description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 18
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 17
- 238000009413 insulation Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000007789 sealing Methods 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000005338 frosted glass Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000004087 circulation Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 238000012876 topography Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 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
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 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
- 230000010355 oscillation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000012360 testing 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
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a preparation method of phosphorus position partial substituted type iron lithium phosphate powder body, belonging to the field of electrochemical power supply material preparation technology. The molecular formula of said positive electrode iron lithium phosphate of lithium ion cell is LiFeP1-yDyO4. Its preparation method includes the following steps: mixing lithium salt, ferrous salt, phosphate and substitution compound according to a certain mole ratio, drying, low-temperature prefiring and high-temperature secondary calcining so as to obtain the phosphorus position partial substituted type iron lithium phosphate powder body. Said invention uses the compound of boron, tungsten, sulfur and silicon or elementary substance as substitution compound.
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 phosphorus position partly substituted iron lithium 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.
Document Goodenough[J.Electrochem.Soc., 144 (1997) 1188] point out, except (PO
4)
3-Tetrahedron, a lot of polyanion groups can with iron Fe chemical combination, thereby reduce Fe
3+/ Fe
2+Oxidation-reduction potential make it reach practical cell potential, as (SO
4)
2-, (AsO
4)
3-, (MoO
4)
2-(WO
4)
2-Deng.Mention compound in the U.S. Pat 2004005265 and consist of A
x(M '
1-aM "
a)
y(XD
4)
z, its X is a kind of among P, S, As, Mo and the W.But S, As, Mo and W all replace P, the combination of this Fe-O key that will weaken, reduce its open circuit voltage, the crystalline structure of Xing Chenging does not have the character of slotting lithium-storage lithium on the other hand, and this patent does not have feasibility checking and the support of embodiment as the compound that all replaces P.
The present invention proposes partly to replace iron lithium phosphate (LiFePO with compound that contains B, W, S and Si element or simple substance (being designated as D, down together) for replacing raw material
4) in the P element, utilize conventional solid-state method to prepare the iron lithium phosphate LiFeP that phosphorus position partly replaces
1-yD
yO
4The basic electrical property of this material has been improved in 0＜y≤0.5 wherein, makes 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 partly to replace phosphate potential, significantly improve a kind of preparation method of phosphorus position partly substituted iron lithium phosphate powder of the anode material for lithium ion battery of parent base batteries performance by B, W, S and Si element.It is characterized in that described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP
1-yD
yO
4Expression, wherein D is the replacement source, 0＜y≤0.5;
Concrete preparation method is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and substituent are pressed element Li: Fe: P: D=1: 1: (1-y): batch mixing of the molar ratio of y, added mix grinding medium mixing and ball milling 6～12 hours, after drying under 40～70 ℃, under inert atmosphere or reducing atmosphere, be heated to 400～550 ℃, be incubated 5～10 hours and carry out precalcining; Pre-imitation frosted glass secondary mixing was ground 6～12 hours, and after 40～70 ℃ of following oven dry, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtain phosphorus position partly substituted iron lithium phosphate LiFeP
1-yX
yO
4Powder.
Described mix grinding medium is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described substituent is that the boron replacement source of boron-containing compound, the tungsten of Tungstenic compound replace the sulphur replacement source of source, sulfurous organic compound and simple substance or the silicon replacement source of silicon-containing compound.
Described boron replacement source is at least a in boric acid, trimethyl borate and the boron oxide.
Described tungsten replacement source is at least a in wolframic acid and the ammonium tungstate.
Described sulphur replacement source is at least a in sulphur S simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
Described silicon replacement source is at least a in silica gel, tetraethoxy, Union carbide A-162 and the Trichloromonosilane.
Described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate and the Lithium Acetate.
Described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
Described phosphoric acid salt comprises in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate at least a.
Described inert atmosphere or reducing atmosphere, be at least a in nitrogen, argon gas and 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, substituent is boron-containing compound, Tungstenic compound, sulfurous organic compound or simple substance and the silicon-containing compound widely of drawing materials, 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 that phosphorus position partly is replaced by boron, tungsten, sulphur and silicon
1-yX
yO
4, 0＜y≤0.5 powder wherein, its median size 0.5～2 μ m, first discharge specific capacity can reach 75 ~ 130mAh/g under the room temperature.The present invention utilizes originate widely boron, tungsten, sulphur and silicon compound or simple substance to be substituent, be easy to realize that at the parent phosphate potential significant part replaces by traditional solid phase method, have obvious effects and advantage more to improving parent basis capacity and cycle electric performance, very with practical value, has 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
uRadiation, 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.
Test conditions: voltage 2.5V-4.2V, discharging current 10～40mgh/g, electrolytic solution is for adopting the LiPF of 1mol/L
6Be dissolved in ethyl-carbonate EC: methylcarbonate DMC=1: the mixed solution of 1 (volume ratio), 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 invention provides and a kind ofly partly replace the phosphoric of phosphate potential in the iron lithium phosphate, significantly improve a kind of preparation method of phosphorus position partly substituted iron lithium phosphate powder of the anode material for lithium ion battery of parent base batteries performance by boron, tungsten, sulphur and element silicon.Described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP
1-yD
yO
4Expression, wherein D is a substituent, 0＜y≤0.5;
The concrete preparation method of described phosphorus position partly substituted iron lithium phosphate powder is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and substituent are pressed Li: Fe: P: D=1: 1: (1-y): batch mixing of the molar ratio of y, add at least a in deionized water, industrial spirit and the dehydrated alcohol, 40～70 ℃ of oven dry down then as mix grinding medium mixing and ball milling 6～12 hours; 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 5～10 hours carries out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ down after the oven dry, 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 phosphorus position partly substituted iron lithium phosphate LiFeP
1-yD
yO
4Powder;
Described substituent is that the boron replacement source of boron-containing compound, the tungsten of Tungstenic compound replace the sulphur replacement source of source, sulfurous organic compound and simple substance and the silicon replacement source of silicon-containing compound.
Described boron replacement source is at least a in boric acid, trimethyl borate and the boron oxide.
Described tungsten replacement source is at least a in wolframic acid and the ammonium tungstate.
Described sulphur replacement source is at least a in sulphur S simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
Described silicon replacement source is at least a in silica gel, tetraethoxy and the Union carbide A-162.
Described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate and the Lithium Acetate.
Described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
Described phosphoric acid salt comprises in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate at least a.
With LiFeP
1-yD
yO
4Powder and conductive carbon black, polyvinylidene difluoride (PVDF), press (9～16): (0.875～2.2): 1 mass ratio is coated on the collector aluminium flake after grinding evenly, makes electrode slice, is negative pole with the metal lithium sheet, with the LiPF of 1.0mol/L
6The mixed solvent that is dissolved in 1: 1 ethyl-carbonate of volume ratio and methylcarbonate is an electrolytic solution, is that barrier film is assembled into the simulation Li-Ion rechargeable battery with the polypropylene microporous film.
The system of discharging and recharging of the respective battery of described assembling is: press 0.05-0.2C multiplying power constant current charge-discharge under the 2.5V-4.2V stopping potential.
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
With 0.05 mole of Quilonum Retard Li
2CO
3, 0.1 mole of Ferrox Fe (C
2O
4) 2H
2O and 0.0975 mole of phosphoric acid ammonium dihydrogen NH
4H
2PO
4With 0.0025 mole of boric acid H
3BO
4Mix, add in the polyester jar, add the 55ml raw spirit, mixed 10 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 400 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, be incubated 8 hours, be cooled to room temperature, obtain pre-imitation frosted glass with stove; Be medium ball milling 6 hours again with the industrial spirit, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, is cooled to room temperature with stove, gained positive electrode material LiFe (P
0.975B
0.025O
4) be designated as sample A.A is gained LiFe (P among Fig. 1
0.975B
0.025O
4) XRD figure, the adding of boron does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that adds due to the boron.A is LiFe (P among Fig. 2
0.975B
0.025O
4) stereoscan photograph, sample topography is 0.3～1 micron a primary particle size.
The chemical property of gained sample is measured as follows: take by weighing 0.9g LiFe (P
0.975B
0.025O
4) 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, A is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.38V, the reversible specific capacity first of battery A is about 130mAh/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 130mAh/g.
Embodiment 2
With 0.1 lithium hydroxide LiOHH
2O, 0.1 mole of Ferrox and 0.07 mole of phosphoric acid hydrogen, two ammonium (NH
4)
2HPO
4With 0.03 mole of trimethyl borate (CH
3O)
3B mixes, and adds in the polyester jar, adds the 40ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 430 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 7.5 hours, cool to room temperature with the furnace.Take out pre-imitation frosted glass, add appropriate amount of deionized water, sealing ball milling 10 hours, discharging oven dry back is at 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio) under, rises to 720 ℃, this temperature insulation 7 hours with 4 ℃/minute temperature rise rates, be cooled to room temperature with stove, gained positive electrode material LiFe (P
0.7B
0.3O
4) be designated as sample B.B is gained LiFe (P among Fig. 1
0.7B
0.3O
4) XRD figure, the adding of boron does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks that adds due to the boron.B is gained LiFe (P among Fig. 2
0.7B
0.3O
4) stereoscan photograph, sample topography is 0.5～2 micron primary particle size and comparatively serious aggregate particle size of reuniting.
Take by weighing 1.125g LiFe (P
0.7B
0.3O
4) positive powder, add the 0.169g carbon black, 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 10mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and 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 battery B is about 95mAh/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 90mAh/g.
Embodiment 3
With 0.1 molar acetate lithium Li (CH
3COO), 0.1 mole of Ferrox and 0.0975 mole of phosphoric acid ammonium (NH
4)
3PO
4With 0.00042 mole of ammonium tungstate N
5H
37W
6O
24H
2O mixes, and adds in the polyester jar, adds the 55ml industrial spirit, mixed 7 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 450 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 5 hours, be cooled to room temperature with stove.Obtain pre-imitation frosted glass, added the appropriate amount of deionized water ball milling 10 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 8 hours, is cooled to room temperature with stove, gained positive electrode material LiFe (P
0.975W
0.025O
4) be designated as sample C.C is gained LiFe (P among Fig. 1
0.975W
0.025O
4) XRD figure, the adding of tungsten does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks due to the tungsten.C is gained LiFe (P among Fig. 2
0.975W
0.025O
4) stereoscan photograph, 3 micron the particle of sample topography for growing up less than 0.5 micron primary particle size and some abnormal grains.
Take by weighing 1.02g LiFe (P
0.975W
0.025O
4) positive powder, add the 0.184g carbon black, 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 34mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and C is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.37V, the reversible specific capacity first of battery C is about 117mAh/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 110mAh/g.
Embodiment 4
With 0.05 mole of lithium oxalate Li
2(C
2O
4), 0.1 mole of Ferrox and 0.05 mole of phosphoric acid hydrogen, two ammoniums and 0.05 mole of wolframic acid H
2WO
4Mix, add in the polyester jar, add the 75ml raw spirit, mixed 11 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 480 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 5 hours, be cooled to room temperature with stove.Take out pre-imitation frosted glass, add appropriate amount of deionized water, sealing back ball milling 6 hours, discharging oven dry back rises to 680 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 11 hours, be cooled to room temperature with stove.Gained positive electrode material LiFe (P
0.5W
0.5O
4) be designated as sample D.D is gained LiFe (P among Fig. 1
0.5W
0.5O
4) XRD figure, the adding of tungsten does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks due to the tungsten.D is gained LiFe (P among Fig. 2
0.5W
0.5O
4) stereoscan photograph, sample topography is primary particle size and the reunion less than 0.5 micron.
Take by weighing 0.9g LiFe (P
0.5W
0.5O
4) positive powder, add the 0.204g carbon black, 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and D is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.35V, the reversible specific capacity first of battery D is about 80mAh/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 80mAh/g.
Embodiment 5
With 0.05 mole of Quilonum Retard, 0.1 mole of Ferrox and 0.095 mole of phosphoric acid ammonium dihydrogen and 0.005 mole of thiocarbamide H
2NCSNH
2Mix, add in the polyester jar, add the 80ml deionized water, mixed 6.5 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 400 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8.5 hours, be cooled to room temperature with stove.Take out pre-imitation frosted glass, add deionized water, sealing back ball milling 6 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute decomposed ammonia atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove.Gained positive electrode material LiFe (P
0.95S
0.05O
4) be sample E.E is gained LiFe (P among Fig. 1
0.95S
0.05O
4) XRD figure, the adding of sulphur does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks due to the sulphur.E is gained LiFe (P among Fig. 2
0.95S
0.05O
4) stereoscan photograph, sample topography is less than 0.5 micron spherical primary particle size and some reunions.
Take by weighing 0.3375g LiFe (P
0.95S
0.05O
4) positive powder, add the 0.0765g carbon black, 0.036g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 34mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and 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 3.38V, the reversible specific capacity first of battery E is about 110mAh/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 105mAh/g.
Embodiment 6
With 0.1 moles of hydrogen Lithium Oxide 98min, the ferrous FeSO of 0.1 mol sulfuric acid
47H
2O and 0.09 mole of phosphoric acid ammonium and 0.01 mole of simple substance sublimed sulphur S mix, add in the polyester jar, add the 80ml raw spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 400 ℃ with 5 ℃/minute temperature rise rates,, cool to room temperature with the furnace this temperature insulation 8 hours.Take out pre-imitation frosted glass, add an amount of industrial spirit, sealing back ball milling 8 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen and hydrogen mixture atmosphere (nitrogen: hydrogen=9: 1, volume ratio), this temperature insulation 8 hours, be cooled to room temperature with stove.Gained positive electrode material LiFe (P
0.9S
0.1O
4) be designated as sample F.F is gained LiFe (P among Fig. 1
0.9S
0.1O
4) XRD figure, the adding of sulphur does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks due to the sulphur.F is gained LiFe (P among Fig. 2
0.9S
0.1O
4) stereoscan photograph, sample topography is for greater than 0.5 micron primary particle size and some crystal grain of growing up unusually, it is more serious to reunite.
Take by weighing 1.125g LiFe (P
0.9S
0.1O
4) positive powder, add the 0.255g carbon black, 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 10mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and 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 3.38V, the reversible specific capacity first of battery F is about 109mAh/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 110mAh/g.
Embodiment 7
With 0.05 mole of Quilonum Retard, 0.1 mole of iron protochloride FeCl
2And 0.0925 mole of phosphoric acid ammonium and 0.0075 mole of silica gel SiO
2Colloidal sol mixes, and adds in the polyester jar, adds the 100ml deionized water, mixed 7 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 400 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove.Take out pre-imitation frosted glass, add an amount of industrial spirit, sealing back ball milling 6 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove.Gained positive electrode material LiFe (P
0.925Si
0.075O
4) be sample G.G is gained LiFe (P among Fig. 1
0.925Si
0.075O
4) XRD 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 silicon.G is gained LiFe (P among Fig. 2
0.925Si
0.075O
4) stereoscan photograph, sample topography is 0.3 ~ 1 micron primary particle size and some reunions.
Take by weighing 0.3g LiFe (P
0.925Si
0.075O
4) positive powder, add the 0.068g carbon black, 0.032g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and G is the discharge curve first of battery among Fig. 3, show that the battery of surveying has the stable discharge voltage plateau of 3.38V, the reversible specific capacity first of battery G is about 78mAh/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 83mAh/g.
Embodiment 8
With 0.5 mole of Quilonum Retard and the ferrous Fe (CH of 1 molar acetate
3COO)
22H
2O and 0.8 mole of phosphoric acid hydrogen, two ammoniums and 0.2 mole of tetraethoxy Si (OC
2H
5)
4Mix, add in the polyester jar, add the 65ml industrial spirit, mixed 7 hours on planetary ball mill the sealing back, and discharging oven dry back rises to 400 ℃ with 5 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove.Take out pre-imitation frosted glass, add an amount of industrial spirit, sealing back ball milling 6 hours, discharging oven dry back rises to 700 ℃ with 4 ℃/minute temperature rise rates under 0.3 liter/minute nitrogen atmosphere, this temperature insulation 8 hours, be cooled to room temperature with stove.Gained positive electrode material LiFe (P
0.8Si
0.2O
4) be designated as sample H.H is gained LiFe (P among Fig. 1
0.8Si
0.2O
4) XRD figure, the adding of silicon does not change LiFePO
4Crystalline structure, keep and LiFePO
4(pure LFP) identical diffraction peak is not observed the impurity peaks due to the silicon.H is gained LiFe (P among Fig. 2
0.8Si
0.2O
4) stereoscan photograph, sample topography is the uneven grain of 0.5 ~ 2 micron primary particle size, unusual grain growth and a large amount of the reunion.
Take by weighing 0.9g LiFe (P
0.8Si
0.2O
4) positive powder, add the 0.204g carbon black, 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed by 20mA/g (in positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and 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 battery H is about 81mAh/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 75mAh/g.
Claims (9)
1. the preparation method of a phosphorus position partly substituted iron lithium phosphate powder is characterized in that, described lithium ion battery anode material lithium iron phosphate molecular formula LiFeP
1-yD
yO
4Expression, wherein D is the replacement source, 0＜y≤0.5;
The preparation method's of described phosphorus position partly substituted iron lithium phosphate powder concrete mode is as follows:
Lithium salts, ferrous salt and phosphoric acid salt and substituent are pressed atomic ratio Li: Fe: P: D=1: 1: (1-y): y, batch mixing of the molar ratio of 0＜y≤0.5 wherein, adding at least a in deionized water, industrial spirit and the dehydrated alcohol mixes as blending agent, 6～12 hours mixing and ball milling time, after drying under 40～70 ℃, under inert atmosphere or reducing atmosphere, heat 400～550 ℃, be incubated 5～10 hours and carry out precalcining; Secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtain phosphorus position partly substituted iron lithium phosphate LiFeP then
1-yD
yO
4Powder.
2. according to the preparation method of the described phosphorus position partly substituted iron lithium phosphate powder of claim 1, it is characterized in that described substituent is that the boron replacement source of boron-containing compound, the tungsten of Tungstenic compound replace the sulphur replacement source of source, sulfurous organic compound and simple substance and the silicon replacement source of silicon-containing compound.
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 boron replacement source is at least a in boric acid, trimethyl borate and the boron oxide.
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 tungsten replacement source is at least a in wolframic acid and the ammonium tungstate.
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 sulphur replacement source is at least a in sulphur S simple substance, thiocarbamide, sodium sulphite and the ammonium sulfide.
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 silicon replacement source is at least a in silica gel, tetraethoxy, Union carbide A-162 and the Trichloromonosilane.
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, at least a in LiOH, lithium oxalate and 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, the ferrous sulfate.
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 in ammonium phosphate, Secondary ammonium phosphate and the primary ammonium phosphate at least a.
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2005
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