CN1803592A - Method for preparing lithium enriched lithium ion phosphate powder - Google Patents
Method for preparing lithium enriched lithium ion phosphate powder Download PDFInfo
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- CN1803592A CN1803592A CNA2005101324314A CN200510132431A CN1803592A CN 1803592 A CN1803592 A CN 1803592A CN A2005101324314 A CNA2005101324314 A CN A2005101324314A CN 200510132431 A CN200510132431 A CN 200510132431A CN 1803592 A CN1803592 A CN 1803592A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium ion
- enriched
- preparation
- phosphate
- Prior art date
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Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 39
- 229910019142 PO4 Inorganic materials 0.000 title claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 17
- 239000010452 phosphate Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims description 18
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000005338 frosted glass Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- 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
- 229910052810 boron oxide Inorganic materials 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 abstract 1
- 150000003017 phosphorus Chemical class 0.000 abstract 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 238000009413 insulation Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008901 benefit 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
- -1 polypropylene Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 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
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 239000002228 NASICON Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 239000002772 conduction electron 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
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 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
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 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
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 229910052726 zirconium Inorganic materials 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 invention discloses a preparation method for lithium-rich ferrous lithium phosphate powder with molecular formula as Li(1+2x)Fe(P1-xBx)O4 in electrochemical power source material. Wherein, mixing the lithium salt, ferrous iron salt, phosphorus salt and substitude of borone-containing compound as given mole ratio; baking, pre-calcining, and hihg-temperature secondary calcining to obtain the product. This invention is convenient to realize part substitude and lithium enrichment on parent body with solid phase method to improve cell capacity and cycle performance, and has wide application future.
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 lithium enriched lithium ion 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
4Become 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.E1ectrochem.Soc., 144 (1997) 1188] research group has synthesized iron lithium phosphate at first, and 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.
Iron lithium phosphate LiFePO
4Mix the material that electricity is led as a kind of, in conduction electron, conductive lithium ionic solid electrolyte material especially.In one's early years the lithium ion solid electrolyte material of a class better performances of research is that to have general formula be LiM
2(PO
4)
3Solid, work as M
4+During for Zr, Ti, Ge, Hf, have the NASICON structure, they are by MO
6Octahedron and PO
4Tetrahedron dihedral altogether becomes [M
2(PO
4)
3]
-Rigid structure, lithium ion move in the three-dimensional structure tunnel.Utilize the bigger low valence metal ion of radius partly to substitute M
4+, find that ionic conductivity can further improve, this doping can obtain Li
1+xM
2-xM '
x(PO
4)
3Type sosoloid is typically Li
1.3Al
0.3Ti
1.7(PO
4)
3Has the highest lithium ion conductivity.Because lithium ion is easy to volatilization loss in calcining, so this type sosoloid has just increased the concentration of migration lithium ion in the compound design.This method of design is at iron lithium phosphate (LiFePO
4) do not use as yet in the material and report.
The present invention proposes partly to substitute iron lithium phosphate LiFePO with the boron element
4In phosphorus, lithium ion surpasses stoichiometry 1 with the compensation charge balance, utilizes two step solid phase methods to prepare iron lithium phosphate Li
1+2xFe (P
1-xB
x) O
4The method of (0＜x＜0.5) powder has improved the base batteries performance of iron lithium phosphate, 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 with the boron element and partly substitute iron lithium phosphate LiFePO
4In phosphorus, lithium ion surpasses stoichiometry 1 with the compensation charge balance, significantly improves a kind of preparation method of lithium enriched lithium ion phosphate powder of the anode material for lithium ion battery of parent base batteries performance.It is characterized in that described lithium ion battery anode material lithium iron phosphate molecular formula Li
1+2xFe (P
1-xB
x) O
4Expression, wherein B is an alternate source, 0＜x＜0.5.
The preparation method's of described lithium enriched lithium ion phosphate powder concrete mode is as follows:
With lithium salts, ferrous salt, phosphoric acid salt and surrogate by element Li: Fe: P: B=(1+2x): 1: (1-x): the molar ratio of x is once weighed, batch mixing, adding the mix grinding medium mixes, 6～12 hours mixing and ball milling time, dry down at 40～70 ℃, heat 400～550 ℃ under inert atmosphere or reducing atmosphere, being incubated 5～10 hours carries out precalcining; Pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down, under inert atmosphere or reducing atmosphere, 550～850 ℃ of secondary clacinings obtain lithium enriched lithium ion phosphate Li then
1+2xFe (P
1-xB
x) O
4Powder.
Described mix grinding medium is at least a in deionized water, industrial spirit and the dehydrated alcohol.
Described boron alternate source is at least a in boric acid, trimethyl borate and the boron oxide.
Described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate, Lithium Acetate and the lithium nitrate.
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 are 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, surrogate is the boron-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, and phosphorus position partly is substituted by boron, and lithium ion surpasses stoichiometry 1 with compensation charge equilibrated anode material for lithium ion battery iron lithium phosphate Li
1+2xFe (P
1-xB
x) O
4(0＜x＜0.5) powder, first discharge specific capacity can reach 90～150mAh/g under the room temperature.The present invention utilizes and originates widely that boron compound is surrogate, be easy to realize that at the parent phosphate potential part substitutes and the enrichment of lithium ion by 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
Figure is the cycle performance graphic representation of embodiment 1～5 prepared lithium ion battery.
Test conditions: voltage 2.5V-4.2V, 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.
Embodiment
The invention provides with the boron element and partly substitute iron lithium phosphate LiFePO
4In phosphorus, lithium ion surpasses stoichiometry 1 with the compensation charge balance, significantly improves a kind of preparation method of lithium enriched lithium ion phosphate powder of the anode material for lithium ion battery of parent base batteries performance.Described lithium ion battery anode material lithium iron phosphate molecular formula Li
1+2xFe (P
1-xB
x) O
4Expression, wherein B is a substituent, 0＜x＜0.5.
The concrete mode of the preparation method of described lithium enriched lithium ion phosphate powder is as follows:
Lithium salts, ferrous salt, phosphoric acid salt and surrogate are pressed element Li: Fe: P: B=(1+2x): 1: (1-x): the molar ratio of x is once reinforced, add at least a in deionized water, industrial spirit and the dehydrated alcohol then as the mix grinding medium, 6～12 hours mixing and ball milling time, dry down at 40～70 ℃, heat 400～550 ℃ under inert atmosphere or reducing atmosphere, being incubated 5～10 hours carries out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down under inert atmosphere or reducing atmosphere, were heated 550～850 ℃ of secondary clacinings then, obtain lithium enriched lithium ion phosphate Li
1+2xFe (P
1-xB
x) O
4Powder.
Described boron replacement source is at least a in boric acid, trimethyl borate and the boron oxide.
Described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate and Lithium Acetate and the lithium nitrate.
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, primary ammonium phosphate and the ferrous phosphate at least a.
With Li
1+2xFe (P
1-xB
x) O
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
6Being dissolved in 1: 1 mixed solvent for ethyl-carbonate and methylcarbonate of volume ratio is electrolytic solution, and 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 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 0.05025 mole of Quilonum Retard Li
2CO
3, 0.1 mole of Ferrox Fe (C
2O
4) 2H
2O and 0.09975 mole of phosphoric acid ammonium dihydrogen NH
4H
2PO
4With 0.00025 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, discharging oven dry back is 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, obtain pre-imitation frosted glass, be medium ball milling 6 hours again with the industrial spirit, discharging oven dry back rose 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, obtain positive electrode material Li
1.005Fe (P
0.9975B
0.0025) O
4, be designated as B1.
The chemical property of gained sample is measured as follows: take by weighing 0.9g Li
1.005Fe (P
0.9975B
0.0025) O
4Positive 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; The alkene microporous membrane is a barrier film in poly-; Metal lithium sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours charges to 4.2 volts by the speed of 20mA/g (in positive pole), be discharged to 2.5 volts, the reversible specific capacity first that obtains battery (B1 in the accompanying drawing) is about 148mAh/g, and through 20 circulations, specific discharge capacity remains on more than the 132mAh/g.
Embodiment 2
With 0.1015 moles of hydrogen Lithium Oxide 98min LiOHH
2O, the ferrous Fe (CH of 0.1 molar acetate
3COO)
22H
2O and 0.09925 mole of phosphoric acid hydrogen, two ammonium (NH
4)
2HPO
4With 0.00075 mole of trimethyl borate (CH
3O)
3B mixes, add in the polyester jar, add the 80ml industrial spirit, mixed 6 hours on planetary ball mill the sealing back, discharging oven dry back rose 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 and be incorporated in the polyester jar, add appropriate amount of deionized water, sealing back 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, obtain positive electrode material Li
1.015Fe (P
0.9925B
0.0075) O
4, be designated as B2.
Take by weighing 1.125gLi
1.015Fe (P
0.9925B
0.0075) O
4Positive powder, add the 0.169g carbon black, 0.12g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible specific capacity first that obtains battery (B2 in the accompanying drawing) is about 119mAh/g, through 20 circulations, specific discharge capacity remains on more than the 106mAh/g.
Embodiment 3
With 0.12 molar nitric acid lithium LiNO
3, the ferrous FeSO of 0.1 mol sulfuric acid
47H
2O and 0.09 mole of phosphoric acid ammonium (NH
4)
3PO
4With 0.005 mole of boron oxide (B
2O
3) mix, add in the polyester jar, add the 55ml deionized water, mixed 7 hours on planetary ball mill the sealing back, discharging oven dry back is 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, obtain pre-imitation frosted glass, be medium ball milling 10 hours again with the deionized water, discharging oven dry back rose 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, obtain positive electrode material Li
1.2Fe (P
0.9B
0.1) O
4, be designated as B3.
Take by weighing 1.02gLi
1.2Fe (P
0.9B
0.1) O
4Positive powder, add the 0.184g carbon black, 0.096g polyvinylidene difluoride (PVDF), press embodiment 1 method system electrode slice and assembled battery, speed in 34mA/g (with positive pole) charges to 4.2 volts, is discharged to 2.5 volts, and the reversible specific capacity first that obtains battery (B3 in the accompanying drawing) is about 110mAh/g, through 20 circulations, specific discharge capacity remains on more than the 110mAh/g.
Embodiment 4
With 0.08 mole of lithium oxalate Li
2(C
2O
4), 0.1 mole of iron protochloride FeCl
2And 0.07 mole of phosphoric acid ammonium dihydrogen and 0.03 mole of boric acid mixing, add in the polyester jar, add the 85ml raw spirit, mixed 11 hours on planetary ball mill the sealing back, discharging oven dry back is under 0.3 liter/minute decomposed ammonia atmosphere, rise to 480 ℃ with 5 ℃/minute temperature rise rates,, be cooled to room temperature with stove this temperature insulation 5 hours, taking out pre-imitation frosted glass is incorporated in the polyester jar, add an amount of industrial spirit, sealing back ball milling 6 hours, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 680 ℃ with 4 ℃/minute temperature rise rates, this temperature insulation 11 hours, be cooled to room temperature with stove, obtain positive electrode material Li
1.6Fe (P
0.7B
0.3) O
4, be designated as B4.
Take by weighing 0.9gLi
1.6Fe (P
0.7B
0.3) O
4Positive 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 the reversible specific capacity first that obtains battery (B4 in the accompanying drawing) is about 95mAh/g, through 20 circulations, specific discharge capacity remains on more than the 82mAh/g.
Embodiment 5
With 0.18 molar acetate lithium Li (CH
3COO), 0.1 mole Ferrox and 0.06 mole of phosphoric acid hydrogen, two ammoniums and 0.04 mole of boric acid mix, add in the polyester jar, add the 65ml raw spirit, mixed 6.5 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,, be cooled to room temperature with stove this temperature insulation 8.5 hours, taking out pre-imitation frosted glass is incorporated in the polyester jar, add appropriate amount of deionized water, sealing back ball milling 6 hours, discharging oven dry back is under 0.3 liter/minute nitrogen atmosphere, rise to 700 ℃ with 4 ℃/minute temperature rise rates, this temperature insulation 8 hours, be cooled to room temperature with stove, obtain positive electrode material Li
1.8Fe (P
0.6B
0.4) O
4, be designated as B5.
Take by weighing 0.3375gLi
1.8Fe (P
0.6B
0.4) O
4Positive 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 the reversible specific capacity first that obtains battery (B5 in the accompanying drawing) is about 113mAh/g, through 20 circulations, specific discharge capacity remains on more than the 100mAh/g.
Claims (5)
1. the preparation method of a lithium enriched lithium ion phosphate powder is characterized in that, described lithium ion battery anode material lithium iron phosphate molecular formula Li
1+2xFe (P
1-xB
x) O
4Expression, wherein B is an alternate source, 0＜x＜0.5;
The preparation method's of described lithium enriched lithium ion phosphate powder concrete mode is as follows:
Lithium salts, ferrous salt, phosphoric acid salt and surrogate are pressed element atomic ratio Li: Fe: P: B=(1+2x): 1: (1-x): the molar ratio of x is once reinforced, add at least a in deionized water, industrial spirit and the dehydrated alcohol then as the mix grinding medium, 6～12 hours mixing and ball milling time, dry down at 40～70 ℃, heat 400～550 ℃ under inert atmosphere or reducing atmosphere, being incubated 5～10 hours carries out precalcining; With pre-imitation frosted glass secondary ball milling 6～12 hours, 40～70 ℃ of oven dry down under inert atmosphere or reducing atmosphere, were heated 550～850 ℃ of secondary clacinings then, obtain lithium enriched lithium ion phosphate Li
1+2xFe (P
1-xB
x) O
4Powder.
2. according to the preparation method of the described lithium enriched lithium ion phosphate powder of claim 1, it is characterized in that described boron alternate source is at least a in boric acid, trimethyl borate and the boron oxide.
3. according to the preparation method of the described lithium enriched lithium ion phosphate powder of claim 1, it is characterized in that described lithium salts is Li
2CO
3, at least a in LiOH, lithium oxalate, Lithium Acetate and the lithium nitrate.
4. according to the preparation method of the described lithium enriched lithium ion phosphate powder of claim 1, it is characterized in that described ferrous salt is at least a in Ferrox, Iron diacetate, iron protochloride and the ferrous sulfate.
5. according to the preparation method of the described lithium enriched lithium ion 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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| CN100440591C (en) * | 2006-10-12 | 2008-12-03 | 卢星河 | Pre-processing method for phosphorous anode material, and obtained phosphorous anode material |
| CN100450920C (en) * | 2006-11-24 | 2009-01-14 | 中南大学 | Method for preparing powder of lithium iron phosphate |
| CN100450919C (en) * | 2006-11-24 | 2009-01-14 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| CN101807697A (en) * | 2010-04-29 | 2010-08-18 | 江苏中欧材料研究院有限公司 | Method for synthesizing lithium iron phosphate with full substitute structure |
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| US6153333A (en) * | 1999-03-23 | 2000-11-28 | Valence Technology, Inc. | Lithium-containing phosphate active materials |
| JP3639468B2 (en) * | 1999-08-04 | 2005-04-20 | 三洋電機株式会社 | Lithium secondary battery |
| JP2002117903A (en) * | 2000-10-05 | 2002-04-19 | Sony Corp | Nonaqueous electrolyte battery |
| FR2848205B1 (en) * | 2002-12-05 | 2006-03-24 | Commissariat Energie Atomique | BORON SUBSTITUTED LITHIUM INSERTION COMPOUNDS, ELECTRODE ACTIVE MATERIALS, ACCUMULATORS AND ELECTROCHROME DEVICES |
| CN1208241C (en) * | 2003-02-17 | 2005-06-29 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
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| CN1305148C (en) * | 2005-01-12 | 2007-03-14 | 清华大学 | Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate |
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2005
- 2005-12-23 CN CNB2005101324314A patent/CN100418255C/en not_active Expired - Fee Related
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| CN101867047A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Lithium ion secondary battery anode lithium-rich active material and method for preparing the same |
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| CN115849454A (en) * | 2022-11-22 | 2023-03-28 | 湖北万润新能源科技股份有限公司 | Preparation method of sodium ferrous sulfate cathode material |
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