CN1903707A - Semiwet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate - Google Patents
Semiwet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate Download PDFInfo
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- CN1903707A CN1903707A CNA2006101114448A CN200610111444A CN1903707A CN 1903707 A CN1903707 A CN 1903707A CN A2006101114448 A CNA2006101114448 A CN A2006101114448A CN 200610111444 A CN200610111444 A CN 200610111444A CN 1903707 A CN1903707 A CN 1903707A
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- lithium
- suspension liquid
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 10
- 229940116007 ferrous phosphate Drugs 0.000 title claims description 9
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims description 9
- 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 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 239000000725 suspension Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000002482 conductive additive Substances 0.000 claims abstract description 15
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000010298 pulverizing process Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 50
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 46
- 238000013019 agitation Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 238000000197 pyrolysis Methods 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 17
- 238000005118 spray pyrolysis Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 14
- 150000001722 carbon compounds Chemical class 0.000 claims description 13
- 239000002019 doping agent Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000003610 charcoal Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- -1 monometallic Chemical compound 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000003595 mist Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005275 alloying Methods 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 229910010710 LiFePO Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 7
- 239000010955 niobium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910007247 Li(CH3COO).2H2O Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 240000007762 Ficus drupacea Species 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a method for preparing ferrous lithium phosphate by using semi-wet method. Said method includes the following steps: in the compounds containing Li, Fe and P selecting one water-insoluble compound and others are water-soluble, placing the above-mentioned water-insoluble compound into the above-mentioned water-soluble compound solution to obtain a suspension; in said suspension Li content, Fe content and P content must be met with the following formula: [mLi+n(1-m)/n M]:Fe:qPO4=1:1:1(1), in formula (1) n is chemical valence of alloying element M, m is mole number of Li, (1-m)/n is mole number of alloying element M and P and q respectively are mole numbers of Fe and PO4; adding reduction electro-conductive additive, spraying and pyrolyzing suspension so as to obtain precursor powder, roasting said precursor powder and pulverizing to obtain the invented product.
Description
Technical field
The present invention relates to a kind of preparation method of energy and material, relate in particular to a kind of preparation method of lithium ion cell positive actives-LiFePO 4.
Background technology
Lithium-ion secondary cell is the new generation of green energy, has advantages such as high-energy-density, high cycle performance, low self-discharge rate, memory-less effect, operating temperature range be wide.In numerous areas widespread uses such as mobile telephone, laptop computer, pick up camera, power tools.March to electric automobiles.But the research and the application of anode material for lithium-ion batteries focus mostly in LiCoO at present
2, LiNiO
2And LiMn
2O
4Deng.Spinel LiMn wherein
2O
4Cost is low, and security is better, but cycle performance and high-temperature behavior are poor; LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, material consistence and poor reproducibility, and have serious safety problem; LiCoO
2Because high comprehensive performance, thus be the anode material for lithium-ion batteries of present unique large-scale commercial production, but cost an arm and a leg, certain toxicity is arranged and have certain safety problem.
Padhi in 1997 and Goodenoagh report the LiFePO of olivine structural first
4Have to insert and take off the lithium function, make LiFePO
4The class material is subjected to extensive concern and actively research and development.Because raw material resources are rich and easy to get, LiFePO
4, FePO
4Structure is all being stablized below 400 ℃.The theoretical specific discharge capacity 170mAh/g and the overwhelming majority can develop, operating voltage 3.0 (high magnification)-3.4V (low range) is very steady, good with the electrolytic solution consistency, volume only reduces 6.5% during charging, little the increasing of volume is complementary when charging with the carbon negative pole, particularly nontoxic, high-temperature behavior, good cycle and security are good, and power truck is popularized hope.Therefore people expect LiFePO
4To make lithium ion battery revolutionary variation occur, lithium ion battery widespread usage in power truck is become a reality.
At present, actual production LiFePO
4Method be mostly to be called the what is called " dry method " of high temperature solid-state method, be about to contain the lithium source, source of iron, the solid chemical compound in phosphorus source is weighed by a certain percentage, placed ball mill long-time (for example 18-36 hour, 18-48 hour etc.) ground and mixed, place High Temperature Furnaces Heating Apparatus then, burn till once or twice at middle and high two temperature sections.The shortcoming of " dry method " is: the milling time that (1) mixes be difficult for to determine, can not continuous production; 2) would rather grind time expand for guaranteeing to mix, time-consuming; (3) it is inhomogeneous etc. each batch products to take place easily.
Summary of the invention
The purpose of this invention is to provide a kind of semi-wet method and prepare the method for LiFePO 4 and the LiFePO 4 of preparation thereof.The method technology that semi-wet method of the present invention prepares LiFePO 4 is simple, the suitability for industrialized serialization is produced, raw material mixes, the product performance uniformity, prepared LiFePO 4 steady quality, thus overcome the problem that present production LiFePO 4 exists.
Semi-wet method of the present invention prepares the method for LiFePO 4, and its step is as follows:
1. preparation contains the suspension liquid of the compound of Li, Fe, P
1) contain lithium, iron, phosphorus and doped element M in the suspension liquid and meet following formula:
[mLi+n(1-m)/n M]∶pFe∶qPO
4＝1∶1∶1 (1)
(1) n is the valency of doped element M in the formula, and m is the mole number of Li, (1-m)/n is the mole number of doped element M, p, q are respectively Fe and PO
4Mole number, (1) formula is by (2) formula
MLi
++ (1-m)/n M
N++ pFe
2++ qPO
4 3-=Li
mM
(1/m)/nFePO
4Determine that (2) when (1-m)/n=0, the mole number that promptly contains the compound of doped element M is zero, that is does not contain the compound of doped element M in the suspension liquid, then the mol ratio of Li: Fe: P meets the requirement of following formula:
MLi: pFe: qPO
4=1: the mole number of 1: 1 (3) solid chemical compound=(weight of compound * its content)/molar mass; Volumetric molar concentration * the liquid volume of More's number=compound solution of compound solution;
2) appoint in the compound that contains Li, Fe, P and get a kind of water-fastly, other is water-soluble; Take by weighing particle diameter and be micro mist below 10 microns or be the sedimentary above-mentioned water-fast compound of having chosen of freshly prepd nanoparticle, and calculate its mole number;
The insoluble compound of water that wherein contains Li is: lithium fluoride, one of Quilonum Retard or Trilithium phosphate (being the phosphorus source simultaneously); The insoluble compound of water that contains Fe is: one of iron protocarbonate, iron protoxide, Ferrox, ferrous phosphate (being the phosphorus source simultaneously), tertiary iron phosphate (being the phosphorus source simultaneously) or ferric oxide; The insoluble compound of water that contains P is: one of Trilithium phosphate (being the lithium source simultaneously), ferrous phosphate (being source of iron simultaneously) or tertiary iron phosphate (being source of iron simultaneously);
The water soluble compound that wherein contains Li is: one of lithium hydroxide, monometallic (being the phosphorus source simultaneously), Lithium Acetate, Lithium Citrate de, lithium chloride or lithium nitrate; The water soluble compound that contains Fe is: one of Iron diacetate, ironic oxalate, iron(ic) chloride, iron protochloride, Iron nitrate or iron nitrate; The water soluble compound that contains P is: one of phosphoric acid, monometallic (being the lithium source simultaneously), ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate; Dopant ion M wherein
N+Be ionic radius and Li
+The high valence ion that ionic radius is close: Mg
2+, Al
3+, Zr
4+Or Nb
5+One of, contain dopant ion M
N+Compound be: contain dopant ion M
N+One of oxide compound, oxyhydroxide, nitrate, organic acid salt or organometallic compound;
3) according to the mole number of the above-mentioned water-fast compound that has selected and (1) formula, calculate respectively and take by weighing required weight other water-soluble compound, contain the compound of dopant ion; Add while stirring respectively again in the entry,, make each solution to all dissolvings; The water-fast compound that contains dopant ion is that particle diameter is a micro mist below 10 microns;
4) under agitation condition, earlier above-mentioned each solution that has prepared and stream are added in the reactor, keep stirring down and continue to add the above-mentioned water-fast compound that has taken by weighing, the water-fast compound that contains dopant ion, stir, make suspension liquid;
2. add the reduction conductive additive
Under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive while stirring, continue again to stir 1-3 hour, make suspension liquid uniform and stable; The reduction conductive additive is that charcoal or pyrolysis can produce one of carbon compound or its arbitrary combination; The conductive additive that perhaps reduces is that charcoal or pyrolysis can produce in the powder of one of carbon compound or its arbitrary combination and thin inert metal or the subsequent technique and can be reduced to one of inert metal compound of this metal-powder; Add charcoal or pyrolysis and can produce the amount of one of carbon compound or its arbitrary combination for estimating the 3-15% of product weight, the amount that adds the powder of thin inert metal is 1% of expectation product weight, and the content of metal is for estimating 1% of product weight in the inert metal compound of adding; Wherein, charcoal is superconduction carbon black or superfine graphite; Wherein can to produce carbon compound be organic compound-sucrose or citric acid, natural high moleculer eompound-starch or one of synthetic macromolecular compound polyethylene powders or polyvinyl alcohol in pyrolysis; Wherein the powder of thin inert metal is the powder of Ag or Cu; The inert metal compound that can be reduced to this metal-powder in subsequent technique is oxide compound, the oxyhydroxide of Ag or Cu, one of nitrate, organic acid salt or organometallics;
3. spray pyrolysis suspension liquid
With above-mentioned uniform and stable suspension liquid under agitation condition, send into the centrifugal energy nozzle that the centrifugal energy nozzle rotating speed is 18000-24000 rev/min a spray pyrolysis device through volume pump, suspension liquid is collected through cyclonic separator and sack cleaner behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, makes to contain Li
mM
(1-m)/nFePO
4Or LiFePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. roasting, pulverizing
Above-mentioned precursor powder is sent in the High Temperature Furnaces Heating Apparatus, under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-20 hour, then be warming up to 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, pulverize, cross 300 mesh sieves and promptly get lithium ion cell positive active material/carbon cladded ferrous lithium phosphate crystalline powder; Or under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, send into again after mixing in the High Temperature Furnaces Heating Apparatus in nonoxidizing atmosphere after 600-800 ℃ of constant temperature calcining 5-20 hour through grinding, take out after being cooled to normal temperature, promptly get lithium ion cell positive active material/carbon cladded ferrous lithium phosphate powder through pulverizing, cross 300 mesh sieves.
Described nonoxidizing atmosphere is oxygen-free N
2Atmosphere, Ar atmosphere, (N
2+ H
2) mixed-gas atmosphere or (Ar+H
2One of) mixed-gas atmosphere.
Described High Temperature Furnaces Heating Apparatus can be tube furnace, box-type furnace, continuous tunnel furnace and vertical heater, but wherein continuous tunnel furnace and vertical heater can be interrupted also continuous production of production.
Reduction conduction of conductive additive and reductive action are meant that carbon adding or that pyrolysis produces is that conductive agent can at high temperature reduce Fe again
3+Be Fe
2+Dual-use function.
In the compound that contains Li, Fe, P, appoint get a kind of water-fast, it is micro mist below 10 microns or freshly prepd nanoparticle throw out for particle diameter, can do nucleus or induced nuclei when generating LiFePO 4, promptly when spray pyrolysis in the solution compound with suspension liquid in solia particle be that the center is gathered and pyrolysis chemical combination generates Li
mM
(1-m)/nFePO
4Or LiFePO
4The process of nucleus; Therefore in subsequent technique through the resulting Li of roasting
mM
(1-m)/nFePO
4Or LiFePO
4Particle diameter is little and even.
The crystal grain of the lithium ion cell positive actives LiFePO 4 that the method that adopts semi-wet method of the present invention to prepare LiFePO 4 is prepared is nano level, the particle size of its reunion is below 10 μ m, can find out that from its x-ray diffraction pattern it is an olivine-type structure, and not have the dephasign peak; Can find out the even and most＜10 μ m of particle from its stereoscan photograph; Its size distribution figure proves that further particle diameter is below 10 μ m.Because its crystal grain is in nano level, particle is in micron order and can reduces Li
+Diffusion length makes Li
+At LiFePO
4Velocity of diffusion increases in the lattice, and LiFePO
4Crystal grain has carbon to coat and LiFePO
4Intercrystalline has atoms metal to build bridge, and adds that the high volence metal ion doping forms LiFePO
4Lattice imperfections etc. have improved LiFePO greatly
4Electron conduction.Adopt the lithium ion battery of the present invention's assembling higher capacity to be arranged, high-rate discharge ability and cycle performance are preferably arranged.
The method technology that semi-wet method of the present invention prepares LiFePO 4 is simple, the suitability for industrialized serialization is produced, and raw material mixes, the product performance uniformity, prepared LiFePO 4 steady quality.
Description of drawings
Fig. 1 is for pressing the LiFePO of embodiment 1 preparation
4X-ray diffracting spectrum.
Fig. 2 is for pressing the prepared LiFePO of embodiment 1
4Stereoscan photograph.
Fig. 3 is for pressing the prepared LiFePO of embodiment 1
4Size distribution figure.
Fig. 4 is for pressing the prepared LiFePO of embodiment 1
4Make the 14500-500mAh cylindrical lithium ion battery 0.2C charging and discharging curve of positive electrode active material preparation.
Fig. 5 is for pressing the prepared LiFePO of embodiment 1
4Make each multiplying power discharging curve of 14500-500mAh cylindrical lithium ion battery of positive electrode active material preparation.
Fig. 6 is for pressing the prepared LiFePO of embodiment 1
4Make the 14500-500mAh cylindrical lithium ion battery 1C/1C cycle life curve (not intact) of positive electrode active material preparation.
Raw material required for the present invention, equipment all have commercially available.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
1. in the compound that contains Li, Fe, P, select FeC
2O
4.2H
2O makes the insoluble compound of water and adopts freshly prepd nanoparticle throw out (without drying operation), and method for making is as follows: take by weighing FeCl
2.4H
2O (content 99.8%) 25kg, in the dissolving 50Kg water, other takes by weighing H
2C
2O
4.H
2O (content 99%) 16.3kg is dissolved in 60Kg, the 50 ℃ of hot water, under 120 rev/mins of stirring velocitys two kinds of solution is merged in 240 liters of reactors, transfers PH=4 with ammoniacal liquor; After reaction is finished, continue to stir 1-3 hour,, move into that whizzer dries and be washed till and use 0.1%AgNO with deionized water with decantation washing and precipitating three times
3The inspection washing lotion does not have white precipitate and generates, and is weighed as 27.37kg, analyzes to contain FeC
2O
4.2H
2O 79.96%, calculate thus 121.65 moles of iron content; 121.65 mole Li amount to LiOH.H
2O (99.5%) 5.13kg; 121.65 mole is amounted to H
3PO
4(85%) 14.03kg is under agitation with LIOH.H
2O (99.5%) 5.13kg is dissolved in 30Kg, the 50 ℃ of hot water, under agitation joins in reactor with 30kg, 50 ℃ of water-reducible 14.03kgH of deionization again
3PO
4(85%) in; Again the above-mentioned freshly prepd Ferrox that contains 20% hygroscopic water of 27.37kg is added, stir, make suspension liquid;
2. under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive, estimate LiFePO
4Output=121.65 * 157.76, about 19kg; The content of metal is the 1%-0.48kg inert metal compound of expectation product weight, i.e. superconduction carbon black 0.27kg, starch 0.3kg and CuC in the inert metal compound that the charcoal of adding expectation finished weight 3%-0.57kg or pyrolysis can produce carbon compound and adding in above-mentioned suspension liquid while stirring
2O
4.1/2H
2O 0.48kg continues to stir 1-3 hour again, makes the suspension liquid uniform mixing;
With above-mentioned uniform and stable suspension liquid under agitation condition, sending into CLF type centrifugal energy nozzle rotating speed through volume pump is the centrifugal energy nozzle of 18000-24000 rev/min spray pyrolysis device, suspension liquid is behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, collect through cyclonic separator and sack cleaner, make and contain LiFePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. in the warm vertical heater, in nitrogen atmosphere, kept 20 hours in above-mentioned precursor powder being moved into, enter and take out after cooling section is reduced to normal temperature, move into again in the high temp tunnel stove, after mixing at (90%N through grinding in 360 ± 10 ℃ of constant temperature
2+ 10%H
2) in the atmosphere, after 700 ± 10 ℃ of constant temperature keep 15 hours, enter and take out after cooling section is reduced to normal temperature, through pulverizing, crossing 300 mesh sieves, promptly get lithium ion cell positive active material/carbon cladded ferrous lithium phosphate powder.
Fig. 1 finds out that from figure it is an olivine-type structure, and does not have the dephasign peak for pressing the x-ray diffraction pattern of the prepared ferrous phosphate lithium powder of embodiment 1.Fig. 2 is for press the stereoscan photograph of the prepared ferrous phosphate lithium powder of embodiment 1, finds out that particle evenly and most＜10 μ m.Fig. 3 is for press the size distribution of the prepared ferrous phosphate lithium powder of embodiment 1, and further the LiFePO 4 powder diameter for preparing of proof is below 10 μ m.The test specific surface area is 19.5m
2, Fig. 4 charges and discharge electric wire for the 1450-500mAh cylindrical lithium ion battery 0.2C that does the preparation of positive electrode active material and graphite carbon negative pole by embodiment 1 prepared LiFePO 4, and the LiFePO 4 specific storage is greater than 130mAh.Each high-multiplying power discharge curve that Fig. 5 charges for the 1450-500mAh cylindrical lithium ion battery 1C that presses Fig. 4, the 5C specific discharge capacity is greater than 120mAh/g, and the 7C specific discharge capacity sees Table 1 greater than 120mAh/g.
Each multiplying power discharging specific storage of LiFePO 4 of table 1, embodiment preparation
| Sample | 0.2C | 0.5C | 1C | 3C | 5C | 7C | 10C |
| Embodiment 1 | 136 | 126 | 126 | 125 | 123 | 124 | 115 |
| | 134 | 123 | 123 | 122 | 119 | 118 | - |
| Embodiment 3 | 133 | 123 | 122 | 121 | 118 | 113 | - |
| Embodiment 4 | 132 | 122 | 122 | 121 | 116 | 112 | - |
| Embodiment 5 | 132 | 123 | 122 | 120 | 124 | 110 | - |
1. in the compound that contains Li, Fe, P, select the iron protocarbonate fine powder to make the insoluble compound of water, take by weighing particle diameter and be iron protocarbonate (containing Fe 38%) the micro mist 17kg below 10 microns, contain 115.67 moles of Fe; Take by weighing 113.36 moles Li reduced Li (CH
3COO) .2H
2O (99.5%) 11.62kg, 115.67 moles of P reduced NH
4H
2PO
4(99.0%) Mg reduced MgO (98.5%) 47.33g of 13.44kg and 1.157 moles is under agitation earlier with Li (CH
3COO) .2H
2O (99.5%) 11.62kg and NH
4H
2PO
4(99.0%) 13.44kg is dissolved in 30kg, 60kg respectively and temperature is a wiring solution-forming in 50 ℃ of hot water; Under agitation two kinds of solution and stream are added reactor, again that 17kg iron protocarbonate (containing Fe 38%) micro mist and 47.33g MgO (98.5%) mixing and ball milling is even, under agitation condition, join then above-mentioned and stream after solution in, stir, make suspension liquid;
2. under agitation condition, in above-mentioned suspension liquid, add reduction conductive additive, meter LiFePO
4Output=115.7 * 157.76, about 18.25kg; Adding charcoal or the pyrolysis of estimating finished weight 3%-0.55kg while stirring in above-mentioned suspension liquid can produce carbon compound and estimate finished weight 1%-182.5g inert metal powder, be superfine graphite 0.22kg, sucrose 0.33kg, and superfine cupper powder 182.5g, continue again to stir 1-3 hour, make the suspension liquid uniform mixing;
With above-mentioned uniform and stable suspension liquid under agitation condition, sending into CLF type centrifugal energy nozzle rotating speed through volume pump is the centrifugal energy nozzle of 18000-24000 rev/min spray pyrolysis device, suspension liquid is behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, collect through cyclonic separator and sack cleaner, make and contain Li
0.98Mg
0.01FePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. above-mentioned precursor powder is moved in the tube type high-temperature furnace, under argon atmospher, kept 5 hours in 360 ± 10 ℃ of constant temperature, the constant temperature that then is warming up to 610 ± 10 ℃ kept after 20 hours, enter and take out after cooling section is reduced to normal temperature, coat Li through pulverizing, cross 300 mesh sieves, promptly get the lithium ion cell positive active material/carbon that contains doped with Mg
0.98Mg
0.01FePO
4Powder.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 2 prepared LiFePO 4s in the table 1.
Embodiment 3,
1. in the compound that contains Li, Fe, P, select FePO
4.4H
2O makes the insoluble compound of water and adopts freshly prepd nanoparticle throw out: take by weighing Fe (NO
3)
3.9H
2O (content 98%) 54.9kg is dissolved in 50 ℃ of hot water of 40Kg, and other takes by weighing (NH
4)
2HPO
4(content 99.8%) 17.62kg is dissolved in 50 ℃ of hot water of 50kg, under 120 rev/mins of stirring velocitys two kinds of solution is merged, transfer PH=5-6 with ammoniacal liquor, after reaction is finished, use decantation washing and precipitating three times, the immigration whizzer dries, the solution of weighing merges, and transfers PH=5-6 with ammoniacal liquor, after reaction is finished, with decantation washing and precipitating three times, the immigration whizzer dries, and is weighed as 34.32kg, analyzes to contain FePO
4.4H
2O (82.5%) calculates to such an extent that contain Fe or P 127.04mol thus; Containing the Li mole number is 96% of Fe or P, and promptly 121.96mol needs Li
3(C
6H
5O
7) .4H
2O (99.5%) [(121.96 * 281.98) ÷ 3] ÷ 0.995=11.52kg, doping 1.27mol Zr needs ZrO
2(99.6%) fine powder 157.1g, under agitation in reactor with Li
3(C
6H
5O
7) .4H
2O (99.5%) 11.52kg is dissolved in 80Kg, the 50 ℃ of hot water; Again under agitation with above-mentioned freshly prepd tertiary iron phosphate of 34.32kg and 157.1gZrO
2(99.6%) fine powder adds, and stirs, and makes suspension liquid;
2. under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive, estimate LiFePO
4Output=127.04 * 157.76, about 20kg; The content that pyrolysis that add to estimate finished weight 15%-3.0kg while stirring in above-mentioned suspension liquid can produce metal in the inert metal compound of carbon compound and adding is the inert metal compound of the 1%-250g that estimates product weight, be that polyethylene powders 1.5kg, weight percent concentration are the aqueous solution 20kg (containing polyvinyl alcohol 1.5kg) of 7.5% polyvinyl alcohol, and CuO (cupric 79.9%) powder 250g, continue again to stir 1-3 hour, make the suspension liquid uniform mixing;
With above-mentioned uniform and stable suspension liquid under agitation condition, sending into CLF type centrifugal energy nozzle rotating speed through volume pump is the centrifugal energy nozzle of 18000-24000 rev/min spray pyrolysis device, suspension liquid is behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, collect through cyclonic separator and sack cleaner, make and contain Li
0.96Zr
0.01FePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. above-mentioned precursor powder is moved in the box High Temperature Furnaces Heating Apparatus, at (90%Ar+10%H
2) in the mixed atmosphere, 490 ± 10 ℃ of constant temperature thermal treatment 20 hours then is warming up to 790 ± 10 ℃ of constant temperature and keeps entering and taking out after cooling section is reduced to normal temperature after 5 hours, through pulverizing, cross 300 mesh sieves, get the carbon cladded ferrous lithium phosphate powder of lithium ion cell positive actives doping zirconium.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 3 prepared LiFePO 4s in the table 1.
Embodiment 4,
1. in the compound that contains Li, Fe, P, select Fe
2O
3Make the insoluble compound of water: take by weighing Fe
2O
310kg (95%) calculates to such an extent that contain Fe118.98m mol thus; Contain lithium 95% and be 113.03mol, containing the 113.03mol lithium needs LiCl (99.5%) (113.05 * 42.4) ÷ 0.995=4.816kg, contains 118.98 moles of P reduced (NH
4)
2HPO
4(99.8%) 15.744kg, containing niobium 1%mol is 1.190mol, containing the 1.190mol niobium needs niobium oxalate H
3[NbO (C
2O
4)
3] (99.5%) 449.6g, under agitation with 4.816kg LiCl (99.5%) and 15.744Kg (NH
4)
2HPO
4(99.8%) and 449.6g H
3[NbO (C
2O
4)
3] (99.5%) to be dissolved in 30kg, 70kg, 5kg and temperature respectively be in 50 ℃ of hot water; Under agitation above-mentioned three kinds of solution and stream are added reactor, under agitation above-mentioned 10kg croci is added again, stir, make suspension liquid;
2. under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive, estimate LiFePO
4Output=expectation LiFePO
4Output=118.98 * 157.76, about 18.77kg; Add charcoal or the pyrolysis of estimating finished weight 15%-2.82kg while stirring and can produce carbon compound in above-mentioned suspension liquid, promptly superconduction carbon black 0.25kg, sucrose 2.57kg continue to stir 1-3 hour again, make the suspension liquid uniform mixing;
With above-mentioned uniform and stable suspension liquid under agitation condition, sending into CLF type centrifugal energy nozzle rotating speed through volume pump is the centrifugal energy nozzle of 18000-24000 rev/min spray pyrolysis device, suspension liquid is behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, collect through cyclonic separator and sack cleaner, make and contain Li
0.95Nb
0.01FePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. above-mentioned precursor powder is moved in the vertical moderate oven, in nitrogen atmosphere,, enter and take out after cooling section is reduced to normal temperature, move into again in the high temp tunnel stove, after mixing at (90%N through grinding in 490 ± 10 ℃ of constant temperature thermal treatments 5 hours
2+ 10%H
2) in the atmosphere, after 610 ± 10 ℃ of constant temperature keep 20 hours, enter and take out after cooling section is reduced to normal temperature, through pulverizing, crossing 300 mesh sieves, promptly get the adulterated lithium ion cell positive active material/carbon coating of niobium Li
0.95Nb
0.01FePO
4Powder.
Listed each high-multiplying power discharge capacity of doing the 1450-500mAh cylindrical lithium ion battery 1C charging of positive electrode active material and the preparation of graphite carbon negative pole by embodiment 4 prepared LiFePO 4s in the table 1.
Embodiment 5
1. in the compound that contains Li, Fe, P, select LiF to make the insoluble compound of water, take by weighing LiF (content 99.8%, particle diameter is less than 8 microns) 3.25kg, calculate to such an extent that contain Li 125mol thus; Fe (the CH that under agitation will contain Fe125mol
3COO)
2.4H
2O (99%) 31.06Kg and the (NH that contains P125mol
4)
2HPO
4(99.5%) 16.59kg, being dissolved in 30kg, 70kg and temperature respectively is in 50 ℃ of hot water; Under agitation above-mentioned two kinds of solution and stream are added reactor, more above-mentioned LiF (content 99.8%, particle diameter is less than 8 microns) 3.25kg powder is added, stir, make suspension liquid;
2. under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive, estimate LiFePO
4Output=125 * 157.76, about 19.7kg; Add the pyrolysis of estimating finished weight 15%-2.96kg while stirring and can produce carbon compound in above-mentioned suspension liquid, promptly citric acid 1.46kg, sucrose 1.5kg continue to stir 1-3 hour again, make the suspension liquid uniform mixing;
3: with above-mentioned uniform and stable suspension liquid under agitation condition, sending into CLF type centrifugal energy nozzle rotating speed through volume pump is the centrifugal energy nozzle of 18000-24000 rev/min spray pyrolysis device, suspension liquid is behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, collect through cyclonic separator and sack cleaner, make LiFePO
4Precursor powder; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4. above-mentioned precursor powder is moved in the vertical moderate oven, in nitrogen atmosphere,, enter and take out after cooling section is reduced to normal temperature, move into the high temp tunnel stove through grinding again after mixing, at (90%N in 490 ± 10 ℃ of constant temperature thermal treatments 10 hours
2+ 10%H
2) in the atmosphere, after 790 ± 10 ℃ of constant temperature keep 5 hours, enter and take out after cooling section is reduced to normal temperature, through pulverizing, crossing 300 mesh sieves, promptly get lithium ion cell positive active material/carbon coating LiFePO
4Powder.
Claims (6)
1. a semi-wet method prepares the method for LiFePO 4, and its step is as follows:
1) preparation contains the suspension liquid of the compound of Li, Fe, P
(1) contain lithium, iron, phosphorus and doped element M in the suspension liquid and meet following formula:
[mLi+n(1-m)/nM]∶pFe∶qPO
4＝1∶1∶1 (i)
(i) n is the valency of doped element M in the formula, and m is the mole number of Li, (1-m)/n is the mole number of doped element M, p, q are respectively Fe and PO
4Mole number, when (1-m)/n=0, the mole number that promptly contains the compound of doped element M is zero, that is does not contain the compound of doped element M in the suspension liquid; Then the mol ratio of Li: Fe: P meets the requirement of following formula:
mLi∶pFe∶qPO
4＝1∶1∶1 (ii)
(2) appoint in the compound that contains Li, Fe, P and get a kind of water-fastly, other is water-soluble; Take by weighing particle diameter and be micro mist below 10 microns or be the sedimentary above-mentioned water-fast compound of having chosen of freshly prepd nanoparticle, and calculate mole number;
(3) according to the mole number of the above-mentioned water-fast compound that has selected and (i) formula, calculate respectively and take by weighing required weight other water-soluble compound, contain the compound of dopant ion; Add while stirring respectively again in the entry,, make each solution to all dissolvings; The water-fast compound that contains dopant ion is that particle diameter is a micro mist below 10 microns;
(4) under agitation condition, earlier above-mentioned each solution that has prepared and stream are added in the reactor, keep stirring down and continue to add the above-mentioned water-fast compound that has taken by weighing, the water-fast compound that contains dopant ion, stir, make suspension liquid;
2) add the reduction conductive additive
Under agitation condition, in above-mentioned suspension liquid, add the reduction conductive additive while stirring, continue again to stir 1-3 hour, make suspension liquid uniform and stable; The reduction conductive additive is that charcoal or pyrolysis can produce one of carbon compound or its arbitrary combination; The conductive additive that perhaps reduces is that charcoal or pyrolysis can produce in the powder of one of carbon compound or its arbitrary combination and thin inert metal or the subsequent technique and can be reduced to one of inert metal compound of this metal-powder; Add charcoal or pyrolysis and can produce the amount of one of carbon compound or its arbitrary combination for estimating the 3-15% of product weight, the amount that adds the powder of thin inert metal is 1% of expectation product weight, and the content of metal is for estimating 1% of product weight in the inert metal compound of adding;
3) spray pyrolysis suspension liquid
With above-mentioned uniform and stable suspension liquid under agitation condition, send into the centrifugal energy nozzle that the centrifugal energy nozzle rotating speed is 18000-24000 rev/min a spray pyrolysis device through volume pump, suspension liquid is collected through cyclonic separator and sack cleaner behind centrifugal energy nozzle atomizing, pyrolysis and preliminary chemical combination, makes to contain Li
mM
(1-m)/nFePO
4Or LiFePO
4Crystal seed or induce the precursor powder of crystal seed; Spray pyrolysis device temperature in is 310-330 ℃, and the bag filter temperature in is 100-120 ℃;
4) roasting, pulverizing:
Above-mentioned precursor powder is sent in the High Temperature Furnaces Heating Apparatus, under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-20 hour, then be warming up to 600-800 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, pulverize, cross 300 mesh sieves and promptly get lithium ion cell positive active material/carbon cladded ferrous lithium phosphate crystalline powder; Or under nonoxidizing atmosphere in 350-500 ℃ of constant temperature calcining 5-20 hour, take out after being cooled to normal temperature then, send into again after mixing in the High Temperature Furnaces Heating Apparatus in nonoxidizing atmosphere after 600-800 ℃ of constant temperature calcining 5-20 hour through grinding, take out after being cooled to normal temperature, promptly get lithium ion cell positive active material/carbon cladded ferrous lithium phosphate powder through pulverizing, cross 300 mesh sieves.
2. semi-wet method prepares the method for LiFePO 4 according to claim 1, it is characterized in that, the insoluble compound of the water of the described Li of containing is: lithium fluoride, one of Quilonum Retard or Trilithium phosphate, the insoluble compound of water that contains Fe is: one of iron protocarbonate, iron protoxide, Ferrox, ferrous phosphate, tertiary iron phosphate or ferric oxide, and the insoluble compound of water that contains P is: one of Trilithium phosphate, ferrous phosphate or tertiary iron phosphate; The water soluble compound of the described Li of containing is: one of lithium hydroxide, monometallic, Lithium Acetate, Lithium Citrate de, lithium chloride or lithium nitrate, the water soluble compound that contains Fe is: one of Iron diacetate, ironic oxalate, iron(ic) chloride, iron protochloride, Iron nitrate or iron nitrate, and the water soluble compound that contains P is: one of phosphoric acid, monometallic, ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate; Described dopant ion M
N+Be ionic radius and Li
+The high valence ion that ionic radius is close: Mg
2+, Al
3+, Zr
4+Or Nb
5+One of, contain dopant ion M
N+Compound for containing dopant ion M
N+One of oxide compound, oxyhydroxide, nitrate, organic acid salt or organometallic compound.
3. prepare the method for LiFePO 4 as semi-wet method as described in the claim 2, it is characterized in that described charcoal is superconduction carbon black or superfine graphite; It is organic compound-sucrose or citric acid, natural high moleculer eompound-starch or one of synthetic macromolecular compound polyethylene powders or polyvinyl alcohol that described pyrolysis can produce carbon compound; The powder of described thin inert metal is the powder of Ag or Cu; The inert metal compound that can be reduced to this metal-powder in subsequent technique is oxide compound, the oxyhydroxide of Ag or Cu, one of nitrate, organic acid salt or organometallics.
4. prepare the method for LiFePO 4 as wet method as described in the claim 3, it is characterized in that described High Temperature Furnaces Heating Apparatus is one of tube furnace, box-type furnace, continuous tunnel furnace or vertical heater, wherein continuous tunnel furnace or vertical heater are two kinds of discontinuous or continous ways.
5. prepare the method for LiFePO 4 as wet method as described in the claim 4, it is characterized in that described nonoxidizing atmosphere is oxygen-free N
2Atmosphere, Ar atmosphere, N
2With H
2Mixed-gas atmosphere, or Ar and H
2One of mixed-gas atmosphere.
6. the LiFePO 4 for preparing the method preparation of LiFePO 4 as semi-wet method as described in one of claim 1-5.
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