CN100491239C - Preparation method of lithium iron phosphate as lithium ion battery anode material and product thereof - Google Patents
Preparation method of lithium iron phosphate as lithium ion battery anode material and product thereof Download PDFInfo
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- CN100491239C CN100491239C CNB2006101547745A CN200610154774A CN100491239C CN 100491239 C CN100491239 C CN 100491239C CN B2006101547745 A CNB2006101547745 A CN B2006101547745A CN 200610154774 A CN200610154774 A CN 200610154774A CN 100491239 C CN100491239 C CN 100491239C
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- anode material
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000010405 anode material Substances 0.000 title claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000004576 sand Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 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 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 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
- 239000003595 mist Substances 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 239000003350 kerosene Substances 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
- 239000011159 matrix material Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 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 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a low-cost preparation method of lithium iron phosphate as a positive material of a lithium ion battery, which comprises the steps of mixing lithium salt and Fe3+The compound, phosphate and additive are mixed according to a certain proportion, then water or alcohol is added to carry out sand grinding and mixing, and the mixture is dried and pressed into blocks, then the blocks are heated and sintered under the protection of inert atmosphere, and finally the blocks are crushed. The method uses Fe3+The compound is an iron source, the cost is low, the process parameters are easy to control, the batch stability is good, the industrial production is easy to realize, and the produced active material has excellent pole piece processing performance, conductivity and electrochemical performance.
Description
Technical field
The present invention relates to preparation method of a kind of anode material for lithium-ion batteries and products thereof, in particular, the present invention relates to preparation method of lithium ion battery anode material lithium iron phosphate and products thereof, belong to the lithium ion battery material technical field.
Background technology
In recent years, the lithium ion battery development is very rapid, and various portable type electronic products and communication tool constantly increase the demand of lithium ion battery, and the large-sized power lithium ion power supply is also in the development upsurge.Positive electrode material is the important component part of lithium ion battery, and the development of novel anode material has become the key of decision lithium ion battery development.The LiCoO of present large-scale commercial
2, toxicity is bigger, costs an arm and a leg, and has certain safety problem.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there is bigger potential safety hazard in poor heat stability.Spinel LiMn
2O
4Cost is low, and security is good, but capacity is low, and high temperature cyclic performance is poor.Therefore need the positive electrode material of the cheap excellent property of development of new to satisfy the growing market requirement.And as the rhombic system olivine-type LiFePO of new type lithium ion battery positive electrode material
4Have the capacity height, steadily particularly it is cheap for charging/discharging voltage, and security is good, and Heat stability is good, environmentally safe etc. more make it become one of the most potential positive electrode material.
LiFePO
4Exist in the form of occurring in nature, have orderly olivine structural with triphylite, belong to rhombic system (D162h, Pmnb).4 LiFePO are arranged in each structure cell
4Its unit cell parameters of unit is
With
In LiFePO4, Sauerstoffatom is approximate, and to be six sides tightly packed, and phosphorus atom is in tetrahedral space, and iron atom, lithium atom are respectively in octahedral space.FeO on crystal b-c plane
6Octahedra concurrent links.A FeO
6Octahedron and two LiO
6Octahedra limit altogether, and a PO
4Tetrahedron then with a FeO
6Octahedron and two LiO
6Octahedra limit altogether.And Li
+Have two-dimentional mobility, in charge and discharge process, can deviate from and embed.Strong P-O covalent linkage forms delocalized 3 D stereo chemical bond, makes LiFePO
4Has very strong thermodynamics and kinetics stability; But natural pure LiFePO
4Exist all lower problem of ionic diffusion coefficient and electron conductivity.
Prior art adopts high temperature solid-state synthetic method to prepare LiFePO 4/LiFePO 4 usually; Preparation method as Chinese patent application (200410039176.4) lithium ferrous phosphate as anode material of lithium ion battery, this method is with a certain proportion of lithium salts, ferrous salt, phosphoric acid salt and organic or macromolecular compound additive agent mixture pyrolysis under inert atmosphere protection, obtains the inferior lithium anode material of phosphoric acid; Though utilize this method can access the inferior lithium anode material of the good phosphoric acid of specific storage height, high-temperature behavior; But divalence source of iron price is more expensive, and owing to need prevent the oxidation of divalence source of iron, complicated process of preparation, product purity is wayward, thereby cost is increased.
People adopt ferric ion to prepare LiFePO 4/LiFePO 4 as raw material by improving; As the preparation method of the anode composite material of lithium ion battery of the ferrous lithium salts-carbon of Chinese patent application (200410017382.5) phosphoric acid, this method adopts a step solid phase method with a certain proportion of lithium salts, Fe
3+Compound and phosphoric acid salt mix, and then with mixture pyrolysis in inert atmosphere, add a certain amount of high molecular polymer before the pyrolysis, obtain ferrous phosphate base lithium salts-carbon anode composite material.Though this method is not used more expensive Fe
2+Starting material have reduced the cost of product; But owing to adopt high molecular polymer, particularly the product of plastic-like such as polyethylene or polypropylene carries out dry grinding as additive in this preparation method, and raw material mixes inhomogeneous; Particle is bigger; The dephasign of producing product is more; Thereby cause product performance relatively poor; And other preparation method of current employing such as liquid phase deposition, hydrothermal method, mechanical ball milling methods etc. owing to the restriction of equipment claimed, are difficult to realize the suitability for industrialized production of tonne batch.Promptly enable small serial production, cost is also higher relatively, and these have all limited the competitive power of iron lithium phosphate on market greatly.
Summary of the invention
The present invention is directed to the defective that prior art adopts the divalence source of iron to cause product cost to increase, it is the preparation method of the lithium ion battery anode material lithium iron phosphate of raw material that a kind of ferric iron source that adopts is provided, and this preparation method's technology is simple, greatly reduces production cost;
The present invention also adopts high molecular polymer to carry out dry grinding as additive at prior art and causes the relatively poor defective of product performance; A kind of preparation method of lithium ion battery anode material lithium iron phosphate is provided; Preparation method of the present invention adopts additive and a small amount of solvent to carry out uniform mixing, and dephasign is few; Product performance are better;
The present invention is also at the available technology adopting liquid phase deposition, hydrothermal method, and methods such as mechanical ball milling method prepare the defective of lithium ion battery anode material lithium iron phosphate; A kind of low-cost preparation method of lithium ion battery anode material lithium iron phosphate is provided, this method production cost is low, is fit to big suitability for industrialized production, and processing parameter is controlled easily, the batch good stability, prepared product has good pole piece processing characteristics, conductivity and chemical property.
Above-mentioned technical problem of the present invention is implemented by the following technical programs: a kind of preparation method of lithium ion battery anode material lithium iron phosphate comprises that the following step poly-:
A, batching: with lithium salts, Fe
3+Compound, phosphoric acid salt and additive carry out proportioning, and wherein the Li:Fe:P mol ratio is (0.95-1.10): 0.95-1.10): 1; The mass percent that the add-on of described additive accounts for mixture is 5～20%;
B, batch mixing: the raw material after the said ratio is put into stirrer or sand mill, and solubilizing agent mixed 0.5-10 hours, and mixed slurry is dried under 40-260 ℃ of temperature with baking oven or mist projection granulating equipment;
C, sintering: with the mixture briquetting behind the above-mentioned batch mixing or directly put into Equipment for Heating Processing, vacuum condition or flow velocity be the 0.01-50 liter/minute inert atmosphere protection in heat treated, temperature rise rate is 1-30 ℃/minutes, thermal treatment temp is 500-900 ℃, heat treatment time is 8-30 hours, cools to room temperature then;
D, powder process: will go up behind the sintering work in-process by secondary ball milling or airflow milling after, obtain the iron lithium phosphate product.
Adopt proportioning process of the present invention can remedy the loss of source of iron in the material preparation process, make the iron lithium phosphate product of preparation have better electrochemical performance; Mixed slurry is dried under 40-260 ℃ of temperature with baking oven or mist projection granulating equipment in mixing procedure; Bake out temperature is 40-120 ℃ when adopting baking oven, and preferred 90-110 ℃ is 120-260 ℃ when adopting mist projection granulating equipment, preferred 170-220 ℃; Any can all can use in sintering process in the Equipment for Heating Processing of even heating under the atmosphere protection, as vacuum oven, box-type furnace, continuous tunnel furnace, rotary atmosphere furnace, bell jar stove, tube furnace, shuttle-type stove, pushed bat kiln etc.; By obtaining the iron lithium phosphate of even particle distribution after the processing of flouring technology of the present invention.
In the preparation method of above-mentioned lithium ion battery anode material lithium iron phosphate, the lithium salts described in the steps A is one or more in Quilonum Retard, lithium hydroxide, lithium oxalate, Trilithium phosphate, Lithium Acetate, the lithium nitrate.
In the preparation method of above-mentioned lithium ion battery anode material lithium iron phosphate, Fe described in the steps A
3+Compound is one or both in ferric oxide, the tertiary iron phosphate.Adopt this two kinds of compounds or its mixture, cost is lower.
As preferably, the Li:Fe:P mol ratio described in the steps A is (1.0-1.10): (1.0-1.10): 1.
In the preparation method of above-mentioned lithium ion battery anode material lithium iron phosphate, additive described in the steps A is one or more in carbon black, acetylene black, sucrose, starch, glucose, gac, the polyvinyl alcohol; As preferably, the mass percent that the add-on of described additive accounts for mixture is 10～15%.The adding of additive can at high temperature realize mixing of molecular level with mixture, final form with amorphous carbon is coated on around the iron lithium phosphate particle uniformly, the good capacity of material performance increases the conductivity of material, so that also can improve the high-rate discharge ability and the cycle performance of material.The additive addition may cause the material conductivity bad very little, and addition too much may make the material tap density reduce and coating property reduces, and during preferred 10%-15% additive, can obtain good comprehensive performances.
In the preparation method of above-mentioned lithium ion battery anode material lithium iron phosphate, the solvent described in the step B is a kind of in deionized water, tap water, alcohol, the kerosene.
In the preparation method of above-mentioned lithium ion battery anode material lithium iron phosphate, the rare gas element described in the step C is one or more mixed gass in nitrogen, argon gas, the hydrogen.
The present invention also provides a kind of lithium ion battery anode material lithium iron phosphate by above-mentioned preparation method's preparation, and this iron lithium phosphate is a matrix material, comprises the composition of following mass percent:
C:1%～8%; All the other are LiFePO
4
In above-mentioned iron lithium phosphate, as preferably, can also further contain mass percent in the described LiFePO 4 material and be 1%～5% Li
4P
2O
7
In sum, the present invention has the following advantages;
1, the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention adopts cheap ferric iron source to adopt the single step reaction legal system to be equipped with the iron lithium phosphate of conductivity excellence;
2, the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention has avoided ferrous salt synthesis step loaded down with trivial details in other synthetic method, has solved the easy oxidation of ferrous salt and has caused the impure problem of product;
3, the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention adopts additive that ferric iron is reduced to divalence, the ferrous iron activity of harsh one-tenth is good, fast with the speed of response in lithium source and phosphorus source, in conjunction with stable, generate the purity height of iron lithium phosphate, prepared product has good pole piece processing characteristics, conductivity and chemical property;
4, the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention adopts wet chemical method, make additive reach mixing of molecular level with lithium source, source of iron, phosphorus source, additive promptly can play the reductive effect in follow-up reaction, also can form iron lithium phosphate particulate coating effect.Additive after the pyroprocessing with the form disperse of amorphous carbon around the iron lithium phosphate particle, can improve the conductivity of positive electrode material greatly;
5, the processing parameter of the preparation method of lithium ion battery anode material lithium iron phosphate of the present invention employing is controlled easily, and technology stability is good, and is with low cost, realizes easily producing in enormous quantities;
6, the lithium ion battery anode material lithium iron phosphate of preparation method's preparation of the present invention has purposes widely, adopt the lithium ion battery security energy of this positive electrode material preparation good, cost is low, can be used for fields such as electric bicycle, battery-operated motor cycle, electromobile, mine lamp, scooter, notebook computer, power tool and some unconventional removable power supplys.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates of the prepared lithium ion battery anode material lithium iron phosphate of preparation method of the present invention;
Fig. 2 is that the prepared prepared lithium ion battery anode material lithium iron phosphate of preparation method of the present invention is tested the gained particle size distribution figure on the laser particle size distribution instrument;
Fig. 3 is the prepared simulation button cell of lithium ion battery anode material lithium iron phosphate of the present invention discharge curve under different charge-discharge magnifications;
Fig. 4 is the cycle performance figure of 17500 prepared cylindrical lithium ion batteries of lithium ion battery anode material lithium iron phosphate of the present invention.
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail; Be not limited to these embodiment but do not invent.
With 3080 gram lithium hydroxides, 5620 gram ferric oxide, 8261 gram ammonium hydrogen phosphates and 2240 gram sucrose mix, and put into sand mill, add 8 liters in water, add 20 kilograms of agate balls, mix 3.5 hours.Mixed slurry is dried with sponging granulator; use the continous way extrusion machine to make bulk then; and put into the bell jar stove; under 10 liters/minute nitrogen atmosphere; be warmed up to 300 ℃ with 3 ℃/minute speed; and then be warmed up to 780 ℃ with 10 ℃/minute speed, and be incubated 23 hours, be cooled to room temperature then.With the material behind the sintering with crusher in crushing after, stage treatment on airflow milling obtains evengranular iron lithium phosphate.
Record that carbon content is 3.8% in the material, its XRD spectra is seen Fig. 1, and the reference standard card is the intact peridotites iron lithium phosphate of crystal formation, does not observe the diffraction peak of carbon, shows that carbon exists with amorphous carbon.
Record the granularity of active material and distribute as shown in Figure 2.As seen from the figure, the iron lithium phosphate uniform particles of the present invention's preparation is tiny, 1.12 microns of median sizes, and D10 is 0.43 micron, and D90 is 2.92 microns, and size-grade distribution is normal state.
Take by weighing the positive electrode material of embodiment 1 gained respectively with the mass ratio of 82:8:10: acetylene black: PVDF, make electrode after grinding evenly, negative pole is selected metal lithium sheet for use, and electrolytic solution is for being dissolved in the LiPF of the 1.0mol/l in ethyl-carbonate+carbonic acid diethyl vinegar (volume ratio 1:1) mixed solvent
6, barrier film is a polypropylene microporous film, is assembled into battery.
Fig. 3 is to be the discharge curve of above-mentioned battery under different charge-discharge magnifications, and the condition that wherein discharges and recharges is that voltage range is 2.0-4.2V, and charge-discharge magnification is respectively 0.1C, 0.5C, and 3C, 5C, 8C, probe temperature are 30 ℃ ± 1 ℃; When 0.1C discharged, the reversible gram volume of material can reach 160mAh/g, and reversible gram volume is 153mAh/g during the 0.5C discharge, and reversible gram volume is 134mAh/g during the 3C discharge, and reversible gram volume is 120mAh/g during the 5C discharge, and gram volume is 110mAh/g during the 8C discharge.Thereby show the lithium ion battery anode material lithium iron phosphate gram volume height that adopts preparation method's preparation of the present invention, discharge platform is stable, superior performance.
Embodiment 2
With 3695 gram Quilonum Retards, 7985 gram ferric oxide, 123206 gram ammonium hydrogen phosphates and 1600 gram sucrose mix, and put into sand mill, add 8 liters in water, add 20 kilograms of agate balls, mix 2 hours.Mixed slurry is dried with sponging granulator, use extrusion machine to make bulk then, put into vacuum oven, be warmed up to 650 ℃, be incubated 15 hours, be cooled to room temperature then with 3 ℃/minute speed.With the material behind the sintering with crusher in crushing after, stage treatment on airflow milling obtains evengranular iron lithium phosphate.
The carbon content that records active material is 5.6%, presses the method preparation simulation button cell of embodiment 1 equally, be assembled into battery after, reversible gram volume is 152mAh/g when recording the 0.1C rate charge-discharge, gram volume is 140mAh/g during the 0.5C rate charge-discharge.
With 3011 gram Trilithium phosphates, 6228 gram ferric oxide, 6869 gram Secondary ammonium phosphates and 2400 gram sucrose and 1200 gram glucose mix, and put into mixer, add 5 liters of alcohol, add 20 kilograms of agate balls, mix 4 hours.With mixed slurry oven for drying, temperature is controlled at about 70 ℃.Use extrusion machine to make bulk then, put into vacuum oven, be warmed up to 700 ℃, be incubated 30 hours, be cooled to room temperature then with 3 ℃/minute speed.With the material behind the sintering with crusher in crushing after, stage treatment on airflow milling obtains evengranular iron lithium phosphate.
Sending lithium ion battery factory to be prepared into electrode slice the gained material and be assembled into 17500 cylindrical batteries, is 2.5-4.2V in voltage range, and charge-discharge magnification is 0.5C, the temperature temperature be 30 ℃ ± 1 ℃ cycle performance that records battery as shown in Figure 4; As can be seen from Figure 4, the iron lithium phosphate product cycle performance that makes is fine, circulates after 300 times substantially without any decay.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (6)
1, a kind of preparation method of lithium ion battery anode material lithium iron phosphate, this iron lithium phosphate is a matrix material, comprises the Li of the composition of following mass percent: C:1%～8%, 1%～5%
4P
2O
7, all the other are LiFePO
4Described preparation method comprises that the following step poly-:
A, batching: with lithium salts, Fe
3+Compound, phosphoric acid salt and additive carry out proportioning, and wherein the mol ratio of Li:Fe:P is (0.95-1.10): (0.95-1.10): 1; The mass percent that the add-on of described additive accounts for mixture is 5～20%; Described additive is one or more in acetylene black, sucrose, starch, glucose, gac, the polyvinyl alcohol;
B, batch mixing: the raw material after the said ratio is put into stirrer or sand mill, and solubilizing agent mixed 0.5-10 hours, and mixed slurry is dried under 40-260 ℃ of temperature with baking oven or mist projection granulating equipment;
C, sintering: with the mixture briquetting behind the above-mentioned batch mixing or directly put into Equipment for Heating Processing, vacuum condition or flow velocity be the 0.01-50 liter/minute inert atmosphere protection in heat treated, temperature rise rate is 1-30 ℃/minutes, thermal treatment temp is 500-900 ℃, heat treatment time is 8-30 hours, cools to room temperature then;
D, powder process: the work in-process behind the above-mentioned sintering by after secondary ball milling or the airflow milling, are obtained the iron lithium phosphate product.
2, the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that: at the lithium salts described in the steps A is in Quilonum Retard, lithium oxalate, Trilithium phosphate, Lithium Acetate, the lithium nitrate one or more.
3, the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that: substitute with lithium hydroxide at the lithium salts described in the steps A.
4, the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that: at Fe described in the steps A
3+Compound is one or both in ferric oxide, the tertiary iron phosphate.
5, the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that: at the solvent described in the step B is a kind of in deionized water, tap water, alcohol, the kerosene.
6, the preparation method of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that: at the inert atmosphere described in the step C is one or more mixed gass in nitrogen, argon gas, the hydrogen.
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| CN101693532B (en) * | 2009-10-16 | 2011-06-29 | 清华大学 | Method for preparing lithium ferrous phosphate |
| CN101916853A (en) * | 2010-08-20 | 2010-12-15 | 中国科学院过程工程研究所 | Method for preparing lithium iron phosphate anode active material with low energy consumption |
| CN101948101A (en) * | 2010-09-09 | 2011-01-19 | 浙江瑞邦科技有限公司 | Method for preparing anode material lithium iron phosphate material of lithium battery |
| CN102082271A (en) * | 2010-12-27 | 2011-06-01 | 东莞市安灿新能源科技有限公司 | Lamellar cathode material and preparation method thereof |
| CN102275887A (en) * | 2011-01-17 | 2011-12-14 | 横店集团东磁股份有限公司 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
| CN102208621A (en) * | 2011-04-21 | 2011-10-05 | 浙江美思锂电科技有限公司 | Preparation method of nanoscale lithium iron phosphate for industrial production |
| CN103258995A (en) * | 2013-06-06 | 2013-08-21 | 郑州瑞普生物工程有限公司 | Preparation method of lithium iron phosphate material |
| CN104269553A (en) * | 2014-09-23 | 2015-01-07 | 上海宝钢磁业有限公司 | Method for preparing lithium iron phosphate material by adopting cold-rolled byproduct iron oxide |
| CN104241647B (en) * | 2014-09-28 | 2016-08-31 | 四川省有色冶金研究院有限公司 | A kind of preparation method of lithium ion battery spherical anode material |
| CN104409732A (en) * | 2014-12-11 | 2015-03-11 | 上海宝钢磁业有限公司 | Preparation method for lithium iron phosphate material by adopting mixed iron source |
| CN114084879B (en) * | 2021-11-22 | 2023-09-12 | 青岛九环新越新能源科技股份有限公司 | Lithium iron phosphate and production method and application thereof |
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