CN1255888C - Method for preparing lithiumion cell positive material iron-lithium phosphate - Google Patents
Method for preparing lithiumion cell positive material iron-lithium phosphate Download PDFInfo
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- CN1255888C CN1255888C CNB2004100184764A CN200410018476A CN1255888C CN 1255888 C CN1255888 C CN 1255888C CN B2004100184764 A CNB2004100184764 A CN B2004100184764A CN 200410018476 A CN200410018476 A CN 200410018476A CN 1255888 C CN1255888 C CN 1255888C
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- phosphate
- lithium
- iron phosphate
- ball milling
- lithium iron
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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 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 5
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims abstract description 4
- 239000006258 conductive agent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000002969 artificial stone Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000012298 atmosphere Substances 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 15
- 229910010710 LiFePO Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910017677 NH4H2 Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- MEOVPKDOYAIVHZ-UHFFFAOYSA-N 2-chloro-1-(1-methylpyrrol-2-yl)ethanol Chemical compound CN1C=CC=C1C(O)CCl MEOVPKDOYAIVHZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910009891 LiAc Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a mechanical solid phase synthesis method of lithium iron phosphate of positive electrode material of a lithium ion battery. Metallic iron powder, ferric phosphate, lithium phosphate, phosphate with adulterated elements, a conducting agent or a precursor of the conducting agent are uniformly mixed in proportion, the mixture is put in a ball milling container filled with inert atmosphere, and the mixture is milled for 18 to 36 hours; the obtained ball milling product is put in a furnace with high temperature, the ball milling product is heated at a heating rate of 10 to 30 DEG C/min in inert atmosphere of nitrogen, argon, etc., and is burned at constant temperature of 450 to 750D EG C for 10 to 60 min; then the mixture is cooled to room temperature at a temperature drop rate of 10 to 30 DEG C /min, and lithium iron phosphate powder or adulterated lithium iron phosphate powder is prepared. The method for synthesizing the lithium iron phosphate material has simple and easy technology, cleanness and no pollution, and the obtained lithium iron phosphate material has high specific capacity and excellent cycle performance, and is suitable for mass industrial production.
Description
The technical field is as follows:
the invention belongs to a preparation method of a lithium ion battery anode material, and particularly relates to a method for preparing a lithium ion battery anode material lithium iron phosphate by adopting a mechanical solid-phase synthesis process.
Background art:
LiFePO was first reported since 1997 a.k.padhi4Olivine-type phosphate Lithium Intercalation Material (LiMPO) having lithium intercalation/deintercalation function4(M: Mn, Fe, Co, Ni) has attracted attention as a positive electrode material for a lithium ion battery having a high potential. Wherein the theoretical capacity is LiFePO of 170mAh/g4The lithium ion battery anode material is considered to have the most development prospect due to the characteristics of abundant iron resources, low price, excellent thermal stability, environmental friendlinessand the like.
The existing methods for synthesizing lithium iron phosphate include a high-temperature solid-phase reaction method, a liquid-phase codeposition method, a hydrothermal method, a liquid-phase oxidation-reduction method, a solid-phase microwave method and a mechanical ball milling method.
Widely used high temperature solid phase reaction methods (e.g. [ J]]A.K.Padhi et al Journal of theelectrochemical Society，Vol144，1188-1194(1997)，[J]Yamada et al Journal of the electrochemical Society, Vol148, A960-A967(2001), US Pat.5910382, CN1401559A) is prepared by mixing a ferrous salt such as iron acetate or iron oxalate with ammonium hydrogen phosphate and a lithium salt such as lithium carbonate or lithium hydroxide, and calcining the mixture in an inert atmosphere such as nitrogen or argon at 300-4. The reaction formula is as follows: this method releases ammonia gas during the reaction and makes it difficult to obtain pure LiFePO4。
In WO02/083555A2, a liquid-phase co-deposition method is adopted to co-deposit ferrous phosphate and lithium phosphate precursors from corresponding salt solutions under the control of pH value, and the precursors are roasted at 650-800C to prepare LiFePO4. The whole preparation process is carried out in the nitrogen protective atmosphere, which is not beneficial to industrialization. When the precursor of the lithium iron phosphate is prepared by the liquid phase codeposition method in the Chinese patent CN1431147A, a closed container is adopted, the nitrogen protection atmosphere is avoided, and the prepared precursor is roasted for 5 to 48 hours in the non-oxidizing atmosphere at the temperature of 500-800 ℃ to prepare the phosphorusAnd (3) lithium iron phosphate nanopowder. The initial capacity of the lithium iron phosphate material prepared bythe patent is in the range of 130-147 mAh/g when 0.5C constant current discharge is carried out, and the capacity fading degree is 3% -7% after 40 cycles.
Croce et al are in [ J]]Preparation of LiFePO by sol-gel method in Electrochemical and Solid-State Letters, 5(3) A47-A50(2002)4A material. I.e. LiOH and Fe (NO)3)3Adding into ascorbic acid solution, and mixing with H3PO4The solutions were mixed. Adjusting pH with ammonia water, and heating at 60 deg.C to obtain gel. The gel is subjected to heat treatment at 350 ℃ for 12 hours in nitrogen atmosphere, and then is baked at 800 ℃ for 24 hours to prepare LiFePO4. The method does not use expensive ferrous salt, but uses ascorbic acid to react Fe3+Reduction to Fe2+However, the process is troublesome. Chinese patent CN 1410349A is prepared by sol-gel method using Fe (Ac)2、LiAc、H4H2PO4And tartaric acid and other organic acids as raw materials, preparing gel at 80-100 ℃ under the condition of introducing nitrogen, and roasting the gel at 350-800 ℃ in a reducing atmosphere to obtain LiFePO4And (3) powder. The whole process for preparing the lithium iron phosphate comprises the raw materials Fe (Ac)2The preparation is carried out in the atmosphere of introducing nitrogen or reducing gas, and the operation is inconvenient.
The hydrothermal synthesis method mainly adopts a high-pressure reaction kettle as a reaction vessel, and the LiFePO is directly synthesized from the precursor solution through high-temperature high-pressure reaction4. Such as Shoufeng Yang et al [ J]]In electrochemistry communications, 3(2001) pp.505-508, FeSO is used4，H3PO4LiFePO is synthesized by hydrothermal reaction of LiOH and LiFePO at 120 ℃ for 5 hours4. Frange et al in document [ J]Fe in electrochmcial and Solid-state letters, 2002, 5(10) A231-A2233PO4·5H2O and Li3PO4Takes the raw material as raw material, reacts for 1 hour at the high temperature and the high pressure of 220 ℃ and 24bar to prepare LiFePO4. The hydrothermal synthesis method needs a high-pressure reaction vessel, which is not favorable for industrial production.
Pier Paolo et al in [ J]In the Journal of the Electrochemical Society, 2002, 149(7) A886-890, H is used2O2FePO4 prepared by oxidizing ferrous salt and then reducing FePO with LiI4Preparation of LiFePO4The lithium iron phosphate material with excellent electrochemical performance can be prepared by the method, but the LiI reagent is expensive and is not suitable for industrial production.
Masashi Higuchi et al in [ J]In Journal of power sources 119-2CO3，NH4H2PO4And Fe (CH)3COO)2Or Fe (CH)3CHOHCOO)2·2H2LiFePO is synthesized by using O as raw material through microwave method4. The synthesis method is simple and easy to implement, but the electrochemical performance of the synthesized product in the document is not ideal.
Japan SONY Corp ([ J)]Journal of power sources 119-238 (2003)232-238, JP2001250555, JP200275356) and Japanese patent JP2003292307A use Fe3(PO4)2·8H2O and Li3PO4Preparing LiFePO by using mechanical ball milling method or high-temperature solid phase method as raw material4. These processes require first preparationFe3(PO4)2·8H2O, JP2003292307A for Fe by liquid phase deposition3(PO4)2·8H2And O. While pure Fe is prepared by liquid phase deposition3(PO4)2·8H2O is difficult.
The invention content is as follows:
aiming at the defects of the method, the invention provides a brand-new preparation method of lithium iron phosphate. According to the invention, the lithium iron phosphate material with high purity and excellent electrochemical performance is directly synthesized in one step by adopting a mechanical solid-phase synthesis process without preparing or using ferrous salt which is easily oxidized in the air, and directly adopting metal iron powder and ferric phosphate as iron sources and lithium phosphate as a lithium source. Avoids the disadvantages of multiple steps or impure products in other synthetic methods. The method is simple and easy to implement, and can realize clean industrial production.
The invention discloses a preparation method of lithium iron phosphate as a lithium ion battery anode material, which mainly adopts a mechanical solid-phase synthesis process and comprises the following steps:
uniformly mixing metal iron powder, iron phosphate, lithium phosphate, doped element phosphate and a conductive agent or a conductive agent precursor, wherein the molar ratio of the metal iron powder to the iron phosphate to the doped element phosphate to the lithium phosphate is 1: 2: 0.95-1.05; the dosage of the conductive agent or the precursor of the conductive agent is 1-20% of the mass of the lithium iron phosphate; the mol ratio of the doped element phosphate to the ferric phosphate is 0-1: 1, and the metal element of the doped element phosphate is selected from one of Mn, Co, Ni, Cr, V and Cu; placing the mixture into a ball milling container filled with argon or nitrogen atmosphere, ball milling for 18-36 hours, placing a ball milling product into a high temperature furnace, heating at a heating rate of 10-30 ℃/min in the argon or nitrogen atmosphere, roasting at a constant temperature of 450-750 ℃ for 10-60min, and cooling to room temperature at a cooling rate of 10-30 ℃/min to obtain lithium iron phosphate powder or doped lithium iron phosphate powder.
The conductive agent used in the invention is selected from one of natural graphite powder, artificial stone toner and carbon black.
The precursor of the conductive agent used in the invention is selected from one of sucrose, dextrin and starch.
The ball milling container used in the invention is selected from one of agate ball milling tank, polyurethane ball milling tank, tungsten carbide ball milling tank and corundum ball milling tank.
The iron phosphate and the doped element phosphate can be directly used as commercial products with purity of more than 97 percent, and can also be made by self. Preparation of MePO4(Me:Fe3+，Mn3+，Co3+，Ni3+，Cu3+) The method comprises the following steps: equimolar of Me (NH)4)2(SO4)2.6H2O or Me (NO)3)2And NH4H2PO4Respectively dissolving the two solutions in deionized water to prepare 0.01-0.1 Mol/L solution, mixing the two solutions, and adding 1-4 ml of 30% H into each liter of solution while stirring2O2Stirring the aqueous solution for 2 hours, filtering, washing and drying the obtained precipitate, and roasting the precipitate at the temperature of 200-450 ℃ for 4-10 hours to prepare MePO4。
The preparation method of the lithium iron phosphate as the positive material of the lithium ion battery has the following remarkable characteristics:
(1) the method directly uses metal iron powderand ferric phosphate as iron sources, avoids the complicated ferrous salt synthesis steps in other synthesis technologies, and solves the problem of impure products in the conventional preparation method of ferrous salt raw materials which are easy to oxidize in the air.
(2) The method for preparing the lithium iron phosphate by the mechanical solid-phase synthesis process has the advantages that the raw material components and the product formula are easy to control, the synthesized lithium iron phosphate product has high purity and excellent electrochemical performance. LiFePO synthesized by the invention4the/C material and a metal lithium sheet are assembled into a test battery, the test battery is charged at 0.1C rate, the reversible specific capacity reaches 164mAh/g when the test battery is discharged at 0.1C rate, and the specific capacity reaches 138mAh/g when the test battery is discharged at 1C rate; and exhibits excellent cycle stability.
(3) The synthesis method of the lithium iron phosphate has simple process and easy operation, and the used raw materials are all bulk chemical products. Easy to realize industrial scale clean production and has no three wastes discharge.
Description of the drawings:
FIG. 1 LiFePO prepared as in example 14X-ray diffraction pattern of/C.
FIG. 2 LiFePO prepared as in example 14Scanning electron micrograph of/C (5000 magnification).
FIG. 3 Charge and discharge curves for lithium ion batteries prepared in example 1The voltage range is 2.0V-4.2V, and the electrolyte is lmol/L LiPF6EC and DMC (1: 1), and the charging and discharging current is 17 mA/g.
FIG. 4 is a graph showing the cycle characteristics of the lithium ion battery prepared in example 1, with a voltage range of 2.0V to 4.2V and an electrolyte of 1mol/L LiPF6DMC (1: 1), charging current 17mA/g, and discharge current 17mA/g (0.1C) and 170mA/g (1C), respectively.
The specific implementation mode is as follows:
the invention is further explained below with reference to the drawings and the embodiments.
Example 1:
2.86 grams (0.05 mole) of iron powder, 15.1 grams (0.1 mole) of iron phosphate, 6.37 grams (0.05 mole) of lithium phosphate, and 2.25 grams of sucrose were mixed well. The mixture was placed in an agate jar filled with argon and ball milled for 24 hours. Placing the ball-milled product in a high-temperature furnace, heating at a heating rate of 10 ℃/min in an argon atmosphere, baking at a constant temperature of 600 ℃ for 30min, and cooling to room temperature at a cooling rate of 20 ℃/min to obtain LiFePO4a/C powder. FIG. 1 shows that the obtained lithium iron phosphate powder is olivine-type LiFePO according to the results of X-ray diffraction analysis4The single-phase structure, no impurity peak exists in a spectrogram, and the product purity is high. FIG. 2 is LiFePO4Electron micrograph of/C powder at 5000 x magnification, product particle size substantially less than 5 microns.
0.8 g of the prepared lithium iron phosphate powder is weighed, 0.1 g of acetylene black and 0.1 g of polyvinylidene fluoride binder dissolved in N-N' dimethyl pyrrolidone are added, and the mixture is uniformly mixed and coated on an aluminum foil to prepare a positive plate. In an argon atmosphere drying glove box, a metal lithium sheet is taken as a counter electrode, Celgard2700 is taken as a diaphragm, and Ethylene Carbonate (EC) + dimethyl carbonate (DMC) +1MLiPF6Is used as electrolyte and is assembled into a battery.
The battery was subjected to a charge-discharge cycle test in a voltage range of 2.0V to 4.2V. Figure 3 is a charge-discharge curve for a 0.1C rate battery. As can be seen from the figure, the discharge voltage of the lithium iron phosphate material prepared by the invention is 3.34-3.40V, the reversible specific capacity is as high as 164mAh/g, which is 96% of the theoretical specific capacity. The battery cycle performance is also excellent, the battery cycle performance of charging at 0.1C rate and discharging at 0.1C and 1C rate respectively is shown in figure 3, and the battery capacity is not attenuated after 60 cycles.
Example 2:
mixing 78 g of Mn (NH4)2(SO4)2.6H2O and 23 g NH4H2PO4Dissolving in 1000ml deionized water, mixing the two solutions, adding 8ml of 30% H under stirring2O2The aqueous solution was stirred for 2 hours. Filtering, washing and drying the generated precipitate, and then roasting at 400 ℃ for 4 hours to prepare MnPO4. 2.86 g (0.05 mol) of iron powder and 8.31 g (0.055 mol) of FePO46.75 g (0.045 mol) MnPO4And 6.37 g (0.05 mol)
LiFe was prepared as in example 1, by mixing with 2.25 g of sucrose0.7Mn0.3PO4a/C powder. The specific capacity of the obtained product is about 146mAh/g when the product is discharged at 0.2C multiplying power, and the voltage of a discharge curve is 3.8V-2.9V.
Example 3:
41 g of Ni (NH) are weighed4)2(SO4)2.6H2O and 12 g NH4H2PO4Dissolving in 500ml deionized water, mixing the two solutions, adding4ml of 30% H under stirring2O2The aqueous solution was stirred for 2 hours. Filtering the generated precipitate, washing and drying, and then roasting at 400 ℃ for 4 hours to prepare NiPO4And (4) crystals. 2.86 g (0.05 mol) of iron powder and 12.84 g (0.085 mol) of FePO42.31 g (0.015 mol) NiPO4And 6.37 g (0.05 mol)
LiFe was prepared as in example 1, mixed with 0.8 g of acetylene black0.9Ni0.1PO4a/C powder. The specific capacity of the obtained product is about 143mAh/g when the product is discharged at 0.2C multiplying power, and the discharge voltage is about 3.45V.
Claims (4)
1. A preparation method of lithium iron phosphate as a positive material of a lithium ion battery is characterized in that metal iron powder, iron phosphate, lithium phosphate, doped element phosphate and a conductive agent or a precursor of the conductive agent are uniformly mixed, wherein the molar ratio of the metal iron powder to the iron phosphate to the doped element phosphate to the lithium phosphate is 1: 2: 0.95-1.05; the dosage of the conductive agent or the precursor of the conductive agent is 1-20% of the mass of the lithium iron phosphate; the mol ratio of the doped element phosphate to the ferric phosphate is 0-1: 1, and the metal element of the doped element phosphate is selected from one of Mn, Co, Ni, Cr, V and Cu; placing the mixture into a ball milling container filled with argon or nitrogen atmosphere, ball milling for 18-36 hours, placing a ball milling product into a high temperature furnace, heating at a heating rate of 10-30 ℃/min in the argon or nitrogen atmosphere, roasting at a constant temperature of 450-750 ℃ for 10-60min, and cooling to room temperature at a cooling rate of 10-30 ℃/min to obtain lithium iron phosphate powder or doped lithium iron phosphate powder.
2. The method for preparing the lithium iron phosphate as the positive electrode material of the lithium ion battery according to claim 1, wherein the conductive agent is selected from one of natural graphite powder, artificial stone toner and carbon black.
3. The method for preparing lithium iron phosphate as the positive electrode material of the lithium ion battery according to claim 1, wherein the precursor of the conductive agent is one selected from sucrose, dextrin and starch.
4. The method for preparing the lithium iron phosphate as the cathode material of the lithium ion battery according to claim 1, wherein the ball milling container is one of an agate ball milling tank, a polyurethane ball milling tank, a tungsten carbide ball milling tank and a corundum ball milling tank.
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| CN1332878C (en) * | 2005-10-11 | 2007-08-22 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
| CN1332462C (en) * | 2005-11-15 | 2007-08-15 | 厦门大学 | Lithium iron phosphate anode material and its preparing method |
| CN100395907C (en) * | 2005-12-22 | 2008-06-18 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
| CN100418255C (en) * | 2005-12-23 | 2008-09-10 | 清华大学 | Method for preparing lithium enriched lithium ion phosphate powder |
| CN101348243B (en) * | 2007-07-20 | 2011-04-06 | 上海比亚迪有限公司 | Lithium iron phosphate anode active material and preparation thereof |
| CN101162776B (en) * | 2007-10-26 | 2010-06-02 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same |
| CN101241987B (en) * | 2008-01-04 | 2011-08-24 | 深圳大学 | An electric chemical synthesis method for positive material ferric lithium phosphate of lithium ion battery |
| CN101591012B (en) * | 2008-05-27 | 2012-06-13 | 北京有色金属研究总院 | Preparation method of lithium iron phosphate as cathode material of lithium ion battery |
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| CN102255078B (en) * | 2011-05-27 | 2012-07-18 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
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| CN102332565B (en) * | 2011-09-30 | 2014-07-02 | 浙江工业大学 | Synthesis method for lithium iron phosphate/carbon composite material |
| CN103303893B (en) * | 2013-06-04 | 2014-12-10 | 清华大学深圳研究生院 | Preparation method of lithium iron phosphate |
| CN103384006B (en) * | 2013-07-29 | 2017-03-01 | 深圳先进技术研究院 | A kind of preparation method of lithium iron phosphate/carbon composite material |
| CN106450232B (en) * | 2016-11-30 | 2019-12-10 | 武汉理工力强能源有限公司 | preparation method and application of novel lithium ion battery anode material ternary phosphate |
| CN108598393B (en) * | 2018-04-03 | 2020-05-15 | 安徽博石高科新材料股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN108682853B (en) * | 2018-04-24 | 2020-09-08 | 江西省金锂科技股份有限公司 | Preparation method of lithium iron phosphate and lithium iron phosphate cathode material prepared by same |
| CN108529584B (en) * | 2018-04-24 | 2020-04-07 | 江西省金锂科技股份有限公司 | Preparation method of high-density lithium iron phosphate cathode material |
| CN114188508B (en) * | 2021-10-28 | 2023-02-14 | 厦门理工学院 | Lithium iron phosphate cathode material, preparation method and application |
| CN114538403B (en) * | 2022-01-27 | 2023-08-22 | 廖小珍 | Preparation method and application of sodium ion battery anode material sodium ferric pyrophosphate phosphate |
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