CN113292058A - Preparation method of nano-doped lithium iron phosphate - Google Patents
Preparation method of nano-doped lithium iron phosphate Download PDFInfo
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- CN113292058A CN113292058A CN202110559460.8A CN202110559460A CN113292058A CN 113292058 A CN113292058 A CN 113292058A CN 202110559460 A CN202110559460 A CN 202110559460A CN 113292058 A CN113292058 A CN 113292058A
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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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 26
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000011265 semifinished product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 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 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- BURBNIPKSRJAIQ-UHFFFAOYSA-N 2-azaniumyl-3-[3-(trifluoromethyl)phenyl]propanoate Chemical compound OC(=O)C(N)CC1=CC=CC(C(F)(F)F)=C1 BURBNIPKSRJAIQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001715 Ammonium malate Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- KGECWXXIGSTYSQ-UHFFFAOYSA-N ammonium malate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)CC([O-])=O KGECWXXIGSTYSQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019292 ammonium malate Nutrition 0.000 claims description 2
- 229940063284 ammonium salicylate Drugs 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 2
- FDIWRLNJDKKDHB-UHFFFAOYSA-N azanium;2-aminoacetate Chemical compound [NH4+].NCC([O-])=O FDIWRLNJDKKDHB-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JCCYXJAEFHYHPP-OLXYHTOASA-L dilithium;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O JCCYXJAEFHYHPP-OLXYHTOASA-L 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000003388 sodium compounds Chemical class 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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 invention relates to the technical field of new energy battery preparation, in particular to a preparation method of nano-doped lithium iron phosphate. The invention takes low-cost iron phosphide as a main raw material, adopts a liquid phase synthesis method, enhances the electrochemical performance of the product by adding doping elements, and has higher charge-discharge capacity, good rate discharge performance and good cycle performance. The lithium iron phosphate material prepared by the invention has the advantages of nano-scale size, fine and uniform particles and high purity. The 0.1C charging capacity of the nano lithium iron phosphate material is 158mAh/g, and the 0.1C charging and discharging efficiency is more than 95%. The preparation method has the advantages of simple process, low cost and easy realization of industrialization.
Description
Technical Field
The invention relates to the technical field of new energy battery preparation, in particular to a preparation method of nano-doped lithium iron phosphate.
Background
With the strong support of the country on the lithium battery new energy battery industry, the market scale of the lithium ion battery is expanding by times. The lithium iron phosphate battery has the advantages of wide raw material source, low price, good safety performance, long cycle life and the like, so that the lithium iron phosphate battery becomes an ideal anode material of a new generation of lithium ion battery. The demand of a 5G base station newly built and modified in 2021 reaches 10GWH, which is very helpful for the lithium iron phosphate battery to open up a new application market in the field of standby power supplies of communication base stations. In the field of power automobiles, because of good safety performance, lithium iron phosphate batteries account for about 78% in 2020. Meanwhile, lithium iron phosphate batteries are also widely applied to the field of energy storage. Therefore, the reduction of the production cost of the lithium iron phosphate has important significance for the cost reduction of the whole lithium iron phosphate battery industrial chain.
At present, the production method of lithium iron phosphate mainly comprises a high-temperature solid phase method, a hydrothermal synthesis method and the like. Wherein, the high-temperature solid phase method comprises the steps of uniformly mixing raw materials according to a certain metering ratio, carrying out flash evaporation drying, uniformly grinding and carrying out high-temperature sintering. The high-temperature solid phase method has the advantages of simple process and easy realization of industrialization; the disadvantages are large consumption of synthetic steam, high cost and non-uniformity in the product synthesis process. The hydrothermal synthesis method is good in homogeneity of synthesized products, can produce high-rate lithium iron phosphate products, but needs high-temperature and high-pressure resistant equipment, and is large in equipment investment, high in operation cost and difficult to industrialize.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of nano-doped lithium iron phosphate, which has the advantages of good product uniformity, higher charge-discharge capacity, good rate discharge performance, good cycle performance, small equipment investment, low operation cost and easy realization of industrialization.
In order to achieve the above object, the present invention provides a method for preparing nano-doped lithium iron phosphate, comprising the following steps:
firstly, preparing ferrophosphorus liquid: taking iron phosphide powder, adding nitric acid for reaction, then adding a complexing agent, and uniformly mixing to obtain iron phosphide liquid;
secondly, wet synthesis: adding a lithium compound, a ferrophosphorus solution and a doping element compound into a reaction kettle, then adding a carbon source into the reaction kettle to carry out stirring reaction, and carrying out coarse crushing and crushing on a reaction product by using a crusher to form a lithium iron phosphate precursor;
thirdly, a calcination section: sintering the precursor product prepared in the second step in a low-temperature nitrogen atmosphere for 10 to 20 hours, and sintering the precursor product in a high-temperature nitrogen atmosphere for 10 to 20 hours; the temperature of the low-temperature area is 400-600 ℃, and the temperature of the high-temperature area is 500-900 ℃;
and fourthly, adding the semi-finished product of the lithium iron phosphate material obtained in the third step into crushing equipment for crushing to obtain the nanoscale lithium iron phosphate.
Preferably, in the first step, the complexing agent is: ammonium citrate, ammonium malate, ammonium tartrate, ammonium oxalate, ammonium salicylate, ammonium succinate, ammonium glycinate, and one or more of ethylenediamine tetraacetic acid.
Preferably, the lithium compound in the second step refers to: one or more of lithium metaphosphate, lithium citrate, lithium dihydrogen phosphate, lithium acetate, lithium tartrate and lithium phosphate.
Preferably, the doping element in the second step refers to: one or more of nickel, cadmium, molybdenum, magnesium, titanium, vanadium, manganese, zinc and sodium compounds.
Preferably, the carbon source in the second step refers to: one or more of asphalt, glucose and sucrose.
Preferably, in the first step, the ratio of Fe to P of the iron phosphide powder is 1.6: 1.
Preferably, 68% nitric acid is added in the step one to react for 8-14 h, and the weight ratio of the iron phosphide powder to the 68% nitric acid is 1 (1-4).
Preferably, in the first step, the mol ratio of the complexing agent to the iron phosphide powder is 1 (0.01-10).
Preferably, in the second step, the Li, Fe, P and the doping elements are mixed according to the molar ratio of (1-1.05) to (0-0.05).
Preferably, in the second step, a carbon source accounting for 10-90% of the total mass of the reactants is added to carry out stirring reaction for 10-30 min.
The invention takes low-cost iron phosphide as a main raw material, adopts a liquid phase synthesis method, enhances the electrochemical performance of the product by adding doping elements, and has higher charge-discharge capacity, good rate discharge performance and good cycle performance. The preparation method has the advantages of simple process, low cost and easy realization of industrialization.
The lithium iron phosphate material prepared by the invention has the advantages of nano-scale size, fine and uniform particles and high purity. The 0.1C charging capacity of the nano lithium iron phosphate material is 158mAh/g, and the 0.1C charging and discharging efficiency is more than 95%.
Drawings
Fig. 1 is an SEM scanning electron microscope image of nano-doped lithium iron phosphate prepared in example 1.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example 1
A preparation method of nano-doped lithium iron phosphate comprises the following steps:
firstly, preparing ferrophosphorus liquid: dissolving 84.84g of iron phosphide powder (Fe: P is 1.6:1) in 165.3g of 68% nitric acid, reacting in a reaction kettle for 5 hours, adding 57.3g of ammonium citrate, stirring and mixing to obtain iron phosphide solution;
secondly, wet synthesis: adding 37.95g of lithium phosphate into a reaction kettle for mixing, then adding 29.6g of glucose for mixing reaction for 1-5 h, and coarsely crushing and crushing reaction products by a crusher to form a lithium iron phosphate precursor;
thirdly, a calcination section: sintering the precursor product prepared in the second step in a nitrogen atmosphere at 500 ℃ in a low-temperature region for 20h, and sintering the precursor product in a nitrogen atmosphere at 700 ℃ in a high-temperature region for 20h to obtain a nano-scale lithium iron phosphate semi-finished product;
and fourthly, adding the semi-finished product of the lithium iron phosphate material obtained in the third step into crushing equipment for crushing to obtain the nanoscale lithium iron phosphate.
Example 2
A preparation method of nano-doped lithium iron phosphate comprises the following steps:
firstly, preparing ferrophosphorus liquid: dissolving 84.84g of iron phosphide powder (Fe: P is 1.6:1) in 165.3g of 68% nitric acid, reacting in a reaction kettle for 5 hours, adding 57.3g of ammonium oxalate, stirring and mixing to obtain iron phosphide solution;
secondly, wet synthesis: adding 37.95g of lithium phosphate into a reaction kettle for mixing, then adding 29.6g of glucose for mixing reaction for 1-5 h, and coarsely crushing and crushing reaction products by a crusher to form a lithium iron phosphate precursor;
thirdly, a calcination section: sintering the precursor product prepared in the second step in a nitrogen atmosphere at 500 ℃ in a low-temperature region for 20h, and sintering the precursor product in a nitrogen atmosphere at 700 ℃ in a high-temperature region for 20h to obtain a nano-scale lithium iron phosphate semi-finished product;
and fourthly, adding the semi-finished product of the lithium iron phosphate material obtained in the third step into crushing equipment for crushing to obtain the nanoscale lithium iron phosphate.
Example 3
A preparation method of nano-doped lithium iron phosphate comprises the following steps:
firstly, preparing ferrophosphorus liquid: dissolving 84.84g of iron phosphide powder (Fe: P is 1.6:1) in 165.3g of 68% nitric acid, reacting in a reaction kettle for 5 hours, adding 57.3g of ammonium tartrate, stirring and mixing to obtain iron phosphide solution;
secondly, wet synthesis: adding 34.06g of lithium dihydrogen phosphate into a reaction kettle, mixing, adding 101.90 g of lithium oxalate, then adding 29.6g of glucose, mixing and reacting for 1-5 h, and coarsely crushing and crushing a reaction product by a crusher to form a lithium iron phosphate precursor;
thirdly, a calcination section: sintering the precursor product prepared in the second step in a nitrogen atmosphere at 500 ℃ in a low-temperature region for 20h, and sintering the precursor product in a nitrogen atmosphere at 700 ℃ in a high-temperature region for 20h to obtain a nano-scale lithium iron phosphate semi-finished product;
and fourthly, adding the semi-finished product of the lithium iron phosphate material obtained in the third step into crushing equipment for crushing to obtain the nanoscale lithium iron phosphate.
The nanoscale lithium iron phosphate product prepared in example 1 was sampled and tested: observing the product with an emission Scanning Electron Microscope (SEM) to form an olivine structure (see figure 1), wherein the particle size is 30 nm; detected as LiFeP04 by X-ray powder diffraction (XRD).
Mixing the nano lithium iron phosphate synthesized in the embodiment 1, PVDF and acetylene black according to the weight ratio of 85:5:10, adding NMP and stirring to prepare slurry; coating the slurry on an aluminum sheet, and drying at 80 ℃ to obtain a positive electrode; a lithium sheet is taken as a counter electrode (negative electrode), a porous polypropylene film is taken as a diaphragm, the thickness of the diaphragm is 20 microns, the porosity is 60%, and the pore diameter is about 30 microns; an organic solvent solution of LiPF6 is used as an electrolyte, and DMC (DMC), EC and/or L is used as an organic solvent; punching the anode, the diaphragm and the cathode into proper diameters, stacking the anode, the diaphragm and the cathode in sequence, putting the stacked anode, diaphragm and cathode into a CR2025 button battery shell, injecting electrolyte, and sealing the battery. Carrying out charge-discharge cycle performance test on the battery; the lithium battery is charged by adopting a constant-current and constant-voltage mode, the charge cut-off potential is 3.8V, the constant-current discharge is adopted, the cut-off voltage is 2V, the charge-discharge current density is 0.5mA/cm2, the first charge-discharge efficiency and the first discharge specific capacity are 95% and 158mAh/g, and the first discharge specific capacity is 112mAh/g after 1000 times of circulation.
Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications, equivalents and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A preparation method of nano-doped lithium iron phosphate is characterized by comprising the following steps: the method comprises the following steps:
firstly, preparing ferrophosphorus liquid: taking iron phosphide powder, adding nitric acid for reaction, then adding a complexing agent, and uniformly mixing to obtain iron phosphide liquid;
secondly, wet synthesis: adding a lithium compound, a ferrophosphorus solution and a doping element compound into a reaction kettle, then adding a carbon source into the reaction kettle to carry out stirring reaction, and carrying out coarse crushing and crushing on a reaction product by using a crusher to form a lithium iron phosphate precursor;
thirdly, a calcination section: sintering the precursor product prepared in the second step in a low-temperature nitrogen atmosphere for 10 to 20 hours, and sintering the precursor product in a high-temperature nitrogen atmosphere for 10 to 20 hours; the temperature of the low-temperature area is 400-600 ℃, and the temperature of the high-temperature area is 500-900 ℃;
and fourthly, adding the semi-finished product of the lithium iron phosphate material obtained in the third step into crushing equipment for crushing to obtain the nanoscale lithium iron phosphate.
2. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: in the first step, the complexing agent refers to: ammonium citrate, ammonium malate, ammonium tartrate, ammonium oxalate, ammonium salicylate, ammonium succinate, ammonium glycinate, and one or more of ethylenediamine tetraacetic acid.
3. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the lithium compound in the second step refers to: one or more of lithium metaphosphate, lithium citrate, lithium dihydrogen phosphate, lithium acetate, lithium tartrate and lithium phosphate.
4. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the doping element in the second step refers to: one or more of nickel, cadmium, molybdenum, magnesium, titanium, vanadium, manganese, zinc and sodium compounds.
5. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the carbon source in the second step refers to: one or more of asphalt, glucose and sucrose.
6. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: and (3) the Fe: P of the iron phosphide powder in the first step is 1.6: 1.
7. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: and adding 68% nitric acid to react for 8-14 h in the step one, wherein the weight ratio of the iron phosphide powder to the 68% nitric acid is 1 (1-4).
8. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: in the first step, the mol ratio of the complexing agent to the iron phosphide powder is 1 (0.01-10).
9. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: in the second step, the Li, Fe, P and the doping elements are mixed according to the molar ratio of (1-1.05) to (0-0.05).
10. The method for preparing nano-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: and adding a carbon source accounting for 10-90% of the total mass of the reactants in the second step, and stirring for reaction for 10-30 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628714A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Carbon-free nanoscale lithium iron phosphate and preparation method thereof |
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
| CN101630730A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate compound and preparation method thereof |
| CN102983332A (en) * | 2012-12-11 | 2013-03-20 | 浙江南都电源动力股份有限公司 | Preparation method for lithium iron phosphate material of positive electrode of lithium ion secondary battery |
-
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- 2021-05-21 CN CN202110559460.8A patent/CN113292058A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628714A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Carbon-free nanoscale lithium iron phosphate and preparation method thereof |
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
| CN101630730A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate compound and preparation method thereof |
| CN102983332A (en) * | 2012-12-11 | 2013-03-20 | 浙江南都电源动力股份有限公司 | Preparation method for lithium iron phosphate material of positive electrode of lithium ion secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114572950A (en) * | 2022-01-28 | 2022-06-03 | 宜昌邦普宜化新材料有限公司 | Preparation method and application of high-purity iron phosphate |
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