CN113321197A - Lithium iron phosphate material and preparation method thereof - Google Patents
Lithium iron phosphate material and preparation method thereof Download PDFInfo
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- CN113321197A CN113321197A CN202110583408.6A CN202110583408A CN113321197A CN 113321197 A CN113321197 A CN 113321197A CN 202110583408 A CN202110583408 A CN 202110583408A CN 113321197 A CN113321197 A CN 113321197A
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- iron phosphate
- lithium
- lithium iron
- mixed slurry
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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 46
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011268 mixed slurry Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 239000008103 glucose Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 11
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- -1 hydrogen ions Chemical class 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229940116007 ferrous phosphate Drugs 0.000 description 4
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 4
- 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 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007709 nanocrystallization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003922 charged colloid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 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
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing 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
- C01B25/45—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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 discloses a lithium iron phosphate material and a preparation method thereof, wherein the preparation method of the lithium iron phosphate material comprises the following steps: preparing a mixed solution from ferroferric oxide, lithium phosphate and a carbon source in pure water; adding phosphoric acid into the mixed solution to obtain mixed slurry; stirring the mixed slurry, and stopping stirring when the viscosity of the mixed slurry is more than 1000mPa & s; and after the mixed slurry is solidified, crushing, sieving and calcining to obtain the lithium iron phosphate material. The preparation method realizes zero discharge of wastewater in the iron phosphate preparation process, avoids energy consumption in the step of drying and calcining the iron phosphate, saves the fine grinding and drying processes in the production process of the lithium iron phosphate, saves a large amount of equipment and energy consumption, and the prepared lithium iron phosphate material has excellent performance and has important significance for energy conservation, consumption reduction and environmental protection in the production process of the lithium iron phosphate material.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a lithium iron phosphate material and a preparation method thereof.
Background
Lithium iron phosphate battery (LiFePO)4) Has the advantages of high energy, long cycle life, good safety performance and the like, and is suitable for portable equipment and power electricityThe fields of pools, electrochemical energy storage and the like are widely applied, however, the ever-increasing contradiction between market demand and insufficient capacity and the problem of three-waste discharge in the production process of lithium iron phosphate need to be solved by a new technical route.
The preparation process of the current mainstream lithium iron phosphate material mainly comprises the following steps: mixing iron phosphate, lithium carbonate and a carbon source in pure water, then carrying out a nanocrystallization process through a sand mill, carrying out spray granulation on the obtained slurry after the nanocrystallization process is completed to obtain a precursor, and calcining and crushing the precursor to obtain the final lithium iron phosphate material. The ferric phosphate in the process is generally prepared by using ferric salts such as ferrous sulfate, ferrous chloride and phosphoric acid through a liquid-phase precipitation method, a large amount of wastewater is generated in the process, and meanwhile, the materials synthesized in the liquid phase need to be dried and calcined, so that a large amount of natural gas and electric energy are consumed; in addition, in the existing processes, iron salts (such as iron phosphate, iron oxide, ferroferric oxide and the like) are also adopted to react with phosphorus salts, lithium salts, carbon sources and the like to prepare the lithium iron phosphate material, but the processes generally need the steps of fine grinding and drying, time and labor are wasted, and a large amount of energy consumption is generated in the drying process, which is not in accordance with the original purpose of reducing carbon emission and green production.
Disclosure of Invention
In view of the above, the present invention needs to provide a lithium iron phosphate material and a preparation method thereof, and the preparation method realizes zero discharge of wastewater in the iron phosphate preparation process, avoids source consumption in the drying and calcining steps of iron phosphate, saves the fine grinding and drying processes in the lithium iron phosphate production process, saves a large amount of equipment and energy consumption, and has important significance for energy saving, consumption reduction and environmental protection in the lithium iron phosphate material production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a lithium iron phosphate material, which comprises the following steps:
uniformly stirring ferroferric oxide, lithium phosphate and a carbon source in pure water to obtain a mixed solution;
adding phosphoric acid into the mixed solution to obtain mixed slurry;
stirring the mixed slurry, and stopping stirring when the viscosity of the mixed slurry is more than 1000mPa & s;
after the mixed slurry is solidified, crushing and sieving to obtain precursor powder;
and calcining the precursor powder to obtain the lithium iron phosphate material.
Furthermore, the ferroferric oxide and the lithium phosphate are micron-sized powder with the D100 being less than or equal to 8 mu m.
Further, the concentrations of the ferroferric oxide, the lithium phosphate and the carbon source in the mixed solution are respectively 360g/L, 180g/L and 70-90g/L, respectively, wherein the concentrations are 270-.
Further, the carbon source is at least one selected from glucose, sucrose and polyethylene glycol.
Further, in the step of obtaining the mixed slurry, an organic acid is further added to the mixed solution, and the organic acid is selected from acetic acid, formic acid or citric acid.
Further, the mass concentration of the phosphoric acid is 30-60%.
Further, during the stirring of the mixed slurry, heating was simultaneously performed while maintaining the temperature at 50 to 80 ℃.
Further, in the step of obtaining the precursor powder, the D100 of the precursor powder is less than or equal to 10 μm.
Further, the calcining step specifically comprises: calcining for 5-6 h at 700-750 ℃ under the anaerobic condition.
Preferably, the anaerobic condition can be formed by introducing a protective atmosphere selected from at least one of inert gas and nitrogen.
The invention also provides a lithium iron phosphate material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, ferroferric oxide, lithium phosphate and a carbon source are premixed in pure water and then mixed with phosphoric acid, the phosphoric acid has strong acidity, so that a large amount of hydrogen ions can be ionized in a solution, the hydrogen ions generated by ionization can react with the ferroferric oxide and the lithium phosphate, the ferroferric oxide particles are dissociated to generate iron phosphate and ferrous phosphate nanoparticles, and the lithium phosphate can be combined with the hydrogen ions to produce lithium dihydrogen phosphate and lithium dihydrogen phosphate. The method comprises the steps of consuming hydrogen ions through reaction, wherein iron phosphate, ferrous phosphate, lithium dihydrogen phosphate and lithium dihydrogen phosphate nano-particles and an organic carbon source which is dissolved in a solution and then uniformly distributed in a system exist in the system, at the moment, iron, phosphorus and carbon elements required by the generated lithium iron phosphate are uniformly distributed in the system, the system is solidified into blocks due to continuous reaction and evaporation of water after constant-temperature heating, and the blocks are crushed, sieved, calcined and crushed to obtain the lithium iron phosphate material.
The preparation method provided by the invention directly utilizes the chemical reaction principle to obtain the nanoscale precursor, has the advantages of simple process flow and high production efficiency, does not need expensive fine grinding equipment to carry out nanocrystallization treatment on the raw materials, omits the step of drying the slurry, has low energy consumption and can greatly reduce the cost.
Drawings
Fig. 1 is an SEM characterization diagram of the lithium iron phosphate material prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of a lithium iron phosphate material, which comprises the following steps:
uniformly stirring ferroferric oxide, lithium phosphate and a carbon source in pure water to obtain a mixed solution;
adding phosphoric acid into the mixed solution to obtain mixed slurry;
stirring the mixed slurry, and stopping stirring when the viscosity of the mixed slurry is more than 1000mPa & s;
after the mixed slurry is solidified, crushing and sieving to obtain precursor powder;
and calcining the precursor powder to obtain the lithium iron phosphate material.
The preparation method utilizes the reaction of hydrogen ions ionized by phosphoric acid in solution on ferroferric oxide and lithium phosphate, reduces the powder granularity, improves the reaction activity, simultaneously, components required by the reaction can reach the uniform distribution of molecular level in a liquid phase system, and the preparation method has important significance on the quality and the stability of products. Specifically, after the hydrogen ions are utilized to react the ferroferric oxide and the lithium iron phosphate, the ferroferric oxide particles are dissociated to generate iron phosphate and ferrous phosphate nanoparticles, and the lithium phosphate is combined with the hydrogen ions to produce lithium dihydrogen phosphate and lithium dihydrogen phosphate. A large amount of hydrogen ions are consumed through reaction, iron phosphate, ferrous phosphate, lithium dihydrogen phosphate and lithium dihydrogen phosphate nanoparticles exist in a system, an organic carbon source which is dissolved in a solution and then uniformly distributed in the system, lithium, iron and phosphorus elements required by the lithium iron phosphate exist in a charged colloid form, a dispersed phase in the colloid is 1-100nm, carbon elements are dissolved in water, and all components can be uniformly mixed at a molecular level, so that all areas are uniform in the later reaction process, the obtained phase is more uniform, and the capacity of the lithium iron phosphate material is improved.
The whole reaction process has no waste water from raw materials to finished products, and only a small amount of carbon dioxide is discharged. It is to be understood that the addition of the iron oxide, lithium phosphate, phosphoric acid and carbon source is not particularly limited, and may be adjusted according to the stoichiometric ratio of the finally prepared iron phosphate lithium, and thus, may not be particularly limited.
Furthermore, generally, the size of the raw material powder in the present invention is not particularly limited, and is preferably a nanoscale powder, but nanoscale preparation is difficult, and micron-sized powder is easy to process and obtain, and is also easy to mix, so that the primary mixing reaction can be complete, and therefore, in some embodiments of the present invention, the ferroferric oxide and the lithium phosphate are both micron-sized powder with D100 ≤ 8 μm.
Further, it is understood that the ratio of the ferroferric oxide to the lithium phosphate in the present invention is not particularly limited, and may be adjusted according to the ratio of iron to lithium in the lithium iron phosphate material, and therefore is not particularly limited, and in some specific embodiments of the present invention, the concentrations of the ferroferric oxide, the lithium phosphate and the carbon source in the mixed solution are 270-.
Further, the carbon source in the present invention may be selected conventionally in the art, and may be any soluble carbohydrate conventionally used in the art, and specific examples include, but are not limited to, at least one of glucose, sucrose, and polyethylene glycol.
Further, in the step of obtaining the mixed slurry, an organic acid is further added to the mixed solution, wherein the organic acid is selected from acetic acid, formic acid or citric acid, and the organic acid is added to the mixed solution as an additive, so that a small amount of hydrogen ions can be provided on one hand, and the organic acid can also be used as a source for coating a carbon source on the other hand.
Further, the phosphoric acid used in the present invention is not particularly limited as long as it is an aqueous solution of phosphoric acid, and the concentration and the amount of addition of phosphoric acid can be adjusted according to the amounts of addition of ferroferric oxide and lithium phosphate, and in some specific embodiments of the present invention, the phosphoric acid has a mass concentration of 30% to 60%.
Further, in the process of stirring the mixed slurry, heating is simultaneously performed and the temperature is maintained at 50-80 ℃, so that the reaction can be ensured to proceed by heating, the reaction rate is increased, the reaction is more complete, the heating mode is not particularly limited, but in order to subsequently maintain the reaction temperature to be uniform, it is preferable that the mixed slurry is heated by a water bath heating mode in some embodiments of the present invention.
Further, the curing time of the mixed slurry in the present invention is not particularly limited as long as the curing can be achieved, and the specific time is not particularly limited since it depends on the final viscosity of the mixed slurry, and the curing time is 1 to 3 hours in some specific embodiments of the present invention.
Further, in the step of obtaining the precursor powder, the crushing and sieving in the present invention may be performed in a conventional manner in the art, and are not specifically limited herein, and in some specific embodiments of the present invention, the jaw crusher is used for crushing and sieving, and the finally obtained precursor powder D100 is less than or equal to 10 μm, it is understood that the size of the precursor powder in the present invention is not particularly limited, and the precursor powder may be crushed as required, but in order to ensure that the powder has good fluidity during the subsequent calcination process, the pipeline transportation is convenient, and the existence of too large material after sintering is avoided, which affects the subsequent transportation and pulverization processes, and therefore, in some specific embodiments of the present invention, the precursor powder is preferably crushed to D100 less than or equal to 10 μm.
Further, the calcining step specifically comprises: calcining for 5-6 h at 700-750 ℃ under the anaerobic condition.
Preferably, the anaerobic condition may be formed by introducing a protective atmosphere selected from at least one of an inert gas or nitrogen, and it is understood that the formation of the anaerobic condition is not particularly limited, and the inert gas may be a gas generally used in the art, such as helium, argon, etc.
The invention provides a lithium iron phosphate material, which is prepared by adopting the preparation method of any one of the above materials.
The technical scheme of the invention is more clearly and completely illustrated by combining specific examples and comparative examples.
Example 1
The preparation method of lithium iron phosphate in this embodiment specifically includes the following steps:
weighing 540kg of ferroferric oxide, 270kg of lithium phosphate and 140kg of glucose, adding the materials into 1500L of pure water, and stirring for 0.5h to obtain a mixed solution;
adding 914kg of phosphoric acid with the concentration of 50% into the mixed solution to obtain mixed slurry;
stirring the mixed slurry, heating the mixed slurry to 60 ℃ in a water bath, and stopping heating and stirring when the viscosity of the slurry is more than 1000mPa & s;
after the mixed slurry is solidified, sieving the solidified mixed slurry after jaw crushing to obtain lithium iron phosphate precursor powder;
and (3) calcining the lithium iron phosphate precursor powder in a nitrogen protective atmosphere furnace at 700 ℃ for 5h to prepare a lithium iron phosphate material, and crushing the lithium iron phosphate material into the required particle size by using a jet mill according to the requirement.
As can be seen from the SEM characterization result in fig. 1, the prepared lithium iron phosphate material in this embodiment is uniformly distributed and is in the nanometer level.
Example 2
The same preparation method as in example 1 was adopted in this example except that: in the step of obtaining the mixed solution, the volume of pure water was 2000L.
Example 3
The same preparation method as in example 1 was adopted in this example except that: in the step of obtaining the mixed slurry, 761kg by mass of phosphoric acid was added at a concentration of 60%.
Example 4
The same preparation method as in example 1 was adopted in this example except that: in the step of obtaining the mixed solution, 600kg of ferroferric oxide, 300kg of lithium phosphate and 160kg of cane sugar are weighed and added into 2000L of pure water;
in the step of obtaining a mixed slurry, 1692.6kg by mass of phosphoric acid was added at a concentration of 30%.
Example 5
The same preparation method as in example 1 was adopted in this example except that: in the step of obtaining the mixed solution, the carbon source was 140kg of glucose and 5kg of polyethylene glycol.
Example 6
The same preparation method as in example 1 was adopted in this example except that: in the step of stirring the mixed slurry, the water bath heating temperature was 50 ℃.
Example 7
The same preparation method as in example 1 was adopted in this example except that: in the step of stirring the mixed slurry, the water bath heating temperature was 80 ℃.
Example 8
The same preparation method as in example 1 was adopted in this example except that: in the step of preparing the lithium iron phosphate material, the calcining temperature is 750 ℃, and the heat preservation time is 6 hours.
Example 9
The same preparation method as in example 1 was adopted in this example except that: in the step of preparing the lithium iron phosphate material, the calcining temperature is 720 ℃, and the heat preservation time is 5.5 h.
Example 10
The same preparation method as in example 1 was adopted in this example except that: in the step of obtaining the mixed slurry, 2kg of acetic acid was further added.
Test example
The lithium iron phosphate material prepared in examples 1 to 3, SP, and polyvinylidene fluoride were mixed in a mass ratio of 80: 10: 10 mixing the raw materials in N-methyl pyrrolidone to prepare slurry, coating the slurry on an aluminum foil, drying, and slicing to prepare a working electrode, wherein the surface density of the composite electrode material is 1mg cm-2。
The test method comprises the following steps: in the lithium ion half-cell, a lithium sheet is taken as a reference electrode, and 1M ethylene carbonate/dimethyl carbonate (mass ratio is 1:1) mixed solution of lithium hexafluorophosphate is selected as electrolyte; the battery charging and discharging test is carried out on a Xinwei battery test system, and the voltage interval is selected to be 2.0-4.2V (vs Li)+and/Li), the charge and discharge rates were calculated according to the mass of the lithium phosphate material, and the test results are shown in table 1.
TABLE 1 test of Electrical Properties of lithium iron phosphate materials
The preparation method of the lithium iron phosphate material directly utilizes the chemical reaction principle to obtain the nano-scale precursor, has simple process flow and high production efficiency, does not need expensive fine grinding equipment to carry out nano-treatment on the raw material, omits the step of drying the slurry, has low energy consumption and can greatly reduce the cost. And the test results in the table 1 show that the lithium iron phosphate material prepared by the method has excellent electrical property while the cost is reduced and the production efficiency is improved, so that the preparation method has wide application prospect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the lithium iron phosphate material is characterized by comprising the following steps of:
uniformly stirring ferroferric oxide, lithium phosphate and a carbon source in pure water to obtain a mixed solution;
adding phosphoric acid into the mixed solution to obtain mixed slurry;
stirring the mixed slurry, and stopping stirring when the viscosity of the mixed slurry is more than 1000mPa & s;
after the mixed slurry is solidified, crushing and sieving to obtain precursor powder;
and calcining the precursor powder to obtain the lithium iron phosphate material.
2. The preparation method according to claim 1, wherein the ferroferric oxide and the lithium phosphate are micron-sized powder with D100 being less than or equal to 8 μm.
3. The method as claimed in claim 1, wherein the concentrations of the ferroferric oxide, the lithium phosphate and the carbon source in the mixed solution are 270-360g/L, 135-180g/L and 70-90g/L, respectively.
4. The method according to claim 1, wherein the carbon source is at least one selected from the group consisting of glucose, sucrose and polyethylene glycol.
5. The method according to claim 1, wherein in the step of obtaining the mixed slurry, an organic acid selected from acetic acid, formic acid, or citric acid is further added to the mixed solution.
6. The method according to claim 1, wherein the phosphoric acid is contained at a concentration of 30 to 60% by mass.
7. The method according to claim 1, wherein heating is simultaneously performed while maintaining the temperature at 50 to 80 ℃ during the stirring of the mixed slurry.
8. The production method according to claim 1, wherein in the step of obtaining the precursor powder, the precursor powder has a D100 of 10 μm or less.
9. The method according to claim 1, characterized in that the calcination step is in particular: calcining for 5-6 h at 700-750 ℃ under an oxygen-free condition, wherein the oxygen-free condition can be formed by introducing a protective atmosphere, and the protective atmosphere is selected from at least one of inert gas or nitrogen.
10. A lithium iron phosphate material, characterized by being produced by the production method according to any one of claims 1 to 9.
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