CN118978137B - A low-temperature lithium iron phosphate positive electrode material and preparation method thereof and battery - Google Patents
A low-temperature lithium iron phosphate positive electrode material and preparation method thereof and battery Download PDFInfo
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- CN118978137B CN118978137B CN202411463910.3A CN202411463910A CN118978137B CN 118978137 B CN118978137 B CN 118978137B CN 202411463910 A CN202411463910 A CN 202411463910A CN 118978137 B CN118978137 B CN 118978137B
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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 64
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 24
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000004246 zinc acetate Substances 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 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 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005955 Ferric phosphate Substances 0.000 claims description 12
- 229940032958 ferric phosphate Drugs 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 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 11
- 239000008103 glucose Substances 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 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 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 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
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001816 cooling Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明公开了一种低温型磷酸铁锂正极材料及其制备方法和电池，属于电池技术领域，包括：以无水磷酸铁、碳酸锂和有机碳源为原料制备得到磷酸铁锂前驱体；将乙二胺四乙酸和氨水加入去离子水中，搅拌均匀，再加入乙酸锌、氧化铈和聚乙烯吡咯烷酮，超声处理，浓缩干燥，将得到的产物研磨后进行热处理，得到添加剂；将磷酸铁锂前驱体和无机碳源混合球磨，再加入添加剂，继续球磨，干燥、烧结，得到低温型磷酸铁锂正极材料。本发明的制备方法能够提高磷酸铁锂正极材料的锂离子扩散速率和电子导电率，有效改善磷酸铁锂正极材料在低温下的电化学性能，制备的低温型磷酸铁锂正极材料在25℃、0.2C放电比容量＞166mAh/g，在‑20℃条件下的0.2C放电容量保持率＞85%。The invention discloses a low-temperature lithium iron phosphate positive electrode material and a preparation method and a battery thereof, belonging to the field of battery technology, including: preparing a lithium iron phosphate precursor with anhydrous iron phosphate, lithium carbonate and an organic carbon source as raw materials; adding ethylenediaminetetraacetic acid and ammonia water to deionized water, stirring evenly, then adding zinc acetate, cerium oxide and polyvinyl pyrrolidone, ultrasonic treatment, concentration and drying, grinding the obtained product and heat treating it to obtain an additive; mixing the lithium iron phosphate precursor and the inorganic carbon source and ball milling, then adding the additive, continuing ball milling, drying and sintering to obtain a low-temperature lithium iron phosphate positive electrode material. The preparation method of the present invention can improve the lithium ion diffusion rate and electronic conductivity of the lithium iron phosphate positive electrode material, effectively improve the electrochemical performance of the lithium iron phosphate positive electrode material at low temperature, and the prepared low-temperature lithium iron phosphate positive electrode material has a discharge capacity of more than 166mAh/g at 25°C and 0.2C, and a 0.2C discharge capacity retention rate of more than 85% at -20°C.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a low-temperature lithium iron phosphate positive electrode material, a preparation method thereof and a battery.
Background
The LiFePO 4 crystal has an ordered olivine structure, belongs to an orthorhombic system, each unit cell has 4 LiFePO 4 units, the interior of the LiFePO 4 crystal is connected in a co-edge mode by FeO 6 octahedron and PO 4 tetrahedron, a stable framework structure is formed, and lithium ions can be inserted into and separated from a one-dimensional channel formed by the framework. The iron ions in the crystal lattice are in a very stable polyanion skeleton structure, and the influence on the structural deformation in the charge-discharge process is small, so that the lithium iron phosphate has good thermal stability. But the ionic conductivity and the electronic conductivity of LiFePO 4 are low, and the diffusion channel of Li + between two phases of LiFePO 4-FePO4 is a one-dimensional channel during charge and discharge, and the low intrinsic conductivity and the slow diffusion rate of lithium ions lead to poor low-temperature performance of LiFePO 4 materials. The method has the advantages of shortening the lithium ion diffusion path, improving the lithium ion diffusion rate, reducing the resistance of lithium ions in the transfer and transmission processes, and improving the electron transfer path, so that the method is widely adopted at present to improve the low-temperature performance.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, a method for preparing a low-temperature lithium iron phosphate positive electrode material is provided, comprising the steps of:
mixing anhydrous ferric phosphate, lithium carbonate and an organic carbon source, ball milling, drying and sintering for the first time to obtain a lithium iron phosphate precursor;
adding ethylenediamine tetraacetic acid (EDTA) and ammonia water into deionized water, uniformly stirring, adding zinc acetate, cerium oxide and polyvinylpyrrolidone, performing ultrasonic treatment, concentrating, drying, grinding the obtained product, and performing heat treatment to obtain the additive;
And thirdly, mixing and ball milling the lithium iron phosphate precursor obtained in the first step with an inorganic carbon source, adding the additive obtained in the second step, continuing ball milling, drying, and sintering for the second time to obtain the low-temperature lithium iron phosphate anode material.
Preferably, in the first step, anhydrous iron phosphate and lithium carbonate are mixed according to a molar ratio of Fe to Li of 1:1.0-1.2, and a mass ratio of the total mass of the anhydrous iron phosphate and the lithium carbonate to the organic carbon source is 1:0.05-0.2.
Preferably, in the first step, the organic carbon source is one or more of glucose, sucrose, starch, cyclodextrin, polyethylene glycol and polyvinyl alcohol, and the technological parameters of the first sintering are that the temperature is 400-700 ℃, the temperature rising speed is 3-10 ℃ per minute, and the time is 3-6 hours.
Preferably, in the second step, the molar ratio of the ethylenediamine tetraacetic acid to the NH 3·H2 O to the zinc acetate is 1:4-6:0.5-1, the molar volume ratio of the ethylenediamine tetraacetic acid to the deionized water is 1 mol:0.7-1.5L, the mass ratio of the zinc acetate to the cerium oxide to the polyvinylpyrrolidone is 1:1-3:0.1-0.3, and the concentration of the ammonia water is 20-30 wt%.
Preferably, in the second step, the ultrasonic treatment is carried out at the power of 200-400W, the frequency of 50-70 kHz and the time of 0.5-2 h, and the heat treatment is carried out at the temperature of 400-500 ℃ and the temperature rising speed of 10-30 ℃ per minute and the time of 2-4 h.
Preferably, in the third step, the mass ratio of the lithium iron phosphate precursor to the inorganic carbon source is 1:0.05-0.2, and the mass ratio of the additive to the lithium iron phosphate precursor is 0.005-0.02:1.
Preferably, in the third step, the inorganic carbon source is one or more of carbon black, acetylene black, graphene and carbon nanotubes, and the technological parameters of the second sintering are that the temperature is 500-800 ℃, the temperature rising speed is 3-10 ℃ per minute, and the time is 4-8 hours.
Preferably, the specific condition of the ball milling is that the rotating speed is 100-500 rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.3-1, the grinding balls are zirconia balls, the ball-material ratio is 8-15:1, and the time is 2-6 hours.
The low-temperature type lithium iron phosphate positive electrode material is prepared by the preparation method of the low-temperature type lithium iron phosphate positive electrode material.
The battery is characterized in that the positive electrode material of the battery is the low-temperature lithium iron phosphate positive electrode material.
The invention at least has the following beneficial effects that zinc acetate and cerium oxide are used as raw materials, an additive is obtained through modification treatment, the additive is added into lithium iron phosphate, the additive can be better combined with the lithium iron phosphate, the spatial structure of the lithium iron phosphate is optimized, the lithium ion diffusion rate is improved, the electronic conductivity is improved, the electrochemical performance of the lithium iron phosphate anode material at low temperature is effectively improved, in addition, the invention combines and optimizes the use of an inorganic carbon source and an organic carbon source, and a carbon-coated conductive network formed in situ is beneficial to the improvement of material conductivity, and the low-temperature lithium iron phosphate anode material with excellent low-temperature performance is prepared, wherein the discharge specific capacity at 25 ℃ and 0.2 ℃ is more than 166mAh/g, and the discharge capacity retention rate at 0.2 ℃ under the condition of minus 20 ℃ is more than 85%.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The preparation method of the low-temperature lithium iron phosphate positive electrode material comprises the following steps:
Mixing anhydrous ferric phosphate, lithium carbonate and glucose, ball milling for 5 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling to room temperature to obtain a lithium iron phosphate precursor, wherein the molar ratio of iron to lithium is 1:1.1, the mass ratio of the total mass of the anhydrous ferric phosphate to the lithium carbonate to the mass of the glucose is 1:0.1, the specific condition of ball milling is that the rotating speed is 300rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball-to-material ratio is 10:1;
Adding EDTA and 25wt% ammonia water into deionized water, stirring uniformly, adding zinc acetate, cerium oxide and polyvinylpyrrolidone, carrying out ultrasonic treatment for 1h at 300W and 55kHz, carrying out evaporation concentration at 80 ℃, carrying out vacuum drying at 100 ℃, grinding the obtained dried product for 10min, transferring into a tube furnace, heating to 450 ℃ at a heating rate of 20 ℃ per min under nitrogen atmosphere, carrying out heat preservation for 3h, and naturally cooling to room temperature to obtain the additive, wherein the molar ratio of EDTA, NH 3·H2 O and zinc acetate is 1:5:1, the molar volume ratio of EDTA and deionized water is 1mol:1L, and the mass ratio of zinc acetate, cerium oxide and polyvinylpyrrolidone is 1:2:0.2;
Mixing and ball milling the lithium iron phosphate precursor obtained in the step one with graphene according to the mass ratio of 1:0.1 for 2 hours, adding an additive, continuing ball milling for 1 hour, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 700 ℃ at the heating rate of 5 ℃ per min under nitrogen atmosphere, preserving heat for 6 hours, and naturally cooling to room temperature to obtain the low-temperature lithium iron phosphate positive electrode material, wherein the mass ratio of the additive to the lithium iron phosphate precursor is 0.01:1, the specific condition of ball milling is that the rotating speed is 500rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball material ratio is 10:1.
Example 2
The preparation method of the low-temperature lithium iron phosphate positive electrode material comprises the following steps:
Mixing anhydrous ferric phosphate, lithium carbonate and polyethylene glycol 2000, ball milling for 5 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling to room temperature to obtain a lithium iron phosphate precursor, wherein the molar ratio of iron to lithium is 1:1.1, the total mass of the anhydrous ferric phosphate to the lithium carbonate to the polyethylene glycol 2000 is 1:0.05, the specific condition of ball milling is that the rotating speed is 300rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball-material ratio is 10:1;
Adding EDTA and 25wt% ammonia water into deionized water, stirring uniformly, adding zinc acetate, cerium oxide and polyvinylpyrrolidone, carrying out ultrasonic treatment for 1h at 300W and 55kHz, carrying out evaporation concentration at 80 ℃, carrying out vacuum drying at 100 ℃, grinding the obtained dried product for 10min, transferring into a tube furnace, heating to 450 ℃ at a heating rate of 20 ℃ per min under nitrogen atmosphere, carrying out heat preservation for 3h, and naturally cooling to room temperature to obtain the additive, wherein the molar ratio of EDTA, NH 3·H2 O and zinc acetate is 1:5:1, the molar volume ratio of EDTA and deionized water is 1mol:1L, and the mass ratio of zinc acetate, cerium oxide and polyvinylpyrrolidone is 1:2:0.2;
Mixing and ball milling the lithium iron phosphate precursor obtained in the step one with acetylene black according to the mass ratio of 1:0.15 for 2 hours, adding an additive, continuing ball milling for 1 hour, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 800 ℃ at the heating rate of 5 ℃ per min under nitrogen atmosphere, preserving heat for 5 hours, and naturally cooling to room temperature to obtain the low-temperature lithium iron phosphate positive electrode material, wherein the mass ratio of the additive to the lithium iron phosphate precursor is 0.01:1, the specific condition of ball milling is that the rotating speed is 500rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball material ratio is 10:1.
Example 3
The preparation method of the low-temperature lithium iron phosphate positive electrode material comprises the following steps:
Mixing anhydrous ferric phosphate, lithium carbonate and glucose, ball milling for 5 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling to room temperature to obtain a lithium iron phosphate precursor, wherein the molar ratio of iron to lithium is 1:1.1, the mass ratio of the total mass of the anhydrous ferric phosphate to the lithium carbonate to the mass of the glucose is 1:0.1, the specific condition of ball milling is that the rotating speed is 300rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball-to-material ratio is 10:1;
Adding EDTA and 25wt% ammonia water into deionized water, stirring uniformly, adding zinc acetate, cerium oxide and polyvinylpyrrolidone, carrying out ultrasonic treatment for 1h at 300W and 55kHz, carrying out evaporation concentration at 80 ℃, carrying out vacuum drying at 100 ℃, grinding the obtained dried product for 10min, transferring into a tube furnace, heating to 450 ℃ at a heating rate of 20 ℃ per min under nitrogen atmosphere, carrying out heat preservation for 3h, and naturally cooling to room temperature to obtain the additive, wherein the molar ratio of EDTA, NH 3·H2 O and zinc acetate is 1:5:1, the molar volume ratio of EDTA and deionized water is 1mol:1L, and the mass ratio of zinc acetate, cerium oxide and polyvinylpyrrolidone is 1:1:0.2;
Mixing and ball milling the lithium iron phosphate precursor obtained in the step one with graphene according to the mass ratio of 1:0.1 for 2 hours, adding an additive, continuing ball milling for 1 hour, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 700 ℃ at the heating rate of 5 ℃ per min under nitrogen atmosphere, preserving heat for 6 hours, and naturally cooling to room temperature to obtain the low-temperature lithium iron phosphate positive electrode material, wherein the mass ratio of the additive to the lithium iron phosphate precursor is 0.01:1, the specific condition of ball milling is that the rotating speed is 500rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball material ratio is 10:1.
Comparative example 1
In this comparative example, glucose was not added, and the rest of the procedure was the same as in example 1.
Comparative example 2
In this comparative example, graphene was not added, and the rest of the procedure was the same as in example 1.
Comparative example 3
In this comparative example, zinc acetate and cerium oxide were directly added as follows:
Mixing anhydrous ferric phosphate, lithium carbonate and glucose, ball milling for 5 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling to room temperature to obtain a lithium iron phosphate precursor, wherein the molar ratio of iron to lithium is 1:1.1, the total mass of the anhydrous ferric phosphate to the lithium carbonate to the mass of the glucose is 1:0.1, the specific condition of ball milling is that the rotating speed is 300rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball-to-material ratio is 10:1;
Mixing and ball milling the lithium iron phosphate precursor obtained in the step one with graphene according to the mass ratio of 1:0.1 for 2 hours, then adding zinc acetate and cerium oxide, continuing ball milling for 1 hour, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 700 ℃ at the heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 6 hours, and naturally cooling to room temperature to obtain the lithium iron phosphate positive electrode material, wherein the mass ratio of the zinc acetate to the cerium oxide is 1:2, the mass ratio of the total mass of the zinc acetate and the cerium oxide to the lithium iron phosphate precursor is 0.01:1, the specific condition of ball milling is that the rotating speed is 500rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball material ratio is 10:1.
Comparative example 4
In this comparative example, no additive was used, the method was as follows:
Mixing anhydrous ferric phosphate, lithium carbonate and glucose, ball milling for 5 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 4 hours, and naturally cooling to room temperature to obtain a lithium iron phosphate precursor, wherein the molar ratio of iron to lithium is 1:1.1, the mass ratio of the total mass of the anhydrous ferric phosphate to the lithium carbonate to the mass of the glucose is 1:0.1, the specific condition of ball milling is that the rotating speed is 300rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconium oxide balls, and the ball-to-material ratio is 10:1;
Mixing and ball milling the lithium iron phosphate precursor obtained in the step one and graphene according to the mass ratio of 1:0.1 for 3 hours, vacuum drying at 80 ℃, transferring into a tube furnace, heating to 700 ℃ at the heating rate of 5 ℃ per minute under nitrogen atmosphere, preserving heat for 6 hours, and naturally cooling to room temperature to obtain the low-temperature lithium iron phosphate positive electrode material, wherein the specific condition of ball milling is that the rotating speed is 500rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.5, the grinding balls are zirconia balls, and the ball material ratio is 10:1.
Comparative example 5
In this comparative example, polyvinylpyrrolidone was not used in the second step, and the other steps were the same as in example 1.
And (3) electrochemical test, namely weighing 0.5g of low-temperature lithium iron phosphate anode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 85:10:5, fully mixing the materials with a proper amount of N-methylpyrrolidone to form uniform slurry, coating the uniform slurry on an aluminum foil, drying the aluminum foil to prepare an anode plate, taking a metal lithium plate as a negative electrode, taking an imported polypropylene microporous membrane (Celgard 2400) as a diaphragm, and assembling the 2025 type button cell in an argon-filled glove box, wherein the electrolyte is an equivalent mixed solution of 1mol/L LiPF 6, ethylene Carbonate (EC) and dimethyl carbonate (DMC). The discharge capacities of examples 1 to 3 and comparative examples 1 to 5 at 25 ℃ and 0.2 ℃ and-20 ℃ and 0.2 ℃ were tested, and the discharge capacity retention rate at-20 ℃ was calculated, as shown in table 1, and the discharge capacity retention rate at-20 ℃ was calculated as follows:
-20 ℃ discharge capacity retention rate = -0.2C discharge capacity at 20 ℃/0.2C discharge capacity at 25 ℃ x 100%
TABLE 1
| Specific discharge capacity (mAh/g) at 25℃and 0.2C | Discharge capacity retention at-20 ℃ (%) | |
| Example 1 | 170.6 | 90 |
| Example 2 | 167.2 | 87 |
| Example 3 | 166.8 | 85 |
| Comparative example 1 | 162.5 | 80 |
| Comparative example 2 | 163.7 | 80 |
| Comparative example 3 | 160.5 | 78 |
| Comparative example 4 | 152.4 | 72 |
| Comparative example 5 | 165.3 | 84 |
As can be seen from Table 1, the specific discharge capacity at 0.2C and the discharge capacity retention rate at-20 ℃ of examples 1-3 are both higher than those of comparative examples 1-5, which demonstrates that the method of the invention can effectively improve the electrochemical performance of lithium iron phosphate materials and improve the low temperature performance thereof.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown, it is well suited to various fields of use for which the invention is suited, and further modifications may be readily made by one skilled in the art, and the invention is therefore not to be limited to the particular details and examples shown and described herein, without departing from the general concepts defined by the claims and the equivalents thereof.
Claims (9)
1. The preparation method of the low-temperature lithium iron phosphate positive electrode material is characterized by comprising the following steps of:
mixing anhydrous ferric phosphate, lithium carbonate and an organic carbon source, ball milling, drying and sintering for the first time to obtain a lithium iron phosphate precursor;
Adding ethylenediamine tetraacetic acid and ammonia water into deionized water, stirring uniformly, adding zinc acetate, cerium oxide and polyvinylpyrrolidone, carrying out ultrasonic treatment, concentrating and drying, grinding an obtained product, and carrying out heat treatment to obtain an additive, wherein the molar ratio of ethylenediamine tetraacetic acid to NH 3·H2 O to zinc acetate is 1:4-6:0.5-1, the molar volume ratio of ethylenediamine tetraacetic acid to deionized water is 1 mol:0.7-1.5L, the mass ratio of zinc acetate to cerium oxide to polyvinylpyrrolidone is 1:1-3:0.1-0.3, and the concentration of ammonia water is 20wt% -30 wt%;
And thirdly, mixing and ball milling the lithium iron phosphate precursor obtained in the first step with an inorganic carbon source, adding the additive obtained in the second step, continuing ball milling, drying, and sintering for the second time to obtain the low-temperature lithium iron phosphate anode material.
2. The method for preparing a low-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the first step, anhydrous iron phosphate and lithium carbonate are mixed according to a molar ratio of Fe to Li of 1:1.0-1.2, and a mass ratio of the total mass of the anhydrous iron phosphate and the lithium carbonate to an organic carbon source of 1:0.05-0.2.
3. The method for preparing the low-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the first step, the organic carbon source is one or more of glucose, sucrose, starch, cyclodextrin, polyethylene glycol and polyvinyl alcohol, and the technological parameters of the first sintering are that the temperature is 400-700 ℃, the temperature rising speed is 3-10 ℃ per minute, and the time is 3-6 hours.
4. The method for preparing the low-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the second step, the ultrasonic treatment process parameters comprise 200-400W of power, 50-70 kHz of frequency and 0.5-2 h of time, and the heat treatment process parameters comprise 400-500 ℃ of temperature, 10-30 ℃ of temperature rising speed per minute and 2-4 h of time.
5. The method for preparing a low-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the third step, the mass ratio of the lithium iron phosphate precursor to the inorganic carbon source is 1:0.05-0.2, and the mass ratio of the additive to the lithium iron phosphate precursor is 0.005-0.02:1.
6. The preparation method of the low-temperature lithium iron phosphate positive electrode material according to claim 1, wherein in the third step, the inorganic carbon source is one or more of carbon black, acetylene black, graphene and carbon nanotubes, and the technological parameters of the second sintering are that the temperature is 500-800 ℃, the temperature rising speed is 3-10 ℃ per minute, and the time is 4-8 hours.
7. The preparation method of the low-temperature lithium iron phosphate positive electrode material is characterized in that the specific condition of ball milling is that the rotating speed is 100-500 rpm, the ball milling medium is absolute ethyl alcohol, the solid-liquid ratio is 1:0.3-1, the grinding balls are zirconium oxide balls, the ball-material ratio is 8-15:1, and the time is 2-6 hours.
8. A low-temperature lithium iron phosphate positive electrode material, characterized in that the material is prepared by the preparation method of the low-temperature lithium iron phosphate positive electrode material according to any one of claims 1 to 7.
9. A battery, wherein the positive electrode material of the battery is the low-temperature lithium iron phosphate positive electrode material of claim 8.
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