WO2024066187A1 - Lithium iron phosphate positive electrode material, preparation method therefor, and application thereof - Google Patents
Lithium iron phosphate positive electrode material, preparation method therefor, and application thereof Download PDFInfo
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- WO2024066187A1 WO2024066187A1 PCT/CN2023/078165 CN2023078165W WO2024066187A1 WO 2024066187 A1 WO2024066187 A1 WO 2024066187A1 CN 2023078165 W CN2023078165 W CN 2023078165W WO 2024066187 A1 WO2024066187 A1 WO 2024066187A1
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- Prior art keywords
- iron phosphate
- lithium iron
- positive electrode
- electrode material
- lithium
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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 72
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 14
- -1 Prussian blue compound Chemical class 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229960003351 prussian blue Drugs 0.000 claims abstract description 12
- 239000013225 prussian blue Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229910002548 FeFe Inorganic materials 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer 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
- H01M4/58—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
- 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
Definitions
- the present invention belongs to the technical field of lithium ion battery materials, and in particular relates to a lithium iron phosphate positive electrode material and a preparation method and application thereof.
- Lithium-ion power batteries have been widely used in the field of electric vehicles, mainly divided into ternary batteries and lithium iron phosphate batteries.
- Ternary lithium batteries have higher gram capacity, but the Ni and Co they require are expensive and in short supply, and the safety and cycle stability of ternary lithium batteries are poor.
- Olivine-configured lithium iron phosphate batteries are one of the most promising positive electrode materials for lithium-ion power batteries because of their low price, good cycle stability, and the absence of toxic heavy metals.
- lithium iron phosphate batteries have poor conductivity and usually require doping modification or coating with conductive materials.
- the conventional coating method is to add a carbon source during the preparation of lithium iron phosphate, but it can generally only be coated on the surface of the lithium iron phosphate and cannot improve the conductivity of the lithium iron phosphate.
- the present invention aims to solve at least one of the technical problems existing in the prior art.
- the present invention provides a lithium iron phosphate positive electrode material and a preparation method and application thereof.
- the lithium iron phosphate positive electrode material prepared by the preparation method has excellent conductive properties.
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- the iron phosphate precursor, lithium source and Prussian blue compound are mixed, calcined in a reducing or inert atmosphere, cooled and acid-leached, and dried to obtain the product.
- the Prussian blue compound is at least one of Li 2 FeFe(CN) 6 and Li 2 MnFe(CN) 6 .
- the Prussian blue compound is Li 2 FeFe(CN) 6 .
- the lithium source is at least one of LiOH and Li 2 CO 3 .
- the calcination method is to first calcine at 200-600° C. for 1-6 hours, and then heat up to 650-1000° C. for calcination for 6-20 hours.
- the calcination method is to first calcine at 400-600° C. for 1-4 hours, and then heat up to 650-850° C. for calcination for 6-12 hours.
- the acid used in the acid leaching is an inorganic acid.
- the acid used in the acid leaching is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
- the pH of the acid leaching is 3.5-6, and the time of the acid leaching is 1-40 hours.
- the pH of the acid leaching is 3.5-5, and the time of the acid leaching is 1-30 hours.
- the drying temperature is 100-500°C.
- the drying temperature is 300-500°C.
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- the iron phosphate precursor, lithium source and Li2FeFe (CN) 6 are mixed evenly, and the mixture is placed in a reducing or inert atmosphere, calcined at 400-600°C for 1-4 hours, then heated to 650-850°C and calcined for 6-12 hours. After cooling, it is immersed in an inorganic acid solution with a pH of 3.5-6 for 1-40 hours, and dried at 100-500°C to obtain a carbon-coated lithium iron phosphate positive electrode material.
- a lithium iron phosphate positive electrode material is prepared by the preparation method as described above.
- a lithium-ion battery comprises the lithium iron phosphate positive electrode material as described above.
- the invention mixes a specific Prussian blue compound, an iron phosphate material precursor and a lithium source, and then calcines the mixture under the condition of 400-600°C.
- the Prussian blue compound is combined with the surface of lithium iron phosphate particles or the gaps between multiple lithium iron phosphate particles during the low-temperature calcination process. Then, during the temperature-raising calcination process, the decomposition existing on the surface of the lithium iron phosphate produces a uniform C coating layer containing Fe, and the Prussian blue compound existing in the gaps between the lithium iron phosphate particles can maintain its large framework network after carbonization, and can provide lithium ions as a channel, thereby improving the conductivity of the lithium iron phosphate material.
- the N2 gas generated during the carbonization process can increase the porosity of the lithium iron phosphate material, increase the contact area between the lithium iron phosphate and the electrolyte, and further improve the conductivity.
- the Fe3C byproduct on the surface and the Fe element existing on the surface of the lithium iron phosphate are removed by immersion in an inorganic acid, thereby improving the safety performance of the battery.
- FIG. 1 is a SEM image of the lithium iron phosphate positive electrode material prepared in Example 1 of the present invention.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- the SEM image of the lithium iron phosphate positive electrode material prepared in Example 1 is shown in FIG. 1 , and it can be seen that a uniform layer of carbon is coated on the surface of the lithium iron phosphate material.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- a lithium iron phosphate positive electrode material is prepared by the above preparation method.
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- a lithium iron phosphate positive electrode material is prepared by the above preparation method.
- Embodiment 4 is a diagrammatic representation of Embodiment 4:
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- a lithium iron phosphate positive electrode material is prepared by the above preparation method.
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- a lithium iron phosphate positive electrode material is prepared by the above preparation method.
- a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
- a lithium iron phosphate positive electrode material is prepared by the above preparation method.
- the lithium iron phosphate positive electrode materials prepared in Examples 1-4 and Comparative Examples 1-2 were assembled into button cells, and the electrochemical performance of lithium ion batteries was tested.
- the specific steps are: using N-methylpyrrolidone as a solvent, the lithium iron phosphate positive electrode material is mixed evenly with acetylene black and PVDF in a mass ratio of 9.2:0.5:0.3, coated on aluminum foil, dried at 80°C with forced air for 8 hours, and then vacuum dried at 120°C for 12 hours.
- the battery was assembled in an argon-protected glove box, the negative electrode was a metal lithium sheet, the diaphragm was a polypropylene film, the electrolyte was 1M LiPF 6 -EC/DMC (1:1, v/v), and a 2032-type button cell shell was used to assemble the button cell in an argon-protected glove box, and then the electrochemical performance was tested at 25°C at 3.0-4.0V. The results are shown in Table 1.
- the 0.1C discharge capacity of the lithium iron phosphate positive electrode material prepared in this application can reach more than 150 mAh/g, and the 0.5C discharge capacity can reach more than 130 mAh/g.
- the capacity retention rate of Comparative Example 2 is improved to a certain extent compared with Comparative Example 1.
- Example 2 Mn is introduced on the surface of lithium iron phosphate. It is generally believed that manganese can increase the voltage platform of lithium iron phosphate, but it will further reduce the conductivity of lithium iron phosphate. In Example 2, due to the treatment of this solution, it still has a high conductivity.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed are a lithium iron phosphate positive electrode material, a preparation method therefor, and an application thereof. The preparation method comprises the following steps: mixing an iron phosphate precursor, a lithium source and a Prussian blue compound, calcining in a reducing or inert atmosphere, cooling and acid leaching, and drying to obtain a product. The lithium iron phosphate positive electrode material obtained via preparation by the preparation method has excellent conductivity.
Description
本发明属于锂离子电池材料技术领域，特别涉及一种磷酸铁锂正极材料及其制备方法和应用。The present invention belongs to the technical field of lithium ion battery materials, and in particular relates to a lithium iron phosphate positive electrode material and a preparation method and application thereof.
锂离子动力电池已经被广泛应用于电动汽车领域，主要分为三元电池和磷酸铁锂电池。三元锂电池具有更高的克容量，然而其需要的Ni、Co成本高昂，资源短缺，而且三元锂电池的安全性和循环稳定性较差。橄榄石构型的磷酸铁锂电池，由于其价格低廉，循环稳定性好，不含有有毒的重金属，因此其是一种最有潜力的锂离子动力电池正极材料。然而，磷酸铁锂电池的导电性较差，通常需要进行掺杂改性或者包覆导电材料。常规的包覆方法是在磷酸铁锂制备过程中加入碳源，但是一般只能包覆在磷酸铁锂的表层，并不能改善磷酸铁锂内部的导电性能。Lithium-ion power batteries have been widely used in the field of electric vehicles, mainly divided into ternary batteries and lithium iron phosphate batteries. Ternary lithium batteries have higher gram capacity, but the Ni and Co they require are expensive and in short supply, and the safety and cycle stability of ternary lithium batteries are poor. Olivine-configured lithium iron phosphate batteries are one of the most promising positive electrode materials for lithium-ion power batteries because of their low price, good cycle stability, and the absence of toxic heavy metals. However, lithium iron phosphate batteries have poor conductivity and usually require doping modification or coating with conductive materials. The conventional coating method is to add a carbon source during the preparation of lithium iron phosphate, but it can generally only be coated on the surface of the lithium iron phosphate and cannot improve the conductivity of the lithium iron phosphate.
因此，有必要提供一种导电性优异的磷酸铁锂正极材料的制备方法。Therefore, it is necessary to provide a method for preparing a lithium iron phosphate positive electrode material with excellent conductivity.
发明内容Summary of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种磷酸铁锂正极材料及其制备方法和应用，该制备方法制备得到的磷酸铁锂正极材料具有优异的导电性能。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a lithium iron phosphate positive electrode material and a preparation method and application thereof. The lithium iron phosphate positive electrode material prepared by the preparation method has excellent conductive properties.
本发明的上述技术目的是通过以下技术方案得以实现的：The above technical objectives of the present invention are achieved through the following technical solutions:
一种磷酸铁锂正极材料的制备方法，包括以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将磷酸铁前驱体、锂源与普鲁士蓝化合物混合，置于还原性或惰性气氛下煅烧，冷却酸浸，烘干后即得。The iron phosphate precursor, lithium source and Prussian blue compound are mixed, calcined in a reducing or inert atmosphere, cooled and acid-leached, and dried to obtain the product.
优选的，所述普鲁士蓝化合物为Li2FeFe(CN)6和Li2MnFe(CN)6中的至少一种。Preferably, the Prussian blue compound is at least one of Li 2 FeFe(CN) 6 and Li 2 MnFe(CN) 6 .
优选的，所述普鲁士蓝化合物为Li2FeFe(CN)6。Preferably, the Prussian blue compound is Li 2 FeFe(CN) 6 .
优选的，所述锂源为LiOH及Li2CO3中的至少一种。Preferably, the lithium source is at least one of LiOH and Li 2 CO 3 .
优选的，所述煅烧的方式为先于200-600℃下煅烧1-6小时，然后升温到650-1000℃煅烧6-20小时。Preferably, the calcination method is to first calcine at 200-600° C. for 1-6 hours, and then heat up to 650-1000° C. for calcination for 6-20 hours.
进一步优选的，所述煅烧的方式为先于400-600℃下煅烧1-4小时，然后升温到650-850℃煅烧6-12小时。
More preferably, the calcination method is to first calcine at 400-600° C. for 1-4 hours, and then heat up to 650-850° C. for calcination for 6-12 hours.
优选的，所述酸浸用到酸为无机酸。Preferably, the acid used in the acid leaching is an inorganic acid.
进一步优选的，所述酸浸用到酸为盐酸、硫酸及磷酸中的至少一种。More preferably, the acid used in the acid leaching is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
优选的，所述酸浸的pH为3.5-6，所述酸浸的时间为1-40小时。Preferably, the pH of the acid leaching is 3.5-6, and the time of the acid leaching is 1-40 hours.
进一步优选的，所述酸浸的pH为3.5-5，所述酸浸的时间为1-30小时。More preferably, the pH of the acid leaching is 3.5-5, and the time of the acid leaching is 1-30 hours.
优选的，所述烘干的温度为100-500℃。Preferably, the drying temperature is 100-500°C.
进一步优选的，所述烘干的温度为300-500℃。More preferably, the drying temperature is 300-500°C.
优选的，一种磷酸铁锂正极材料的制备方法，包括以下步骤：Preferably, a method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将磷酸铁前驱体、锂源与Li2FeFe(CN)6混合均匀，将上述混合物置于还原性或者惰性气氛下，于400-600℃下煅烧1-4小时，然后升温到650-850℃煅烧6-12小时，冷却后置于pH为3.5-6的无机酸溶液中浸泡1-40h，100-500℃烘干后即得到碳包覆的磷酸铁锂正极材料。The iron phosphate precursor, lithium source and Li2FeFe (CN) 6 are mixed evenly, and the mixture is placed in a reducing or inert atmosphere, calcined at 400-600℃ for 1-4 hours, then heated to 650-850℃ and calcined for 6-12 hours. After cooling, it is immersed in an inorganic acid solution with a pH of 3.5-6 for 1-40 hours, and dried at 100-500℃ to obtain a carbon-coated lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由如上所述的制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the preparation method as described above.
如上所述的磷酸铁锂正极材料在制备锂离子电池中的应用。The application of the lithium iron phosphate positive electrode material as described above in the preparation of lithium ion batteries.
一种锂离子电池，包括如上所述的磷酸铁锂正极材料。A lithium-ion battery comprises the lithium iron phosphate positive electrode material as described above.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明将特定的普鲁士蓝化合物、磷酸铁材料前驱体及锂源混匀后，在400-600℃的条件下煅烧，普鲁士蓝化合物在低温煅烧过程中结合于磷酸铁锂颗粒的表面或者多个磷酸铁锂颗粒的间隙中；然后升温煅烧过程中，存在于磷酸铁锂表面的分解产生均匀的含有Fe的C包覆层，而存在于磷酸铁锂颗粒间隙的普鲁士蓝化合物碳化后可以保持其大框架网络，可以供锂离子作为通道，提高磷酸铁锂材料的导电性能；碳化过程中产生的N2气体可以增加磷酸铁锂材料的多孔性，增大磷酸铁锂和电解液的接触面积，进一步提高导电性能；最终通过无机酸浸泡的方式去除其表面的Fe3C副产物，以及磷酸铁锂表面存在的Fe单质，以提高电池的安全性能。The invention mixes a specific Prussian blue compound, an iron phosphate material precursor and a lithium source, and then calcines the mixture under the condition of 400-600°C. The Prussian blue compound is combined with the surface of lithium iron phosphate particles or the gaps between multiple lithium iron phosphate particles during the low-temperature calcination process. Then, during the temperature-raising calcination process, the decomposition existing on the surface of the lithium iron phosphate produces a uniform C coating layer containing Fe, and the Prussian blue compound existing in the gaps between the lithium iron phosphate particles can maintain its large framework network after carbonization, and can provide lithium ions as a channel, thereby improving the conductivity of the lithium iron phosphate material. The N2 gas generated during the carbonization process can increase the porosity of the lithium iron phosphate material, increase the contact area between the lithium iron phosphate and the electrolyte, and further improve the conductivity. Finally, the Fe3C byproduct on the surface and the Fe element existing on the surface of the lithium iron phosphate are removed by immersion in an inorganic acid, thereby improving the safety performance of the battery.
图1为本发明实施例1制备得到的磷酸铁锂正极材料的SEM图。FIG. 1 is a SEM image of the lithium iron phosphate positive electrode material prepared in Example 1 of the present invention.
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Embodiment 1:
一种磷酸铁锂正极材料的制备方法，包含以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂与10g Li2FeFe(CN)6于球磨机中混合2小时，将上述混合
物转移到辊道炉中，于氮气气氛下，于400℃下煅烧1小时，然后升温到650℃煅烧6小时，冷却后置于pH为3.5的磷酸溶液中浸泡5h，与烘箱500℃烘干后，即得到碳包覆的磷酸铁锂正极材料。42.38 g of iron phosphate, 44.12 g of lithium carbonate and 10 g of Li 2 FeFe(CN) 6 were mixed in a ball mill for 2 hours. The material was transferred to a roller furnace and calcined at 400°C for 1 hour under a nitrogen atmosphere, then heated to 650°C and calcined for 6 hours. After cooling, it was immersed in a phosphoric acid solution with a pH of 3.5 for 5 hours, and dried in an oven at 500°C to obtain a carbon-coated lithium iron phosphate positive electrode material.
实施例1制备得到的磷酸铁锂正极材料的SEM图如图1所示，可以看到磷酸铁锂材料的表面包覆了一层均匀的碳。The SEM image of the lithium iron phosphate positive electrode material prepared in Example 1 is shown in FIG. 1 , and it can be seen that a uniform layer of carbon is coated on the surface of the lithium iron phosphate material.
实施例2：Embodiment 2:
一种磷酸铁锂正极材料的制备方法，包含以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂与10g Li2MnFe(CN)6于球磨机中混合2小时，将上述混合物转移到辊道炉中，于氮气气氛下，于400℃下煅烧1小时，然后升温到650℃煅烧6小时，冷却后置于pH为3.5的磷酸溶液中浸泡5h，与烘箱500℃烘干后，即得到碳包覆的磷酸铁锂正极材料。42.38g of iron phosphate, 44.12g of lithium carbonate and 10g of Li2MnFe (CN) 6 were mixed in a ball mill for 2 hours, and the mixture was transferred to a roller furnace and calcined at 400°C for 1 hour under a nitrogen atmosphere, then heated to 650°C and calcined for 6 hours. After cooling, it was immersed in a phosphoric acid solution with a pH of 3.5 for 5 hours, and dried in an oven at 500°C to obtain a carbon-coated lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由上述制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the above preparation method.
实施例3：Embodiment 3:
一种磷酸铁锂正极材料的制备方法，包含以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂与10g Li2FeFe(CN)6于球磨机中混合2小时，将上述混合物转移到辊道炉中，于氮气气氛下，于500℃下煅烧1小时，然后升温到850℃煅烧6小时，冷却后置于pH为3.5的磷酸溶液中浸泡5h，与烘箱500℃烘干后，即得到碳包覆的磷酸铁锂正极材料。42.38g of iron phosphate, 44.12g of lithium carbonate and 10g of Li2FeFe (CN) 6 were mixed in a ball mill for 2 hours, and the mixture was transferred to a roller furnace and calcined at 500℃ for 1 hour under a nitrogen atmosphere, then heated to 850℃ and calcined for 6 hours. After cooling, it was immersed in a phosphoric acid solution with a pH of 3.5 for 5 hours, and dried in an oven at 500℃ to obtain a carbon-coated lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由上述制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the above preparation method.
实施例4：Embodiment 4:
一种磷酸铁锂正极材料的制备方法，包含以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂与10g Li2FeFe(CN)6于球磨机中混合2小时，将上述混合物转移到辊道炉中，于氮气气氛下，于400℃下煅烧4小时，然后升温到650℃煅烧12小时，冷却后置于pH为3.5的磷酸溶液中浸泡5h，与烘箱500℃烘干后，即得到碳包覆的磷酸铁锂正极材料。42.38g of iron phosphate, 44.12g of lithium carbonate and 10g of Li2FeFe (CN) 6 were mixed in a ball mill for 2 hours, and the mixture was transferred to a roller furnace and calcined at 400°C for 4 hours under a nitrogen atmosphere, then heated to 650°C and calcined for 12 hours. After cooling, it was immersed in a phosphoric acid solution with a pH of 3.5 for 5 hours, and dried in an oven at 500°C to obtain a carbon-coated lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由上述制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the above preparation method.
对比例1：(与实施例4相比，未加入Li2FeFe(CN)6)Comparative Example 1: (Compared with Example 4, Li 2 FeFe(CN) 6 was not added)
一种磷酸铁锂正极材料的制备方法，包含以下步骤：
A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂于球磨机中混合2小时，将上述混合物转移到辊道炉中，于氮气气氛下，于400℃下煅烧4小时，然后升温到650℃煅烧12小时，冷却后置于pH为3.5的磷酸溶液中浸泡5h，与烘箱500℃烘干后，即得到磷酸铁锂正极材料。Mix 42.38g of iron phosphate and 44.12g of lithium carbonate in a ball mill for 2 hours, transfer the mixture to a roller furnace, calcine at 400°C for 4 hours under a nitrogen atmosphere, then heat to 650°C and calcine for 12 hours. After cooling, soak in a phosphoric acid solution with a pH of 3.5 for 5 hours, and dry in an oven at 500°C to obtain a lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由上述制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the above preparation method.
对比例2：(与实施例4相比，未在400℃下进行一段煅烧且未酸浸)Comparative Example 2: (Compared with Example 4, no one-stage calcination at 400°C and no acid leaching)
一种磷酸铁锂正极材料的制备方法，包含以下步骤：A method for preparing a lithium iron phosphate positive electrode material comprises the following steps:
将42.38g磷酸铁、44.12g碳酸锂与10g Li2FeFe(CN)6于球磨机中混合2小时，将上述混合物转移到辊道炉中，于氮气气氛下，于650℃煅烧12小时，即得到磷酸铁锂正极材料。42.38 g of iron phosphate, 44.12 g of lithium carbonate and 10 g of Li 2 FeFe(CN) 6 were mixed in a ball mill for 2 hours, and the mixture was transferred to a roller furnace and calcined at 650° C. for 12 hours under a nitrogen atmosphere to obtain a lithium iron phosphate positive electrode material.
一种磷酸铁锂正极材料，由上述制备方法制备得到。A lithium iron phosphate positive electrode material is prepared by the above preparation method.
试验例：Test example:
将实施例1-4和对比例1-2制备的磷酸铁锂正极材料，配成扣式电池，并对其进行锂离子电池电化学性能测试。其具体步骤为：以N-甲基吡咯烷酮为溶剂，按照质量比9.2：0.5：0.3的比例将磷酸铁锂正极材料与乙炔黑、PVDF混合均匀，涂覆于铝箔上，经80℃鼓风干燥8h后，于120℃真空干燥12h。在氩气保护的手套箱中装配电池，负极为金属锂片，隔膜为聚丙烯膜，电解液为1M LiPF6-EC/DMC(1：1，v/v)，采用2032型扣式电池壳在氩气保护的手套箱中组装成扣式电池，然后在25℃下3.0-4.0V进行电化学性能测试。结果如表1所示。The lithium iron phosphate positive electrode materials prepared in Examples 1-4 and Comparative Examples 1-2 were assembled into button cells, and the electrochemical performance of lithium ion batteries was tested. The specific steps are: using N-methylpyrrolidone as a solvent, the lithium iron phosphate positive electrode material is mixed evenly with acetylene black and PVDF in a mass ratio of 9.2:0.5:0.3, coated on aluminum foil, dried at 80°C with forced air for 8 hours, and then vacuum dried at 120°C for 12 hours. The battery was assembled in an argon-protected glove box, the negative electrode was a metal lithium sheet, the diaphragm was a polypropylene film, the electrolyte was 1M LiPF 6 -EC/DMC (1:1, v/v), and a 2032-type button cell shell was used to assemble the button cell in an argon-protected glove box, and then the electrochemical performance was tested at 25°C at 3.0-4.0V. The results are shown in Table 1.
表1：电化学性能测试结果
Table 1: Electrochemical performance test results
Table 1: Electrochemical performance test results
由表1可知，本申请制备得到的磷酸铁锂正极材料的0.1C放电容量能达到150mAh/g以上，0.5C放电比容量能达到130mAh/g以上。对比例2的容量保持率相对于对比例1有一定提高，这是因为对比例2的磷酸铁锂的表面形成了一层碳包覆层，一定程度
上提高了磷酸铁锂导电性能，然而对比例2的克容量并没有明显提升，这是因为仅仅表面包覆碳并不能克服因为包覆碳而导致的活性物质比例降低；实施例1、3、4的容量保持率明显高于对比例1-2，这是因为本方案使用了特定的普鲁士蓝化合物、磷酸铁材料前驱体及锂源混匀后，在400-600℃的条件下煅烧，普鲁士蓝化合物在低温煅烧过程中结合于磷酸铁锂颗粒的表面或者多个磷酸铁锂颗粒的间隙中；然后升温煅烧过程中，存在于磷酸铁锂表面的分解产生均匀的含有Fe的C包覆层，而存在于磷酸铁锂颗粒间隙的普鲁士蓝化合物碳化后可以保持其大框架网络，可以供锂离子作为通道，提高磷酸铁锂材料的导电性能；碳化过程中产生的N2气体可以增加磷酸铁锂材料的多孔性，增大磷酸铁锂和电解液的接触面积，进一步提高导电性能。As shown in Table 1, the 0.1C discharge capacity of the lithium iron phosphate positive electrode material prepared in this application can reach more than 150 mAh/g, and the 0.5C discharge capacity can reach more than 130 mAh/g. The capacity retention rate of Comparative Example 2 is improved to a certain extent compared with Comparative Example 1. This is because a carbon coating layer is formed on the surface of the lithium iron phosphate in Comparative Example 2, which is to a certain extent The conductivity of lithium iron phosphate is improved, but the gram capacity of comparative example 2 is not significantly improved, because only surface coating with carbon cannot overcome the reduction in the proportion of active substances caused by coating with carbon; the capacity retention rates of embodiments 1, 3, and 4 are significantly higher than those of comparative examples 1-2, because the present scheme uses a specific Prussian blue compound, an iron phosphate material precursor, and a lithium source to be mixed and then calcined at 400-600°C, and the Prussian blue compound is combined with the surface of the lithium iron phosphate particles or the gaps between multiple lithium iron phosphate particles during the low-temperature calcination process; then during the temperature-raising calcination process, the decomposition present on the surface of the lithium iron phosphate produces a uniform C coating layer containing Fe, and the Prussian blue compound present in the gaps between the lithium iron phosphate particles can maintain its large framework network after carbonization, which can provide lithium ions as a channel, thereby improving the conductivity of the lithium iron phosphate material; the N2 gas generated during the carbonization process can increase the porosity of the lithium iron phosphate material, increase the contact area between the lithium iron phosphate and the electrolyte, and further improve the conductivity.
实施例2在磷酸铁锂的表面引入了Mn，一般认为锰可以提高磷酸铁锂的电压平台，但是会进一步降低磷酸铁锂的导电性，而实施例2中，因为进行了本方案的处理，仍然具有较高的导电率。In Example 2, Mn is introduced on the surface of lithium iron phosphate. It is generally believed that manganese can increase the voltage platform of lithium iron phosphate, but it will further reduce the conductivity of lithium iron phosphate. In Example 2, due to the treatment of this solution, it still has a high conductivity.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims (10)
- 一种磷酸铁锂正极材料的制备方法，其特征在于：包括以下步骤：A method for preparing a lithium iron phosphate positive electrode material, characterized in that it comprises the following steps:将磷酸铁前驱体、锂源与普鲁士蓝化合物混合，置于还原性或惰性气氛下煅烧，冷却酸浸，烘干后即得。The iron phosphate precursor, lithium source and Prussian blue compound are mixed, calcined in a reducing or inert atmosphere, cooled and acid-leached, and dried to obtain the product.
- 根据权利要求1所述的磷酸铁锂正极材料的制备方法，其特征在于：所述普鲁士蓝化合物为Li2FeFe(CN)6和Li2MnFe(CN)6中的至少一种。The method for preparing a lithium iron phosphate positive electrode material according to claim 1, wherein the Prussian blue compound is at least one of Li 2 FeFe(CN) 6 and Li 2 MnFe(CN) 6 .
- 根据权利要求1所述的磷酸铁锂正极材料的制备方法，其特征在于：所述锂源为LiOH及Li2CO3中的至少一种。The method for preparing a lithium iron phosphate positive electrode material according to claim 1, wherein the lithium source is at least one of LiOH and Li 2 CO 3 .
- 根据权利要求1所述的磷酸铁锂正极材料的制备方法，其特征在于：所述煅烧的方式为先于200-600℃下煅烧1-6小时，然后升温到650-1000℃煅烧6-20小时。The method for preparing a lithium iron phosphate positive electrode material according to claim 1 is characterized in that: the calcination method is to first calcine at 200-600°C for 1-6 hours, and then heat up to 650-1000°C for calcination for 6-20 hours.
- 根据权利要求1所述的一种磷酸铁锂正极材料的制备方法，其特征在于：所述酸浸用到酸为无机酸。The method for preparing a lithium iron phosphate positive electrode material according to claim 1 is characterized in that the acid used in the acid leaching is an inorganic acid.
- 根据权利要求1所述的磷酸铁锂正极材料的制备方法，其特征在于：所述酸浸的pH为3.5-6，所述酸浸的时间为1-40小时。The method for preparing a lithium iron phosphate positive electrode material according to claim 1, characterized in that the pH of the acid leaching is 3.5-6, and the time of the acid leaching is 1-40 hours.
- 根据权利要求1所述的磷酸铁锂正极材料的制备方法，其特征在于：所述烘干的温度为100-500℃。The method for preparing a lithium iron phosphate positive electrode material according to claim 1, wherein the drying temperature is 100-500°C.
- 一种磷酸铁锂正极材料，其特征在于：由权利要求1-7任一项所述的制备方法制备得到。A lithium iron phosphate positive electrode material, characterized in that it is prepared by the preparation method described in any one of claims 1 to 7.
- 如权利要求8所述的磷酸铁锂正极材料在制备锂离子电池中的应用。Use of the lithium iron phosphate positive electrode material as claimed in claim 8 in the preparation of lithium ion batteries.
- 一种锂离子电池，其特征在于，包括权利要求8所述的磷酸铁锂正极材料。 A lithium-ion battery, characterized by comprising the lithium iron phosphate positive electrode material according to claim 8.
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- 2023-02-24 WO PCT/CN2023/078165 patent/WO2024066187A1/en unknown
- 2023-08-23 FR FR2308872A patent/FR3140216A1/en active Pending
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| CN107240676A (en) * | 2016-03-28 | 2017-10-10 | 北京大学深圳研究生院 | A kind of positive electrode of surface modification and its preparation method and application |
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| CN107492679A (en) * | 2017-08-07 | 2017-12-19 | 河南师范大学 | A kind of preparation method of the Prussian blue electrode material of oxide coated by zinc |
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| CN114784239A (en) * | 2022-04-08 | 2022-07-22 | 深圳华钠新材有限责任公司 | Mixed positive electrode material, electrode and electrical device |
| CN115520848A (en) * | 2022-09-28 | 2022-12-27 | 广东邦普循环科技有限公司 | A kind of lithium iron phosphate cathode material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118970018A (en) * | 2024-10-14 | 2024-11-15 | 宁波容百新能源科技股份有限公司 | Positive electrode material and preparation method thereof, positive electrode sheet, battery and electric device |
Also Published As
| Publication number | Publication date |
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| CN115520848A (en) | 2022-12-27 |
| CN115520848B (en) | 2024-03-08 |
| FR3140216A1 (en) | 2024-03-29 |
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