WO2025112043A1 - 一种磷酸铁及其制备方法与用途 - Google Patents

一种磷酸铁及其制备方法与用途 Download PDF

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Publication number
WO2025112043A1
WO2025112043A1 PCT/CN2023/135892 CN2023135892W WO2025112043A1 WO 2025112043 A1 WO2025112043 A1 WO 2025112043A1 CN 2023135892 W CN2023135892 W CN 2023135892W WO 2025112043 A1 WO2025112043 A1 WO 2025112043A1
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Prior art keywords
preparation
solvent
precursor solution
phosphate
iron phosphate
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PCT/CN2023/135892
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English (en)
French (fr)
Inventor
余海军
李爱霞
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to PCT/CN2023/135892 priority Critical patent/WO2025112043A1/zh
Priority to CN202380012423.2A priority patent/CN117897356B/zh
Publication of WO2025112043A1 publication Critical patent/WO2025112043A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • 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
    • 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 field of battery materials and relates to iron phosphate and a preparation method and application thereof.
  • the positive electrode material is a key material that directly determines the energy density and safety of the battery. It affects the overall performance of the lithium-ion battery. Different types of positive electrode materials also bring about differences in performance.
  • Lithium iron phosphate (molecular formula LiFePO 4 , Lithium Iron Phosphate, also known as lithium iron phosphate, lithium iron phosphorus, abbreviated as LFP) is an important positive electrode material for lithium-ion batteries. Because it does not contain precious elements such as cobalt, the reserves and content of phosphorus, lithium, and iron resources it uses are abundant. Therefore, compared with other positive electrode materials, lithium iron phosphate has the advantages of wide raw materials, stable supply, and low cost. In addition, it has a moderate operating voltage (3.2V), large capacity (170mAh/g), high discharge power, fast charging, long cycle life, and high stability in high temperature and high heat environments.
  • LFP Lithium Iron phosphate
  • Lithium iron phosphate materials have occupied a place in the power battery market with their excellent safety performance and low price.
  • their low electronic conductivity about 10-9 S/cm
  • ionic conductivity about 10-13 ⁇ 10-16 S/cm
  • people have proposed a variety of methods to improve the rate performance of lithium iron phosphate materials.
  • reducing the particle size of lithium iron phosphate materials is a very effective method. By preparing small-sized lithium iron phosphate particles, the distance of ion diffusion can be effectively shortened, thereby achieving the purpose of improving the rate performance of lithium iron phosphate.
  • the purpose of the present disclosure is to provide an iron phosphate and a preparation method and use thereof.
  • the preparation method prepares a precursor solution prepared from an iron source, a phosphate source, an amide substance and a first solvent and fills it into a mesoporous material to form a filling body, then adds a second solvent that is immiscible with the first solvent and has a different density, and uses the second solvent to wrap the filling body, so that the precursor solution is sealed in the cavity/pore in the mesoporous material.
  • the mesoporous material produces a blocking and limiting effect, so that the precursor solution in the cavity can generate iron phosphate particles smaller than the volume of the cavity/pore after reaction, and then after removing the mesoporous material by calcination, discrete small-size iron phosphate particles can be obtained.
  • the present invention adopts the following technical solutions:
  • the present disclosure provides a method for preparing iron phosphate, the preparation method comprising:
  • the precursor solution includes an iron source, a phosphate source, an amide substance and a first solvent;
  • the coating solution is heated to react, and iron phosphate is generated inside the coating to obtain a sealed body;
  • the sealed body is calcined to obtain iron phosphate.
  • the preparation method disclosed in the present invention uses a mesoporous material as a sacrificial template, mixes the mesoporous material with a precursor solution, fills the pores or cavities of the mesoporous material with the precursor solution to form a filling body, then adds a second solvent to wrap the filling body, removes the precursor solution outside the filling body, and fills the cavity with the precursor solution inside.
  • the precursor solution is sealed, that is, the second solvent plays a role similar to "oil seal" to obtain a coating body.
  • the second solvent and the first solvent are mutually immiscible and have different densities (immiscible), so that when the filling body is transferred to the second solvent, the second solvent can exclude the first solvent and cover the surface of the filling body; at this time, the coating body is heated, and the amide substance in the precursor solution filled in the cavity will decompose, and then the pH of the sealed precursor solution is adjusted so that the precursor solution reaches the conditions for generating iron phosphate to perform a generation reaction.
  • the preparation method can control and adjust the particle size, and is conducive to obtaining discrete non-agglomerated products.
  • the preparation method can mix the iron source, phosphate source, amide substance and the first solvent with the mesoporous material at the same time, or form a precursor solution first, and then mix it with the mesoporous material.
  • the iron source, phosphate source, and amide substance can be completely dissolved to form a precursor solution, and the formed precursor solution can fill the cavity and pores of the mesoporous material to form a filling body. Therefore, the specific amount of the precursor solution and the mesoporous material can be adjusted according to actual conditions and needs. If the precursor solution is used in excess, the excess precursor solution can be collected and mixed with a new mesoporous material.
  • the amount of the iron source, phosphate source and amide substance is controlled, for example, 1:1:1, 1:1:1.5, 1:1:2, 1:1:2.5, 1:1:3, 1:1:3.5, 1:1:4, 1:1:4.5, 1:1:5, 1:1:5.5, 1:1:6, 1:1:6.5, 1:1:7, 1:1:7.5 or 1:1:8, but it is not limited to the values listed above, and other values within the above numerical range are not limited thereto. The listed values also apply.
  • the amide substance includes any one of urea, formamide or acetamide, or a combination of at least two of them.
  • Typical but non-limiting examples of the combination include a combination of urea and formamide, a combination of urea and acetamide, or a combination of formamide and acetamide.
  • Amide substances are used to decompose during subsequent heating to increase the pH of the solution to support the generation of iron phosphate. However, if the amount is too large, impurities such as iron phosphate or iron hydroxide will be generated in the precursor solution before heating.
  • the iron source comprises a ferric iron salt.
  • the ferric salt comprises ferric nitrate and/or ferric chloride.
  • the phosphate source includes any one of sodium phosphate, ammonium hydrogen phosphate or diammonium phosphate, or a combination of at least two of them.
  • Typical but non-limiting examples of the combination include a combination of sodium phosphate and ammonium hydrogen phosphate, a combination of sodium phosphate and diammonium dihydrogen phosphate, or a combination of ammonium hydrogen phosphate and diammonium dihydrogen phosphate.
  • an iron source and a phosphate source are used to generate iron phosphate.
  • the pH value of the precursor solution is 1 to 1.5, for example, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45 or 1.5, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the temperature of the precursor solution is ⁇ 20°C.
  • the pH range needs to be adjusted to a strongly acidic range when the precursor solution is prepared. At this time, the temperature of the precursor solution can be lowered to further inhibit the decomposition of amide substances, thereby preventing the premature generation of iron phosphate and allowing the precursor solution to be smoothly filled into the mesoporous material.
  • the mesoporous material includes a mesoporous polymer.
  • Mesoporous polymers have strong capillary forces, which is conducive to the precursor solution filling the mesoporous polymer. In the channels and cavities of the body.
  • the mesoporous polymer includes any one of methacrylate polymer, styrene polymer, styrene derivative polymer or a combination of at least two thereof, and typical but non-limiting examples of the combination include a combination of methacrylate polymer and styrene polymer, a combination of methacrylate polymer and styrene derivative polymer, or a combination of styrene polymer and styrene derivative polymer.
  • the polymer includes a monomer or a copolymer.
  • the mesoporous material is microsphere particles, and the particle size of the microsphere particles is 2 to 50 ⁇ m, for example 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 45 ⁇ m, 48 ⁇ m or 50 ⁇ m, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the precursor liquid that the mesoporous polymer can accommodate determines the liquid that participates in the reaction. Therefore, the particle size of the output iron phosphate can be adjusted by regulating the particle size of the mesoporous conjugate microspheres, and iron phosphate products of 0.1 to 10 ⁇ m can be produced, such as 0.1 ⁇ m, 0.3 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m or 10 ⁇ m, etc., but are not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the preparation method includes, when mixing the precursor solution and the mesoporous material, performing a vacuum treatment so that the precursor solution is filled in the mesoporous material.
  • the vacuum degree of the vacuum treatment is 0.05-0.2 MPa, for example, 0.05 MPa, 0.08 MPa, 0.1 MPa, 0.12 MPa, 0.14 MPa, 0.16 MPa, 0.18 MPa or 0.2 MPa, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the present disclosure can further promote the increase of the amount of precursor solution in the mesoporous material by applying vacuum, thereby ensuring the complete filling of the pores and cavities in the mesoporous material and increasing the output efficiency of iron phosphate.
  • the second solvent comprises edible oil and/or liquid paraffin.
  • the first solvent includes water, which is also conducive to the dissolution of amide substances;
  • the second solvent is selected to be a solvent that is immiscible with water to exclude water on the surface of the mesoporous material so as to play an oil sealing role.
  • organic solvents that are immiscible with water have certain volatility and toxicity, edible oil and/or liquid paraffin can be used. Of course, reasonable adjustments can also be made according to actual conditions.
  • the temperature of the heating reaction is 80-120°C, for example, 80°C, 83°C, 86°C, 89°C, 92°C, 95°C, 98°C, 100°C, 103°C, 106°C, 109°C, 112°C 115°C, 118°C or 120°C, and the time is 2-4h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h or 4h, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the temperature of the heating reaction is the appropriate temperature for the production of ferric phosphate.
  • this temperature it should also be considered that the amide substances can be decomposed to promote the increase of the pH value of the solution.
  • the calcination temperature is 550-650°C, for example, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C or 650°C, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the calcination temperature has little effect on the particle size of iron phosphate.
  • the preparation method comprises:
  • deionized water as the first solvent, first adjusting the pH of the deionized water to 1 with an acid, adding an iron source, a phosphate source and an amide substance under stirring, controlling the added amount according to the molar ratio of the iron element, the phosphate and the amide group being 1:1:(1-1.8), then adjusting the pH to 1.0-1.5 with an acid, maintaining the temperature below 20° C., to obtain a precursor solution;
  • mesoporous styrene polymer microsphere particles with a particle size range of 2 to 50 ⁇ m as the mesoporous material, the mesoporous material is placed in a precursor solution, fully stirred, and evacuated to a vacuum degree of 0.05 to 0.2 MPa to fill the precursor solution in the mesoporous material to form a filling body, thereby obtaining a filling body solution;
  • the coating solution is heated at 80 to 120° C. for 2 to 4 hours to generate iron phosphate nanoparticles inside the coating, and after cooling and filtering, a sealed body is obtained;
  • the sealed body is calcined at 550-650° C., washed with water for multiple times, and then dried to obtain discrete iron phosphate particles.
  • the present disclosure provides an iron phosphate, which is obtained using the preparation method described in the first aspect.
  • the present disclosure provides a lithium iron phosphate positive electrode material, wherein the lithium iron phosphate positive electrode material is prepared using the iron phosphate described in the second aspect.
  • the present invention has at least the following beneficial effects:
  • the present disclosure provides a preparation method that can control the particle size of iron phosphate and obtain small-size iron phosphate.
  • the preparation method uses a mesoporous material as a sacrificial template, and a precursor solution is wrapped inside and then decomposed by an amide substance to make the precursor solution reach the conditions for generating iron phosphate and perform a generation reaction.
  • the physical restriction and isolation effect of the mesoporous material can be used to effectively control the particle size of iron phosphate and obtain discrete small-particle iron phosphate.
  • FIG. 1 is a scanning electron microscope test image of the iron phosphate obtained in Example 1.
  • This embodiment provides a method for preparing iron phosphate, the preparation method comprising:
  • the pH value of the deionized water solution was adjusted to 1 with nitric acid, and then ferric nitrate was added under stirring, and after being fully stirred and mixed, sodium hydrogen phosphate was added, and the molar ratio of ferric nitrate and sodium hydrogen phosphate was kept at 1:1, and then urea was added and stirred and mixed evenly, and the molar ratio of ferric nitrate, sodium hydrogen phosphate and urea was kept at 1:1:1.4, and then the pH value of the solution was adjusted to 1.2 with nitric acid, and the temperature was kept below 20°C during the process to form a precursor solution.
  • Mesoporous polystyrene microsphere particles with a diameter of 20 ⁇ m were immersed in the precursor solution, and after being fully stirred, the vacuum degree was set to 0.1 MPa for vacuum treatment for 15 minutes to form a filling body; soybean oil was then introduced into the upper layer of the reaction liquid, and the reaction liquid of the lower layer was removed to form a coating body; the remaining liquid was heated to 80°C for heating reaction for 3 hours, and then cooled and filtered to obtain a sealed body, which was calcined at 600°C for 30 minutes, washed with water, and dried at 110°C to obtain small discrete iron phosphate particles.
  • This embodiment provides a method for preparing iron phosphate, the preparation method comprising:
  • the pH value of the solution was adjusted to 1 by acid, and the temperature was kept below 20°C during the process to form a precursor solution.
  • Mesoporous polystyrene microsphere particles with a diameter of 50 ⁇ m were immersed in the precursor solution, and after sufficient stirring, the vacuum degree was set to 0.05 MPa for vacuum treatment for 15 minutes to form a filling body; soybean oil was then introduced into the upper layer of the reaction liquid, and the reaction liquid in the lower layer was removed to form a coating body; the remaining liquid was heated to 120°C for 4 hours, and then cooled and filtered to obtain a sealed body, which was calcined at 650°C for 60 minutes, washed with water, and dried at 110°C to obtain small discrete iron phosphate particles.
  • This embodiment provides a method for preparing iron phosphate, the preparation method comprising:
  • the pH value of the deionized water solution was adjusted to 1 with sulfuric acid, and then ferric nitrate was added under stirring conditions, and after sufficient stirring and mixing, ammonium dihydrogen phosphate was added, and the molar ratio of ferric chloride and ammonium dihydrogen phosphate was maintained at 1:1, and then acetamide was added and stirred and mixed, and the molar ratio of ferric nitrate, ammonium dihydrogen phosphate and acetamide was maintained at 1:1:1.8, and then the pH value of the solution was adjusted to 1 with phosphoric acid, and the temperature was kept below 20°C during the process to form a precursor solution.
  • Mesoporous polystyrene microsphere particles with a diameter of 2 ⁇ m were immersed in the precursor solution, and after sufficient stirring, the vacuum degree was set to 0.2 MPa for vacuum treatment for 15 minutes to form a filling body; soybean oil was then introduced into the upper layer of the reaction liquid, and the reaction liquid of the lower layer was removed to form a coating body; the remaining liquid was heated to 100°C for heating reaction for 2 hours, and then cooled and filtered to obtain a sealed body, which was calcined at 550°C for 120 minutes, washed with water, and dried at 110°C to obtain small discrete iron phosphate particles.
  • This embodiment provides a method for preparing iron phosphate, wherein the diameter of the mesoporous polystyrene microsphere particles is adjusted from 20 ⁇ m to 0.9 ⁇ m. Except for the above, other conditions are exactly the same as those in Example 1.
  • This embodiment provides a method for preparing iron phosphate, wherein the diameter of the mesoporous polystyrene microsphere particles is adjusted from 20 ⁇ m to 2 ⁇ m. Except for the above, other conditions are exactly the same as those in Example 1.
  • This embodiment provides a method for preparing iron phosphate, in which the vacuum degree of the vacuum treatment is adjusted from 0.1 MPa to 0.05 MPa. Except for the above, other conditions are exactly the same as those in Example 1.
  • This comparative example provides a method for preparing iron phosphate, wherein the preparation method does not use amide substances, that is, does not use urea. Except for the above, other conditions are exactly the same as those in Example 1.
  • This comparative example provides a method for preparing iron phosphate, in which soybean oil, a second solvent, is not used.
  • the obtained filler is directly subjected to heating reaction, and then calcined and crushed. Except for the above, other conditions are exactly the same as those in Example 1.
  • This comparative example provides a method for preparing iron phosphate, which does not use mesoporous materials, does not perform vacuum treatment, and does not use soybean oil as a second solvent.
  • the obtained precursor solution is directly heated to react, and then calcined and crushed. Except for the above, other conditions are exactly the same as those in Example 1.
  • FIG1 is a scanning electron microscope test image of the iron phosphate obtained in Example 1. It can be seen from FIG1 that the obtained iron phosphate is spherical, the particles are discrete, and no agglomeration occurs. There are gaps left by mesoporous polystyrene microspheres inside the particles, and the particle size is 2 to 4 ⁇ m.
  • the particle size of the mesoporous polymer By controlling the particle size of the mesoporous polymer to be small, the particle size of the iron phosphate can be controlled; at the same time, it can be seen that the filling amount of the reaction solution in the cavity of the mesopores can be increased by vacuuming, thereby changing the particle size of the iron phosphate.
  • Electrochemical performance test The iron phosphate obtained in Example 1, Comparative Example 1 and Comparative Example 3 was used as a precursor raw material and was loaded into a ball mill with Li2CO3 , and was wet-milled with anhydrous ethanol at a speed of 600 rpm for 5 hours; glucose, lithium carbonate and the prepared iron phosphate precursor in a molar ratio of 0.05:1.05:1.0 were calcined at 600°C under a nitrogen atmosphere to obtain a lithium iron phosphate material.
  • the prepared lithium iron phosphate positive electrode material was mixed with acetylene black and polyvinylidene fluoride (PVDF) cyclohexane solution at room temperature and pressure to form a slurry (the weight ratio of positive electrode material: acetylene black: PVDF was 75:15:10), and evenly coated on an aluminum foil substrate as the positive electrode of the simulated battery.
  • the negative electrode of the simulated battery used a lithium sheet, and the The electrolyte is 1 mol LiPF 6 dissolved in 1L EC (ethylene carbonate) and DMC (dimethyl carbonate) mixed solvent (volume ratio 1:1).
  • the positive electrode, negative electrode, electrolyte, and diaphragm are assembled into a simulated battery in an argon-protected glove box.
  • the diaphragm is a polypropylene porous membrane.
  • the rate test steps of the simulated battery are: first charge to 4.2V at 30mA/g, then discharge to 2.0V at the rate current, and the released capacity is the discharge capacity at the rate. After the discharge is completed, discharge to 2.0V at 30mA/g. Then perform the next rate test. The results are shown in Table 2:
  • the iron phosphate precursor formed in Comparative Example 1 without adding urea at a low pH has a poor effect as a precursor material for lithium iron phosphate; and the precursor formed by Comparative Example 3 cannot obtain iron phosphate with uniform discrete particle size after crushing, and the performance of the obtained lithium iron phosphate is significantly worse.

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Abstract

一种磷酸铁及其制备方法与用途，将铁源、磷酸根源、酰胺类物质及第一溶剂配制得到的前驱体溶液并填充于介孔物料之内，形成填充体，再加入与第一溶剂互不相溶且密度不同的第二溶剂，利用第二溶剂包裹填充体，使前驱体溶液密封于介孔物料内部的空腔或孔道，介孔物料产生阻挡和限制作用，从而使空腔或孔道内的前驱体溶液反应后可生成小于空腔体积的磷酸铁颗粒，再通过煅烧去除介孔物料后，可以获得离散的小粒径磷酸铁颗粒。

Description

一种磷酸铁及其制备方法与用途 技术领域
本公开属于电池材料领域，涉及一种磷酸铁及其制备方法与用途。
背景技术
正极材料是直接决定电池能量密度和安全性的关键材料，其影响锂离子电池的综合性能，不同种类的正极材料也带来了性能情况的差异。
磷酸锂铁(分子式LiFePO4，Lithium Iron Phosphate，又称磷酸铁锂、锂铁磷，简称LFP)，是一种重要的锂离子电池正极材料。由于它不含钴等贵重元素，其使用的磷、锂、铁资源的储量及含量丰富，因此，相比于其他正极材料，磷酸铁锂具有原料广泛、供应稳定、成本低廉等优势。而且，其工作电压适中(3.2V)、电容量大(170mAh/g)，还具备高放电功率、可快速充电、循环寿命长，在高温与高热环境下的稳定性高等优势。
磷酸铁锂材料凭借着优异的安全性能和低廉的价格，在动力电池市场占据了一席之地。但是由于其较低的电子电导率(约10-9S/cm)和离子电导率(约10-13～10-16S/cm)制约了其大电流充放电的能力。为了解决这一问题，人们提出了多种办法来提升磷酸铁锂材料的倍率性能，其中，降低磷酸铁锂材料的粒径大小是一种非常有效的方法，通过制备小尺寸的磷酸铁锂颗粒可以有效地缩短离子扩散的距离，从而达到提升磷酸铁锂倍率性能的目的。
可见，作为制备磷酸铁锂重要的原料之一，磷酸铁(FePO4)的微观结构及化学组分的微小变化都会对磷酸铁锂的性能产生巨大的影响。控制磷酸铁材料的合成质量，确保小尺寸磷酸铁材料的稳定生产及其性质的均一稳定，对制备高性能的磷酸铁锂材料非常关键。因此，开发一种新的可以控制磷酸铁粒径的 方法，以制备出小尺寸的磷酸铁颗粒具有重要意义。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
鉴于现有技术中存在的问题，本公开的目的在于提供一种磷酸铁及其制备方法与用途，所述制备方法将铁源、磷酸根源、酰胺类物质及第一溶剂配制得到的前驱体溶液并填充于介孔物料之内，形成填充体，再加入与第一溶剂互不相溶且密度不同的第二溶剂，利用第二溶剂包裹填充体，使前驱体溶液密封于介孔物料内的空腔/孔道，介孔物料产生阻挡和限制作用，从而使空腔内的前驱体溶液反应后可生成小于空腔/孔道体积的磷酸铁颗粒，再通过煅烧去除介孔物料后，可以获得离散的小粒径磷酸铁颗粒。
为达此目的，本公开采用以下技术方案：
第一方面，本公开提供了一种磷酸铁的制备方法，所述制备方法包括：
混合前驱体溶液与介孔物料，使前驱体溶液填充于介孔物料之内，形成填充体，得到填充体溶液；所述前驱体溶液包括铁源、磷酸根源、酰胺类物质及第一溶剂；
混合填充体溶液与第二溶剂，使第二溶剂覆盖填充体的表面形成包覆体，得到包覆体溶液；
将包覆体溶液进行加热反应，在包覆体的内部生成磷酸铁，得到封存体；
将封存体进行煅烧，得到磷酸铁。
本公开所述制备方法使用介孔物料作为牺牲模板，将介孔物料与前驱体溶液混合，使介孔物料的孔道或空腔中充满前驱体溶液，形成填充体，再加入第二溶剂包裹填充体，去除填充体外部的前驱体溶液，将内部的填充在空腔中的 前驱体溶液进行封存，即，第二溶剂起到类似于“油封”的作用，从而得到包覆体，可以理解的是，所述第二溶剂与所述第一溶剂互不相溶且密度不同(不互溶)，才能使填充体转移至第二溶剂中时，使得第二溶剂能够排除第一溶剂并且覆盖在填充体表面；此时，加热包覆体，填充于空腔内部的前驱体溶液中的酰胺类物质将分解，进而调节已被封存的前驱体溶液的pH，使前驱体溶液达到生成磷酸铁的条件，以进行生成反应。此时，由于介孔物料的存在，物理上限制了磷酸铁的生长，可以得到小粒径的磷酸铁锂颗粒，且由于介孔物料起到的物理隔离作用，相邻的包覆体中所生长的磷酸铁不会合并长大，因而得到离散形式的小颗粒磷酸铁。最后，通过煅烧，去除掉作为牺牲模板的介孔物料，得到最终产品。因此，所述制备方法能够控制并调节粒径，且有利于得到离散不团聚的产品。
需要说明的是，所述制备方法可以将铁源、磷酸根源、酰胺类物质及第一溶剂与介孔物料同时混合，也可以先形成前驱体溶液，再与介孔物料混合，只要保证混合均匀充分，铁源、磷酸根源、酰胺类物质均能完全溶解形成前驱体溶液，且所形成的前驱体溶液能充满介孔物料的空腔和孔道，形成填充体即可。因此，可以根据实际情况和需要调整前驱体溶液及介孔物料的具体用量。如前驱体溶液用量过多后，多余的前驱体溶液可以收集并与新的介孔物料混合使用。
以下作为本公开可选的技术方案，但不作为本公开提供的技术方案的限制，通过以下技术方案，可以更好地达到和实现本公开的技术目的和有益效果。
作为本公开可选的技术方案，按照铁元素、磷酸根及酰胺基团的摩尔比为1:1:(1～1.8)，控制所述铁源、磷酸根源及酰胺类物质的用量，例如1:1:1、1:1:1.5、1:1:2、1:1:2.5、1:1:3、1:1:3.5、1:1:4、1:1:4.5、1:1:5、1:1:5.5、1:1:6、1:1:6.5、1:1:7、1:1:7.5或1:1:8等，但并不仅限于所列举的数值，上述数值范围内其他未 列举的数值同样适用。
在一个实施方式中，所述酰胺类物质包括尿素、甲酰胺或乙酰胺中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括尿素与甲酰胺的组合、尿素与乙酰胺的组合或甲酰胺与乙酰胺的组合。
酰胺类物质用于后续加热时分解，提高溶液pH，以支持磷酸铁的产生。而其用量过大，会导致在加热前前驱体溶液中提前产生磷酸铁或氢氧化铁等杂质。
在一个实施方式中，所述铁源包括三价铁盐。
在一个实施方式中，所述三价铁盐包括硝酸铁和/或氯化铁。
在一个实施方式中，所述磷酸根源包括磷酸钠、磷酸氢铵或磷酸二氢铵中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括磷酸钠与磷酸氢铵的组合、磷酸钠与磷酸二氢铵的组合，或磷酸氢铵与磷酸二氢铵的组合。
本公开中，铁源及磷酸根源用于生成磷酸铁。
作为本公开可选的技术方案，所述前驱体溶液的pH值为1～1.5，例如1、1.05、1.1、1.15、1.2、1.25、1.3、1.35、1.4、1.45或1.5等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
在一个实施方式中，所述前驱体溶液的温度≤20℃。
由于前驱体溶液中含有酰胺类物质，为了抑制酰胺类物质在前驱体溶液进行加热反应前的分解，在前驱体溶液配制时，需要调节为强酸性的pH范围，此时，可以降低前驱体溶液的温度，进一步抑制酰胺类物质的分解，从而防止磷酸铁的提前产生，使前驱体溶液顺利填充于介孔物料之内。
作为本公开可选的技术方案，所述介孔物料包括介孔聚合物。
介孔聚合物具有强毛细作用力，有利于使其前驱体溶液充满介孔聚合物内 部的孔道和空腔中。
在一个实施方式中，所述介孔聚合物包括甲基丙烯酸酯聚合物、苯乙烯聚合物、苯乙烯衍生物聚合物中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括基丙烯酸酯聚合物与苯乙烯聚合物的组合、基丙烯酸酯聚合物与苯乙烯衍生物聚合物的组合，或苯乙烯聚合物与苯乙烯衍生物聚合物的组合。所述聚合物包括单聚物或共聚物。
在一个实施方式中，所述介孔物料为微球颗粒，所述微球颗粒的粒径为2～50μm，例如2μm、5μm、8μm、10μm、12μm、15μm、18μm、20μm、22μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、45μm、48μm或50μm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
介孔聚合物所能容纳的前驱体液体决定其参与反应的液体，因此可以通过调控介孔结合物微球的粒径来调整产出的磷酸铁粒径，能够产出0.1～10μm的磷酸铁产品，例如0.1μm、0.3μm、0.5μm、0.8μm、1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm、5.5μm、6μm、6.5μm、7μm、7.5μm、8μm、8.5μm、9μm、9.5μm或10μm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本公开可选的技术方案，所述制备方法包括，在混合前驱体溶液与介孔物料时，通过抽真空处理，使得使前驱体溶液填充于介孔物料之内。
在一个实施方式中，所述抽真空处理的真空度为0.05～0.2MPa，例如0.05MPa、0.08MPa、0.1MPa、0.12MPa、0.14MPa、0.16MPa、0.18MPa或0.2MPa等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
本公开可以进一步通过施加真空促介孔物料之内的前驱体溶液量的增加，确保介孔物料内的孔道和空腔的完全填充，增大磷酸铁的产出效率。
作为本公开可选的技术方案，所述第一溶剂包括水。
在一个实施方式中，所述第二溶剂包括食用油和/或液体石蜡。
由于铁源、磷酸根源一般为无机盐类，其溶解在水中，因此第一溶剂包括水，也有利于酰胺类物质的溶解；第二溶剂选择与水不互溶的溶剂，以排除介孔物料表面的水从而能起到油封作用，考虑到与水不互溶的有机溶剂具有一定挥发性和毒性，因此可选使用食用油和/或液体石蜡，当然也可以根据实际情况进行合理的调整。
作为本公开可选的技术方案，所述加热反应的温度为80～120℃，例如80℃、83℃、86℃、89℃、92℃、95℃、98℃、100℃、103℃、106℃、109℃、112℃115℃、118℃或120℃等，时间为2～4h，例如2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h或4h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
加热反应的温度是磷酸铁产生的适宜温度，选择此温度时也应考虑到能使酰胺类物质分解而促进溶液pH值的提升。
在一个实施方式中，所述煅烧的温度为550～650℃，例如550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃或650℃等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
在适宜的范围内，煅烧温度对磷酸铁的粒径的影响较小。
作为本公开可选的技术方案，所述制备方法包括：
使用去离子水作为第一溶剂，先利用酸调节去离子水的pH为1，在搅拌下加入铁源、磷酸根源和酰胺类物质，按照铁元素、磷酸根及酰胺基团的摩尔比为1:1:(1～1.8)控制加入量，再利用酸调节pH为1.0～1.5，保持温度为20℃以下，得到前驱体溶液；
使用粒径范围为2～50μm的介孔苯乙烯聚合物微球颗粒作为介孔物料，将介孔物料放入到前驱体溶液中，充分搅拌，通过抽真空至真空度为0.05～0.2MPa，使前驱体溶液填充于介孔物料之内，形成填充体，得到填充体溶液；
向填充体溶液中倒入第二溶剂，所述第二溶剂与所述第一溶剂互不相溶且密度不同，使填充体转移并浸没在第二溶剂中，且第二溶剂覆盖填充体的表面形成包覆体，移除与第二溶剂相分层的液体后，得到包覆体溶液；
将包覆体溶液于80～120℃下进行加热反应2～4h，在包覆体的内部生成磷酸铁纳米颗粒，冷却并过滤后，得到封存体；
将封存体于550～650℃下煅烧，进行多次水洗后干燥，获得离散的磷酸铁颗粒。
第二方面，本公开提供了一种磷酸铁，所述磷酸铁使用第一方面所述的制备方法得到。
第三方面，本公开提供了一种磷酸铁锂正极材料，所述磷酸铁锂正极材料使用第二方面所述的磷酸铁制备得到。
与现有技术方案相比，本公开至少具有以下有益效果：
本公开提供了一种能控制磷酸铁粒径并获得小粒径磷酸铁的制备方法，所述制备方法使用介孔物料作为牺牲模板，前驱体溶液包裹于内部后再通过酰胺类物质的分解，使前驱体溶液达到生成磷酸铁的条件，进行生成反应；此时，利用介孔物料起到的物理限制和隔绝作用，可以有效控制磷酸铁的粒径，获得离散的小颗粒磷酸铁。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分， 与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是实施例1所得磷酸铁的扫描电镜测试图。
具体实施方式
下面通过具体实施方式来进一步说明本公开的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
本实施例提供了一种磷酸铁的制备方法，所述制备方法包括：
用硝酸调节去离子水溶液的pH＝1，然后在搅拌条件下加入硝酸铁，充分搅拌混合后，加入磷酸氢钠，保持硝酸铁和磷酸氢钠的摩尔比为1:1，后加尿素充分搅拌混合均匀，保持硝酸铁、磷酸氢钠和尿素的摩尔比为1:1:1.4，再用硝酸调节溶液pH值为1.2，过程持续保持温度在20℃以下，形成前驱体溶液。将直径为20μm的介孔聚苯乙烯微球颗粒浸没在前驱体溶液中，充分搅拌后，设置真空度为0.1MPa进行抽真空处理15min，形成填充体；后将大豆油导入反应液体上层，再移除下层的反应液，形成包覆体；将剩余液体升高温度至80℃进行加热反应3h后，经冷却、过滤得到封存体，经600℃煅烧30min后，再经过水洗后在110℃下干燥，获得小颗粒离散磷酸铁颗粒。
实施例2
本实施例提供了一种磷酸铁的制备方法，所述制备方法包括：
用盐酸调节去离子水溶液的pH＝1，然后在搅拌条件下加入氯化铁，充分搅拌混合后，加入磷酸氢铵，保持氯化铁和磷酸氢铵的摩尔比为1:1，后加甲酰胺充分搅拌混合均匀，保持氯化铁、磷酸氢铵和甲酰胺的摩尔比为1:1:1，再用盐 酸调节溶液pH值为1，过程持续保持温度在20℃以下，形成前驱体溶液。将直径为50μm的介孔聚苯乙烯微球颗粒浸没在前驱体溶液中，充分搅拌后，设置真空度为0.05MPa进行抽真空处理15分钟，形成填充体；后将大豆油导入反应液体上层，再移除下层的反应液，形成包覆体；将剩余液体升高温度至120℃进行加热反应4h后，经冷却、过滤得到封存体，经650℃煅烧60min后，再经过水洗后在110℃下干燥，获得小颗粒离散磷酸铁颗粒。
实施例3
本实施例提供了一种磷酸铁的制备方法，所述制备方法包括：
用硫酸调节去离子水溶液的pH＝1，然后在搅拌条件下加入硝酸铁，充分搅拌混合后，加入磷酸二氢铵，保持氯化铁和磷酸二氢铵的摩尔比为1:1，后加乙酰胺充分搅拌混合均匀，保持硝酸铁、磷酸二氢铵和乙酰胺的摩尔比为1:1:1.8，再用磷酸调节溶液pH值为1，过程持续保持温度在20℃以下，形成前驱体溶液。将直径为2μm的介孔聚苯乙烯微球颗粒浸没在前驱体溶液中，充分搅拌后，设置真空度为0.2MPa进行抽真空处理15分钟，形成填充体；后将大豆油导入反应液体上层，再移除下层的反应液，形成包覆体；将剩余液体升高温度至100℃进行加热反应2h后，经冷却、过滤得到封存体，经550℃煅烧120min后，再经过水洗后在110℃下干燥，获得小颗粒离散磷酸铁颗粒。
实施例4
本实施例提供了一种磷酸铁的制备方法，所述制备方法将介孔聚苯乙烯微球颗粒的直径由20μm调整为0.9μm，除以上外，其他条件与实施例1完全相同。
实施例5
本实施例提供了一种磷酸铁的制备方法，所述制备方法将介孔聚苯乙烯微球颗粒的直径由20μm调整为2μm，除以上外，其他条件与实施例1完全相同。
实施例6
本实施例提供了一种磷酸铁的制备方法，所述制备方法将介孔聚苯乙烯微球颗粒的直径由20μm调整为30μm，除以上外，其他条件与实施例1完全相同。
实施例7
本实施例提供了一种磷酸铁的制备方法，所述制备方法将抽真空处理的真空度由0.1MPa调整为0.05MPa，除以上外，其他条件与实施例1完全相同。
对比例1
本对比例提供了一种磷酸铁的制备方法，所述制备方法不使用酰胺类物质，即不使用尿素，除以上外，其他条件与实施例1完全相同。
对比例2
本对比例提供了一种磷酸铁的制备方法，所述制备方法不使用第二溶剂大豆油，将所得填充体直接进行加热反应，然后煅烧、破碎，除以上外，其他条件与实施例1完全相同。
对比例3
本对比例提供了一种磷酸铁的制备方法，所述制备方法不使用介孔物料、不进行抽真空处理，且不使用第二溶剂大豆油，将所得前驱体溶液直接进行加热反应，然后煅烧、破碎，除以上外，其他条件与实施例1完全相同。
图1为实施例1所得磷酸铁的扫描电镜测试图，从图1中可以看出，所得磷酸铁为类球形，颗粒之间为离散状态，未发生团聚，颗粒内部具有介孔聚苯乙烯微球留下的空隙，其粒径在2～4μm。
将实施例及对比例所得磷酸铁进行粒径测试，结果记录于表1。
表1
由表1可以看出：
通过控制介孔聚合物的粒径小，可以控制磷酸铁的粒径大小；同时可以看出，通过抽真空作用，可以增加介孔内空腔反应溶液的填充量，从而使磷酸铁粒径变化。
电化学性能测试：将实施例1、对比例1及对比例3所得磷酸铁作为前驱体原料与Li2CO3装入球磨机内，用无水乙醇湿法球磨以600rpm的转速球磨5h；按照摩尔比为0.05:1.05:1.0的葡萄糖、碳酸锂和制得的磷酸铁前驱体在氮气氛围下，经过600℃煅烧得到磷酸铁锂材料。
将制得的磷酸铁锂正极材料与乙炔黑和聚偏氟乙烯(PVDF)的环己烷溶液在常温常压下混合形成浆料(按照正极材料:乙炔黑:PVDF重量份比为75:15:10)，均匀涂敷于铝箔衬底上，作为模拟电池的正极。模拟电池的负极使用锂片，电 解液为1mol LiPF6溶于1L EC(碳酸乙烯酯)和DMC(碳酸二甲酯)的混合溶剂中(体积比1:1)。将正极、负极、电解液，隔膜在氩气保护的手套箱内组装成模拟电池，所述隔膜为聚丙烯多孔膜。模拟电池的倍率测试步骤：首先以30mA/g充电至4.2V，然后倍率电流放电至2.0V，所放出的容量即为该倍率下的放电容量，放电结束后再以30mA/g放电至2.0V。然后进行下一倍率的测试。结果如表2所示：
表2
由上表可知，与实施例1相比，对比例1不添加尿素，在低pH下形成的磷酸铁前驱体，作为磷酸铁锂的前驱体材料，其作用效果差；而通过对比例3所形成的前驱体经破碎，不能得到离散粒度均一的磷酸铁，则所得磷酸铁锂，性能效果明显更差。

Claims (17)

  1. 一种磷酸铁的制备方法，包括：
    混合前驱体溶液与介孔物料，使前驱体溶液填充于介孔物料内部，形成填充体，得到填充体溶液；所述前驱体溶液包括铁源、磷酸根源、酰胺类物质及第一溶剂；
    混合填充体溶液与第二溶剂，使第二溶剂覆盖填充体的表面形成包覆体，得到包覆体溶液；
    将包覆体溶液进行加热反应，在包覆体的内部生成磷酸铁，得到封存体；
    将封存体进行煅烧，得到磷酸铁。
  2. 根据权利要求1所述的制备方法，其中，按照铁元素、磷酸根及酰胺基团的摩尔比为1:1:(1～1.8)，控制所述铁源、磷酸根源及酰胺类物质的用量。
  3. 根据权利要求1或2所述的制备方法，其中，所述酰胺类物质包括尿素、甲酰胺或乙酰胺中的任意一种或至少两种的组合。
  4. 根据权利要求1-3任一项所述的制备方法，其中，所述前驱体溶液的pH值为1～1.5。
  5. 根据权利要求1-4任一项所述的制备方法，其中，所述前驱体溶液的温度≤20℃。
  6. 根据权利要求1-5任一项所述的制备方法，其中，所述介孔物料包括介孔聚合物。
  7. 根据权利要求6所述的制备方法，其中，所述介孔聚合物包括甲基丙烯酸酯聚合物、苯乙烯聚合物、苯乙烯衍生物聚合物中的任意一种或至少两种的组合。
  8. 根据权利要求1-7任一项所述的制备方法，其中，所述介孔物料为微球颗粒，所述微球颗粒的粒径为2～50μm。
  9. 根据权利要求1-8任一项所述的制备方法，其中，所述制备方法包括，在混合前驱体溶液与介孔物料时，通过抽真空处理，使得使前驱体溶液填充于介孔物料之内。
  10. 根据权利要求9所述的制备方法，其中，所述抽真空处理的真空度为0.05～0.2MPa。
  11. 根据权利要求1-10任一项所述的制备方法，其中，所述第一溶剂包括水。
  12. 根据权利要求1-11任一项所述的制备方法，其中，所述第二溶剂包括食用油和/或液体石蜡。
  13. 根据权利要求1-12任一项所述的制备方法，其中，所述加热反应的温度为80～120℃，时间为2～4h。
  14. 根据权利要求1-13任一项所述的制备方法，其中，所述煅烧的温度为550～650℃，时间为0.5～2h。
  15. 根据权利要求1-14任一项所述的制备方法，其中，所述制备方法包括：
    使用去离子水作为第一溶剂，先利用酸调节去离子水的pH为1，在搅拌下加入铁源、磷酸根源和酰胺类物质，按照铁元素、磷酸根及酰胺基团的摩尔比为1:1:(1～1.8)控制加入量，再利用酸调节pH为1.0～1.5，保持温度为20℃以下，得到前驱体溶液；
    使用粒径范围为2～50μm的介孔苯乙烯聚合物微球颗粒作为介孔物料，将介孔物料放入到前驱体溶液中，充分搅拌，通过抽真空至真空度为0.05～0.2MPa，使前驱体溶液填充于介孔物料之内，形成填充体，得到填充体溶液；
    向溶填充体溶液中倒入第二溶剂，所述第二溶剂与所述第一溶剂互不相溶且密度不同，使填充体转移并浸没在第二溶剂中，且第二溶剂覆盖填充体的表 面形成包覆体，移除与第二溶剂相分层的液体后，得到包覆体溶液；
    将包覆体溶液于80～120℃下进行加热反应2～4h，在包覆体的内部生成磷酸铁纳米颗粒，冷却并过滤后，得到封存体；
    将封存体于550～650℃下煅烧0.5～2h，进行多次水洗后干燥，获得离散的磷酸铁颗粒。
  16. 一种使用权利要求1-15任意一项所述制备方法得到的磷酸铁。
  17. 一种使用权利要求16所述磷酸铁制备得到的磷酸铁锂正极材料。
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