WO2025129503A1 - 纳米磷酸铁锂的制备方法及其应用 - Google Patents

纳米磷酸铁锂的制备方法及其应用 Download PDF

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Publication number
WO2025129503A1
WO2025129503A1 PCT/CN2023/140308 CN2023140308W WO2025129503A1 WO 2025129503 A1 WO2025129503 A1 WO 2025129503A1 CN 2023140308 W CN2023140308 W CN 2023140308W WO 2025129503 A1 WO2025129503 A1 WO 2025129503A1
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Prior art keywords
preparation
iron phosphate
suspension
lithium
laser
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English (en)
French (fr)
Inventor
余海军
谢英豪
李爱霞
王涛
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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Priority to PCT/CN2023/140308 priority Critical patent/WO2025129503A1/zh
Priority to CN202380012860.4A priority patent/CN117999242B/zh
Publication of WO2025129503A1 publication Critical patent/WO2025129503A1/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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • C01B32/15—Nano-sized carbon materials
    • 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
    • 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
    • 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 positive electrode materials, and specifically relates to a preparation method of nano lithium iron phosphate and application thereof.
  • lithium iron phosphate As a positive electrode material for lithium-ion batteries, lithium iron phosphate has high specific capacity, good safety, long cycle life, and good thermal stability. At the same time, the raw material source is wide and the price is cheap. It is a positive electrode material that coexists with ternary materials for a long time. Although lithium iron phosphate, a positive electrode material for lithium-ion batteries, has the characteristics of low price, stable working voltage, non-toxic and environmentally friendly, stable structure, safe and reliable, good thermal stability, and long cycle life, it also has disadvantages such as low ion conductivity, poor low temperature performance, and low tap density.
  • the synthesis of lithium iron phosphate positive electrode materials is mainly through high-temperature solid-phase reaction method, that is, the lithium source, iron source, phosphorus source, doping or coating material are ground and mixed together, and then sintered at high temperature.
  • high-temperature solid-phase reaction method that is, the lithium source, iron source, phosphorus source, doping or coating material are ground and mixed together, and then sintered at high temperature.
  • other methods for synthesizing lithium iron phosphate such as hydrothermal method, coprecipitation method, microemulsion method, etc.
  • the preparation of lithium iron phosphate using nano-microscale iron phosphate as raw material is also attracting widespread attention.
  • the preparation method of small-size iron phosphate has problems such as low yield, high cost, or insufficient particle size of the prepared material, and insufficient material activity.
  • mechanical grinding is used to prepare iron phosphate materials with small particle size. This method is usually time-consuming, energy-intensive, and the particles are prone to agglomeration, which makes it
  • the present disclosure aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • the present disclosure proposes a preparation method of nano lithium iron phosphate and its application.
  • the method mainly controls the product by adjusting the single pulse energy and the time of laser action.
  • the laser acts on the continuously stirred alcoholic iron phosphate solvent, and while efficiently refining the iron phosphate, the further reaction of the nano iron phosphate particles with the surrounding liquid environment is increased, thereby obtaining nano iron phosphate particles modified with hydroxyl functional groups.
  • the product has no agglomeration and high dispersibility.
  • a method for preparing nano lithium iron phosphate comprising the following steps:
  • S2 treating the suspension A with a laser, with a laser wavelength of 220-760 nm, a pulse width of 5-15 ns, a pulse frequency of 10-100 Hz, and a single pulse energy of 100-300 mJ, and stirring the suspension A during the laser treatment;
  • the particle size D50 of the iron phosphate is 1-20 ⁇ m.
  • the alcohol solvent is at least one of isopropanol, ethanol, propanol, butanol, ethylene glycol or isobutanol.
  • step S1 the frequency of the ultrasound is 40-60 KHz, and the time of the ultrasound is 10-30 min.
  • step S2 the stirring speed is 400-700 r/min.
  • step S3 the mass ratio of the iron phosphate to the carbon source is 1:(0.14-0.17).
  • the carbon source is at least one of glucose, citric acid, sucrose or ascorbic acid.
  • step S4 the inlet air temperature of the spray drying is 180-200° C.; the feed rate of the spray drying is 500-700 ml/h.
  • step S4 the sintering temperature is 600-900°C.
  • step S4 the sintering time is 8-14 hours.
  • step S4 the particle size D50 of the nano lithium iron phosphate is 8-40 nm.
  • the present disclosure also provides application of the preparation method in preparing lithium-ion batteries.
  • the present invention discloses a nano-iron phosphate material with uniform particles and good dispersibility prepared by laser liquid phase dissolution technology.
  • the iron phosphate in the stirred liquid is irradiated by laser, a large amount of high-temperature plasma is generated after the pulse laser passes through the liquid and interacts with the material, forming a local environment of high temperature and high pressure, and a laser-induced plasma plume is generated at the solid-liquid interface between the material and the liquid.
  • the atoms or ions of the material have very high kinetic energy.
  • the molten solid phase material is ejected into the liquid phase environment.
  • the plasma plume is quenched in the liquid constraint.
  • the nucleation and growth of the new phase occur in this process.
  • the newly generated product diffuses outward into the liquid phase environment and quickly cools down to become the final nano material.
  • the quenching time of the plasma plume in the liquid is very short (about 100ns), which makes the grain size grown in the plasma plume quenching process generally in the nanometer scale.
  • the prepared iron phosphate has good dispersibility, and its sample particle size reaches the nanometer level and has a regular shape.
  • the lithium iron phosphate materials prepared by this method Compared with the lithium iron phosphate materials prepared by mechanical ball milling and dissolution in aqueous solution, the lithium iron phosphate materials prepared by this method have small particle size and good dispersion, which is conducive to the embedding and removal of lithium ions and improves the utilization rate of active substances.
  • FIG2 is a SEM image of lithium iron phosphate of Comparative Example 1 of the present disclosure.
  • FIG3 is a TEM image of lithium iron phosphate of Comparative Example 2 of the present disclosure.
  • This embodiment prepares a nano lithium iron phosphate, and the specific process is as follows:
  • the suspension A was laser treated using a Nd:YAG pulse laser with a laser wavelength of 532 nm, a pulse width of 10 ns, a pulse frequency of 10 Hz, a single pulse energy of 100 mJ, and an action time of 30 min.
  • the suspension was stirred with a magnetic stirrer to keep the solution uniformly mixed at a stirring speed of 400 r/min.
  • the suspension B was spray dried at an inlet air temperature of 190°C and a feed rate of 600 ml/h to obtain a dry powder.
  • the dry powder was then sintered in a nitrogen atmosphere by heating to 600°C at a rate of 3°C/min and then kept at this temperature for 8 hours.
  • the powder was cooled and discharged to obtain a LiFePO 4 /C material with a particle size D50 of 40 nm.
  • FIG. 1 is a TEM image of lithium iron phosphate in this embodiment. It can be seen from FIG. 1 that the prepared LiFePO 4 /C is in the form of dispersed nanoparticles with relatively uniform particle sizes.
  • This embodiment prepares a nano lithium iron phosphate, and the specific process is as follows:
  • the suspension B was spray dried at an inlet air temperature of 190°C and a feed rate of 600 ml/h to obtain a dry powder.
  • the dry powder was then sintered in a nitrogen atmosphere, heated to 700°C at a rate of 3°C/min, and then kept at this temperature for 10 hours.
  • the material was cooled and discharged to obtain a LiFePO 4 /C material with a particle size D50 of 34 nm.
  • This embodiment prepares a nano lithium iron phosphate, and the specific process is as follows:
  • the suspension A was laser treated using a Nd:YAG pulse laser with a laser wavelength of 532 nm, a pulse width of 10 ns, a pulse frequency of 10 Hz, a single pulse energy of 200 mJ, and an action time of 1.5 h.
  • the suspension was stirred with a magnetic stirrer to keep the solution uniformly mixed at a stirring speed of 600 r/min.
  • the suspension B was spray dried at an inlet air temperature of 190°C and a feed rate of 600 ml/h to obtain a dry powder.
  • the dry powder was then sintered in a nitrogen atmosphere at a rate of 3°C/min to 800°C and then kept at this temperature for 12 h.
  • the powder was cooled and discharged to obtain a LiFePO 4 /C material with a particle size D50 of 26 nm.
  • This embodiment prepares a nano lithium iron phosphate, and the specific process is as follows:
  • the suspension A was laser treated using a Nd:YAG pulse laser with a laser wavelength of 760 nm, a pulse width of 10 ns, a pulse frequency of 10 Hz, a single pulse energy of 300 mJ, and an action time of 2 h.
  • the suspension was stirred with a magnetic stirrer to keep the solution uniformly mixed at a stirring speed of 700 r/min.
  • lithium carbonate is added to the mixed solution A and stirred to disperse evenly, wherein the molar ratio of Fe in the iron phosphate to Li in the lithium carbonate is 1:1, and then glucose is added, wherein the mass of glucose is 0.14 times that of the iron phosphate, and stirred to disperse evenly to obtain a mixed solution B.
  • the mixed solution B was spray dried with an inlet air temperature of 190°C and a feed rate of 600 ml/h to obtain a dry powder.
  • the dry powder was then sintered in a nitrogen atmosphere, heated to 600°C at a rate of 3°C/min, and then kept at this temperature for 8 hours.
  • the powder was cooled and discharged to obtain a LiFePO 4 /C material with a particle size D50 of 1 ⁇ m.
  • This embodiment prepares a lithium iron phosphate, which is different from the embodiment 3 in that isopropanol is replaced by deionized water.
  • the specific process is as follows:
  • This embodiment prepares a lithium iron phosphate, which is different from the embodiment 3 in that the laser parameters are different.
  • the specific process is as follows:
  • the LiFePO 4 /C material prepared in the above embodiment and comparative example was selected as the positive electrode material, acetylene black was selected as the conductive agent, PVDF was selected as the binder, the positive electrode material, the conductive agent and the binder were weighed in a ratio of 92:4:4, and an organic solvent NMP was added, and the mixture was coated on an aluminum foil after stirring to prepare a positive electrode sheet, and a metal lithium sheet was selected as the negative electrode to prepare a button cell in a glove box filled with argon. The electrochemical performance of the button cell was tested, and the results are shown in Table 1.

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Abstract

本公开属于锂离子电池正极材料技术领域，公开了一种纳米磷酸铁锂的制备方法及其应用。该方法包括将磷酸铁分散于醇类溶剂中，经超声后得到悬浊液A，对悬浊液A进行激光处理，激光处理期间对悬浊液A进行搅拌，向激光处理后的悬浊液A中加入锂源和碳源，混合后得到悬浊液B，将悬浊液B进行喷雾干燥得到干燥粉体，将干燥粉体置于惰性气氛下烧结，即得纳米磷酸铁锂。

Description

纳米磷酸铁锂的制备方法及其应用 技术领域
本公开属于锂离子电池正极材料技术领域，具体涉及一种纳米磷酸铁锂的制备方法及其应用。
背景技术
作为锂离子电池正极材料，磷酸铁锂比容量高、安全性好、循环寿命长、热稳定性好，同时原材料来源广泛、价格便宜，是一种与三元材料长期共存的正极材料。锂离子电池正极材料磷酸铁锂具虽然具有价格低廉、工作电压稳定、无毒环保、结构稳定、安全可靠、热稳定性好、循环寿命长等特点，但同样存在离子电导率低，低温性能差和振实密度小等缺点。目前，合成磷酸铁锂正极材料主要是通过高温固相反应法，即将锂源、铁源、磷源、掺杂或包覆物质一起研磨混合均匀，然后在高温下烧结而成。同时合成磷酸铁锂也有水热法，共沉淀法、微乳液法等其他方式。尽管制备磷酸铁锂的方法有多种，但是以纳微尺度的磷酸铁为原料，制备磷酸铁锂，也正受到人们的广泛关注。目前，小尺寸磷酸铁的制备方法存在产量低，成本高抑或是制备的材料粒度不够小，材料活性不足等问题。例如采用机械研磨的方式制备颗粒粒径小的磷酸铁材料，此种方法通常耗时长，能耗高，且颗粒容易团聚，无法暴露更多的活性位点。
发明内容
本公开旨在至少解决上述现有技术中存在的技术问题之一。为此，本公开提出一种纳米磷酸铁锂的制备方法及其应用。该方法主要通过调节单脉冲能量和激光作用的时间进行产物的控制，激光作用于不断搅拌的磷酸铁醇类溶剂，在高效细化磷酸铁的同时增加纳米磷酸铁颗粒与周围液体环境的进一步反应，进而制得羟基官能团修饰的纳米磷酸铁颗粒，产物无团聚，分散性高。
根据本公开的一个方面，提出了一种纳米磷酸铁锂的制备方法，包括以下步骤：
S1：将磷酸铁分散于醇类溶剂中，经超声后得到悬浊液A；
S2：对所述悬浊液A进行激光处理，激光波长220-760nm，脉冲宽度5-15ns，脉冲频率10-100Hz，单脉冲能量100-300mJ，激光处理期间对所述悬浊液A进行搅拌；
S3：向激光处理后的悬浊液A中加入锂源和碳源，混合后得到悬浊液B；
S4：将所述悬浊液B进行喷雾干燥得到干燥粉体，将所述干燥粉体置于惰性气氛下烧结，即得所述纳米磷酸铁锂。
在本公开的一些实施方式中，步骤S1中，所述磷酸铁的粒径D50为1-20μm。
在本公开的一些实施方式中，步骤S1中，所述醇类溶剂为异丙醇、乙醇、丙醇、丁醇、乙二醇或异丁醇中的至少一种。
在本公开的一些实施方式中，步骤S1中，所述超声的频率为40-60KHz，超声的时间为10-30min。
在本公开的一些实施方式中，步骤S1中，所述磷酸铁与醇类溶剂的质量比为1：(2-4)。
在本公开的一些实施方式中，步骤S2中，所述激光处理的时间为0.5-2h。
在本公开的一些实施方式中，步骤S2中，所述搅拌的速度为400-700r/min。
在本公开的一些实施方式中，步骤S3中，所述锂源为氢氧化锂、碳酸锂、硝酸锂或氯化锂中的至少一种。
在本公开的一些实施方式中，步骤S3中，所述磷酸铁中Fe与锂源中Li的摩尔比为1：(1-1.05)。
在本公开的一些实施方式中，步骤S3中，所述磷酸铁和碳源的质量比为1：(0.14-0.17)。
在本公开的一些实施方式中，步骤S3中，所述碳源为葡萄糖、柠檬酸、蔗糖或抗坏血酸中的至少一种。
在本公开的一些实施方式中，步骤S4中，所述喷雾干燥的进风温度为180-200℃；所述喷雾干燥的进料速率为500-700ml/h。
在本公开的一些实施方式中，步骤S4中，所述烧结的温度为600-900℃。
在本公开的一些实施方式中，步骤S4中，所述烧结的时间为8-14h。
在本公开的一些实施方式中，步骤S4中，所述纳米磷酸铁锂的粒径D50为8-40nm。
本公开还提供所述的制备方法在制备锂离子电池中的应用。
根据本公开的实施方式，至少具有以下有益效果：
1、本公开通过激光液相溶蚀技术制备得到颗粒均匀，分散性好的纳米磷酸铁材料，当处于搅拌下的液体中的磷酸铁被激光照射，脉冲激光穿过液体与材料相互作用后产生大量的高温等离子体，形成一个高温高压的局部环境，在材料与液体的固液界面处产生激光诱导的等离子体羽，在高能量的激光溶烛作用下，材料的原子或离子具备很高的动能，同时由于等离子羽内部有很大的内压作用，使得溶融的固相材料物质派射到液相环境中，最后等离子体羽在液体束缚中淬灭，新相的成核与生长就发生在这一过程，新生成的产物向外扩散到液相环境中，并快速冷却下来成为最终的纳米材料。等离子体羽在液体中的淬灭时间非常的短暂(大约为100ns)，这使得生长在等离子体羽淬灭过程中的晶粒尺度一般都在纳米尺度。制备得到的磷酸铁具有良好的分散性能，同时其样品粒径均达到纳米级，且形状规整。
2、选择醇类溶剂作为液相激光溶蚀的溶剂，并且在特定的激光参数下，通过激光的作用对纳米粒子表面进行官能团修饰，即在含有-OH的溶剂中溶蚀磷酸铁，可以获得表面有羟基基团修饰的纳米粒子，基团吸附于粒子表面，能够减少纳米粒子的团聚，提高颗粒分散性，在后续烧结制备磷酸铁锂时，控制晶粒的生长。该种制备方法能够在不添加表面活性剂的情况下将目标官能团修饰到纳米磷酸铁上，而且没有副产物。相比采用机械球磨方法和在水溶液中溶蚀的方法制备得到的磷酸铁锂材料，本方法制备得到的磷酸铁锂材料颗粒粒径小，分散性好，有利于锂离子的嵌入与脱出，提高活性物质的利用率。
附图说明
下面结合附图和实施例对本公开做进一步的说明，其中：
图1为本公开实施例1磷酸铁锂的TEM图；
图2为本公开对比例1磷酸铁锂的SEM图；
图3为本公开对比例2磷酸铁锂的TEM图。
具体实施方式
以下将结合实施例对本公开的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本公开的目的、特征和效果。
实施例1
本实施例制备了一种纳米磷酸铁锂，具体过程为：
(1)称取粒径D50为10μm的磷酸铁分散于异丙醇溶剂中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：4，超声分散的频率为53KHz，分散时间为10min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长532nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量100mJ，作用时间为30min，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为400r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1，再加入葡萄糖，葡萄糖为磷酸铁质量的0.14倍，搅拌分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至600℃，然后保温维持8h，冷却出料即得到粒径D50为40nm的LiFePO4/C材料。
图1为本实施例磷酸铁锂的TEM图，从图1中可以看出，制备得到LiFePO4/C呈分散的纳米颗粒形态，并且粒径较为均匀。
实施例2
本实施例制备了一种纳米磷酸铁锂，具体过程为：
(1)称取粒径D50为10μm的磷酸铁分散于异丙醇溶剂中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：2.5，超声分散的频率为53KHz，分散时间为15min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长355nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量150mJ，作用时间为1h，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为500r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1.02，再加入葡萄糖，葡萄糖为磷酸铁质量的0.15倍，搅拌分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至700℃，然后保温维持10h，冷却出料即得到粒径D50为34nm的LiFePO4/C材料。
实施例3
本实施例制备了一种纳米磷酸铁锂，具体过程为：
(1)称取粒径D50为20μm的磷酸铁分散于异丙醇溶剂中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：3，超声分散的频率为53KHz，分散时间为20min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长532nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量200mJ，作用时间为1.5h，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为600r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1.03，再加入葡萄糖，葡萄糖为磷酸铁质量的0.16倍，搅拌分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至800℃，然后保温维持12h，冷却出料即得到粒径D50为26nm的LiFePO4/C材料。
实施例4
本实施例制备了一种纳米磷酸铁锂，具体过程为：
(1)称取粒径D50为3μm的磷酸铁分散于异丙醇溶剂中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：4，超声分散的频率为53KHz，分散时间为30min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长760nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量300mJ，作用时间为2h，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为700r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1.05，再加入葡萄糖，葡萄糖为磷酸铁质量的0.17倍，搅拌分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至900℃，然后保温维持14h，冷却出料即得到粒径D50为10nm的LiFePO4/C材料。
对比例1
本对比例制备了一种磷酸铁锂，与实施例1的区别在于，采用普通机械研磨的方式制备颗粒粒径小的磷酸铁材料，具体过程为：
(1)将粒径D50为10μm的磷酸铁称量20克加入到卧式高能球磨机的研磨仓体内，加入异丙醇作为溶剂，球磨罐中料、球、异丙醇的质量比为1：3：4，1200r/min的转速下球磨18h，获得混合溶液A；
(2)向混合溶液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1，再加入葡萄糖，葡萄糖为磷酸铁质量的0.14倍，搅拌分散均匀，得到混合溶液B。
(3)将混合溶液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至600℃，然后保温维持8h，冷却出料即得到粒径D50为1μm的LiFePO4/C材料
对比例2
本实施例制备了一种磷酸铁锂，与实施例3的区别在于，异丙醇替换为去离子水，具体过程为：
(1)称取粒径D50为20μm的磷酸铁分散于去离子水中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：3，超声分散的频率为53KHz，分散时间为20min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长532nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量200mJ，作用时间为1.5h，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为600r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1.03，再加入葡萄糖，葡萄糖为磷酸铁质量的0.16倍，搅拌分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至800℃，然后保温维持12h，冷却出料即得到粒径D50为27nm的LiFePO4/C材料。
对比例3
本实施例制备了一种磷酸铁锂，与实施例3的区别在于，激光参数不同，具体过程为：
(1)称取粒径D50为20μm的磷酸铁分散于异丙醇中，在室温条件下进行超声分散以得到悬浊液A，其中，控制磷酸铁与异丙醇的质量比为1：3，超声分散的频率为53KHz，分散时间为20min；
(2)将上述悬浊液A进行激光处理，使用Nd：YAG脉冲激光器，激光波长1064nm，脉冲宽度10ns，脉冲频率10Hz，单脉冲能量60mJ，作用时间为1.5h，激光处理期间使用磁力搅拌器对悬浊液进行搅拌，保持溶液混合均匀，搅拌速度为600r/min；
(3)向激光处理后的悬浊液A中加入碳酸锂搅拌分散均匀，其中磷酸铁中Fe与碳酸锂中的Li的摩尔比为1:1.03，再加入葡萄糖，葡萄糖为磷酸铁质量的0.16倍，搅拌 分散均匀，得到悬浊液B。
(4)将悬浊液B进行喷雾干燥，进风温度为190℃、进料速率600ml/h，得到干燥粉体，随后对干燥粉体于氮气气氛下进行烧结，以3℃/min进行升温至800℃，然后保温维持12h，冷却出料即得到粒径D50为53nm的LiFePO4/C材料。
试验例
选择上述实施例和对比例中制备得到的LiFePO4/C材料为正极材料，导电剂选用乙炔黑，粘结剂采用PVDF，以92:4:4的比例称取正极材料，导电剂及粘结剂，并加入有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片，负极采用金属锂片，在充满氩气的手套箱内制成扣式电池。测试扣式电池的电化学性能，结果如表1所示。
表1
由表1可见，对比例1、对比例2、对比例3的放电容量均比实施例低，这是因为对比例1采用机械球磨将原材料破碎分散制备磷酸铁锂，从图2中可以看出得到的碎片形态的磷酸铁锂团聚较为严重，无法暴露更多的活性位点，导致容量降低，同时机械球磨耗能高，反应时间长。对比例2使用去离子水作为液相进行激光溶蚀，虽然也可以制备得到纳米形态的颗粒，但从图3可以看到存在颗粒团聚现象，分散性差于使用醇类溶 剂作为液相制备得到的材料，说明使用有醇类溶剂能够在激光过程中实现磷酸铁的表面官能团修饰，可阻止颗粒团聚，避免后续烧结过程中出现晶界融合，得到分散性好的纳米颗粒。对比例3采用较低的激光能量，不仅颗粒细度不够，还达不到羟基表面修饰的条件，颗粒存在团聚，降低了材料容量。

Claims (16)

  1. 一种纳米磷酸铁锂的制备方法，其特征在于，包括以下步骤：
    S1：将磷酸铁分散于醇类溶剂中，经超声后得到悬浊液A；
    S2：对所述悬浊液A进行激光处理，激光波长220-760nm，脉冲宽度5-15ns，脉冲频率10-100Hz，单脉冲能量100-300mJ，激光处理期间对所述悬浊液A进行搅拌；
    S3：向激光处理后的悬浊液A中加入锂源和碳源，混合后得到悬浊液B；
    S4：将所述悬浊液B进行喷雾干燥得到干燥粉体，将所述干燥粉体置于惰性气氛下烧结，即得所述纳米磷酸铁锂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述磷酸铁的粒径D50为1-20μm。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述醇类溶剂为异丙醇、乙醇、丙醇、丁醇、乙二醇或异丁醇中的至少一种。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述超声的频率为40-60KHz，超声的时间为10-30min。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述磷酸铁与醇类溶剂的质量比为1：(2-4)。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述激光处理的时间为0.5-2h。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述搅拌的速度为400-700r/min。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述锂源为氢氧化锂、碳酸锂、硝酸锂或氯化锂中的至少一种。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述磷酸铁中Fe与锂源中Li的摩尔比为1：(1-1.05)。
  10. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述磷酸铁和碳源 的质量比为1：(0.14-0.17)。
  11. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述碳源为葡萄糖、柠檬酸、蔗糖或抗坏血酸中的至少一种。
  12. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述喷雾干燥的进风温度为180-200℃；所述喷雾干燥的进料速率为500-700ml/h。
  13. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述烧结的温度为600-900℃。
  14. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述烧结的时间为8-14h。
  15. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述纳米磷酸铁锂的粒径D50为8-40nm。
  16. 如权利要求1-15任一项所述的制备方法在制备锂离子电池中的应用。
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