WO2024055516A1 - 喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用 - Google Patents

喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用 Download PDF

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WO2024055516A1
WO2024055516A1 PCT/CN2023/077682 CN2023077682W WO2024055516A1 WO 2024055516 A1 WO2024055516 A1 WO 2024055516A1 CN 2023077682 W CN2023077682 W CN 2023077682W WO 2024055516 A1 WO2024055516 A1 WO 2024055516A1
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manganese
iron
source
lithium
spray
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PCT/CN2023/077682
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English (en)
French (fr)
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王涛
余海军
李爱霞
谢英豪
张学梅
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Priority to GB2309851.0A priority Critical patent/GB2628441A/en
Publication of WO2024055516A1 publication Critical patent/WO2024055516A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 invention belongs to the technical field of lithium battery cathode materials, and specifically relates to a method for preparing lithium manganese iron phosphate cathode materials by spray combustion and its application.
  • lithium iron phosphate batteries Compared with ternary batteries, lithium iron phosphate batteries have higher safety and lower cost advantages. They have the advantages of good thermal stability, long cycle life, environmental friendliness, and rich sources of raw materials. They are currently the most potential power source. Lithium-ion battery cathode materials are gaining favor from more automobile manufacturers, and their market share continues to increase.
  • the LiFePO 4 material has a low lithium deintercalation potential platform (about 3.4V), which reduces the overall energy density of the battery and limits its development in electric vehicles.
  • the working voltage of LiMnPO 4 to Li is 4.1V. If LiMnPO 4 can obtain a specific capacity equivalent to that of LiFePO 4 , it means that the energy density will be 35% higher than that of LiFePO 4 .
  • low raw material cost and environmental friendliness are also the advantages of LiMnPO 4 .
  • the conductivity of LiMnPO 4 is very low and is almost an insulator, only one thousandth that of LiFePO 4.
  • the Jahn-Teller effect occurs during the redox reaction, resulting in poor rate performance and low discharge specific capacity of the material.
  • LiMn x Fe (1-x) PO 4 cathode material contains high energy density, which can compensate for the shortcomings of LiFePO 4 cathode material in this area, while improving the rate and discharge specific capacity of LiMnPO 4 cathode material. problem, increasing the possibility of phosphoric acid-based cathode materials becoming power lithium-ion battery materials.
  • the co-precipitation reaction of phosphate and ferrous salt, manganese salt and oxidant has the following problems: because the pH of iron phosphate precipitation is low, and the pH of manganese phosphate precipitation is high, and at a higher pH, ferrous salt Reaction with the oxidant will produce iron hydroxide, resulting in high iron hydroxide content, low purity of lithium iron manganese phosphate, and low phosphorus content.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • a method for preparing lithium iron manganese phosphate cathode material by spray combustion which includes the following steps:
  • the second solid material is calcined in an inert atmosphere to obtain the lithium iron manganese phosphate.
  • the manganese source is at least one of manganese acetate or manganese lactate; the iron source is at least one of iron acetate or iron nitrate; and the phosphorus source is At least one of diethyl phosphate or triethyl phosphate.
  • the organic solvent is at least one of ethanol or glycerol.
  • step S1 the solid-liquid ratio of the mixture of manganese source, iron source and phosphorus source and the organic solvent is (30-50) g/100 mL.
  • the usage ratio of the organic solution, surfactant and combustion accelerator is (100-200) mL: (0.5-1.0) g: (1.0-2.0) g.
  • the surfactant in step S2, is laureth polyoxyethylene ether or At least one of nonylphenol polyoxyethylene ethers.
  • the combustion accelerant is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxynitroaniline or nitrobenzophenone.
  • the spray combustion temperature is 550-700°C
  • the aperture of the nozzle used is 30-50 ⁇ m
  • the spray pressure is 0.8-1.5MPa.
  • the mixed liquid enters the combustion chamber of the spray combustion device through a carrier gas flow for combustion.
  • the carrier gas is air or oxygen
  • the carrier gas flow rate is 100-150L/h.
  • step S4 after the first solid material is mixed with a lithium source and water, acid is added to adjust the pH to 2.5-4.0, and then the hydrothermal reaction is performed.
  • step S4 the amount of water used is 100%-200% of the total mass of the first solid material and the lithium source solid.
  • the lithium source is at least one of lithium nitrate, lithium acetate, lithium hydroxide or lithium carbonate.
  • step S4 the temperature of the hydrothermal reaction is 100-120°C. Further, the hydrothermal reaction time is 2-4h.
  • step S4 the amount of carbon source used is 0.3-0.5 times the molar amount of iron element in the first solid material.
  • the carbon source is at least one of glucose, sucrose or fructose.
  • step S5 the calcination temperature is 600-850°C. Further, the calcination time is 6-20h.
  • the invention also provides the application of the method in preparing lithium-ion batteries.
  • the manganese source, iron source and phosphorus source are dissolved in an organic solvent to mix the phosphorus, iron and manganese evenly, and then spray Combustion uses the different stabilities of iron and manganese phosphates to generate different iron and manganese phosphates.
  • iron exists in the form of iron phosphate
  • manganese exists stably in the form of manganese pyrophosphate to obtain iron phosphate and pyrophosphate.
  • a mixture of manganese is further hydrothermally hydrolyzed through hydrothermal reaction under acidic conditions, and the manganese pyrophosphate in the precipitate is preliminarily formed into lithium manganese phosphate, and then a carbon source is added, and after spray drying, sintering is prepared.
  • the reaction equation is as follows:
  • Spray combustion reaction (taking iron acetate, manganese acetate, and triethyl phosphate as examples): Fe(CH 3 COO) 3 +PO 4 (CH 3 CH 2 ) 3 +15O 2 ⁇ FePO 4 +12CO 2 +12H 2 O; 2Mn(CH 3 COO) 2 +2PO 4 (CH 3 CH 2 ) 3 +26O 2 ⁇ Mn 2 P 2 O 7 +20CO 2 +21H 2 O;
  • Figure 1 is an SEM image of lithium iron manganese phosphate prepared in Example 1 of the present invention.
  • spray combustion is used to prepare lithium iron manganese phosphate.
  • the specific process is:
  • Step 3 Add the mixed liquid into the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 30 ⁇ m, the spray pressure is 1.5MPa, the carrier gas is oxygen, and the carrier gas flow rate is 100L/h. Control the combustion chamber temperature to 550°C;
  • Step 5 After the hydrothermal reaction is completed, add glucose with 0.3 times the molar amount of iron element into the reaction kettle, mix evenly and spray-dry to obtain a solid material;
  • Step 6 Calculate the solid material obtained in Step 5 at 750°C for 14 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • spray combustion is used to prepare lithium iron manganese phosphate.
  • the specific process is:
  • Step 3 Add the mixed liquid to the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 40 ⁇ m, the spray pressure is 1.2MPa, the carrier gas is air, and the carrier gas flow rate is 120L/h. control
  • the combustion chamber temperature is 600°C;
  • Step 5 After the hydrothermal reaction is completed, add 0.4 times the molar amount of sucrose of iron element into the reaction kettle, mix evenly and spray-dry to obtain a solid material;
  • Step 6 Calculate the solid material obtained in Step 5 at 600°C for 20 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • spray combustion is used to prepare lithium iron manganese phosphate.
  • the specific process is:
  • Step 3 Add the mixed liquid into the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 50 ⁇ m, the spray pressure is 0.8MPa, the carrier gas is air or oxygen, and the carrier gas flow rate is 150L/ h, control the combustion chamber temperature to 700°C;
  • Step 5 After the hydrothermal reaction is completed, add fructose with 0.5 times the molar amount of iron into the reaction kettle, mix evenly and spray-dry to obtain a solid material;
  • Step 6 Calculate the solid material obtained in Step 5 at 850°C for 6 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • a kind of lithium iron manganese phosphate was prepared in this comparative example.
  • the difference from Example 1 is that no hydrothermal reaction was carried out.
  • the specific process is:
  • Step 3 Add the mixed liquid into the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 30 ⁇ m, the spray pressure is 1.5MPa, the carrier gas is oxygen, and the carrier gas flow rate is 100L/h. Control the combustion chamber temperature to 550°C;
  • Step 5 Calculate the solid material obtained in Step 4 at 750°C for 14 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • a kind of lithium iron manganese phosphate was prepared in this comparative example.
  • the difference from Example 2 is that no hydrothermal reaction was carried out.
  • the specific process is:
  • Step 3 Add the mixed liquid to the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 40 ⁇ m, the spray pressure is 1.2MPa, the carrier gas is air, and the carrier gas flow rate is 120L/h. Control the combustion chamber temperature to 600°C;
  • Step 5 Calculate the solid material obtained in Step 4 at 600°C for 20 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • a kind of lithium iron manganese phosphate was prepared in this comparative example.
  • the difference from Example 3 is that no hydrothermal reaction was carried out.
  • the specific process is:
  • Step 3 Add the mixed liquid into the spray combustion device and enter the combustion chamber through the carrier gas flow for combustion; the nozzle aperture of the spray device is 50 ⁇ m, the spray pressure is 0.8MPa, the carrier gas is air or oxygen, and the carrier gas flow rate is 150L/ h, control the combustion chamber temperature to 700°C;
  • Step 5 Calculate the solid material obtained in Step 4 at 850°C for 6 hours under the protection of inert gas, and then naturally cool to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • the lithium iron manganese phosphate obtained in the Examples and Comparative Examples was used as the cathode material, acetylene black was used as the conductive agent, and PVDF was used as the binder.
  • the mixture was mixed at a mass ratio of 8:1:1, and a certain amount of organic solvent NMP was added. After stirring, Coated on aluminum foil to make a positive electrode sheet.
  • the slurry prepared from the lithium iron manganese phosphate cathode material obtained in the comparative example was mostly jelly-like and difficult to coat. It is speculated that there is too much residual lithium, and it is difficult to further sinter manganese pyrophosphate and lithium source to prepare phosphorus manganese lithium battery cathode materials. , check The residual lithium content of the examples and comparative examples was measured, and the results are shown in Table 1;
  • the negative electrode is a metallic lithium sheet; the separator is a Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is a solution composed of EC, DMC and EMC in a mass ratio of 1:1:1, the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/ L; Assemble the Model 2023 button cell battery in the glove box.
  • the charge and discharge cycle performance of the battery was tested, and the discharge specific capacity of 0.1C and 1C was tested in the cut-off voltage range of 2.2-4.3V; the electrochemical performance results of the test are shown in Table 1.
  • the specific capacities of the comparative examples are very low. This is because the manganese pyrophosphate has not undergone hydrothermal reaction and cannot be successfully converted into lithium manganese phosphate by spray drying with the lithium source, and qualified lithium manganese iron phosphate cannot be prepared.

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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

本发明公开了一种喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用，将锰源、铁源和磷源混合溶解于有机溶剂中，得到含磷铁锰的有机溶液，再加入表面活性剂和助燃剂，将所得混合液进行喷雾燃烧，所得固体料与锂源、水混合进行水热反应，再加入碳源进行喷雾干燥，煅烧，即得磷酸锰铁锂。本发明通过有机溶剂将磷源、锰源、铁源混合溶解，避免磷酸锰铁沉淀物的生成，经过喷雾燃烧反应得到对应的磷酸铁和焦磷酸锰，使铁锰混合更均匀，提高材料的比容量和循环性能。

Description

喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用 技术领域
本发明属于锂电池正极材料技术领域，具体涉及一种喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用。
背景技术
磷酸铁锂电池相对于三元电池具备更高的安全性和更低的成本优势，其具备热稳定性好、循环寿命长、环境友好，原料来源丰富等优势，是目前最具应用潜力的动力锂离子电池正极材料，正获得更多汽车厂商的青睐，市场占有率不断提升。
然而，LiFePO4材料由于脱嵌锂电位平台(约3.4V)较低，降低了电池整体的能量密度，限制了其在电动汽车上的发展。而LiMnPO4对Li的工作电压为4.1V，如果LiMnPO4能够获取与LiFePO4相当的比容量，就意味着与LiFePO4相比较将高出35％的能量密度。同时原料成本低、对环境友好也是LiMnPO4的优势。但是，LiMnPO4的电导率很低，几乎属于绝缘体，只有LiFePO4的千分之一；同时在发生氧化还原反应过程中会存在Jahn-Teller效应导致材料倍率性能差以及放电比容量低。
从目前的研究现状能够看出，LiMnxFe(1-x)PO4正极材料含有高能量密度，可以补偿LiFePO4正极材料在这方面的不足，同时改善LiMnPO4正极材料倍率及放电比容量低的问题，提高磷酸系正极材料变为动力锂离子电池材料的可能性。
磷酸锰铁锂的合成方法有很多，目前使用单一高温固相法制备LiMnxFe(1-x)PO4材料，但是该方法在制备前驱体时很难准确控制铁和锰的配比，过渡金属很难均匀分布于材料主体结构中，会导致Mn3+的Jahn-Teller效应严重，影响电池的循环和倍率性能。而采用磷酸盐与亚铁盐、锰盐与氧化剂共沉淀反应，存在以下问题：由于磷酸铁沉淀的pH较低，而磷酸锰沉淀的pH较高，而在较高的pH下，亚铁盐与氧化剂反应会得到氢氧化铁，导致氢氧化铁的含量高，磷酸锰铁锂的纯度低，磷含量低。
因此，需要寻求一种既能够使铁锰达到原子层面的均匀混合，又能使磷与铁锰的比 例达到理论值，从而制备得到高容量、高循环性能的磷酸锰铁锂正极材料的方法。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种喷雾燃烧制备磷酸锰铁锂正极材料的方法及其应用，该方法可制备得到磷：(铁+锰)＝1:1，且铁锰均匀混合的磷酸锰铁锂正极材料，该材料具有较高的比容量和循环性能。
根据本发明的一个方面，提出了一种喷雾燃烧制备磷酸锰铁锂正极材料的方法，包括以下步骤：
S1：将锰源、铁源和磷源混合溶解于有机溶剂中，得到含磷铁锰的有机溶液；
S2：向所述有机溶液中加入表面活性剂和助燃剂，得到混合液；
S3：将所述混合液进行喷雾燃烧，得到第一固体料；
S4：将所述第一固体料与锂源、水混合，在酸性条件下进行水热反应，反应结束后加入碳源混合，进行喷雾干燥，得到第二固体料；
S5：所述第二固体料在惰性气氛下煅烧，即得所述磷酸锰铁锂。
在本发明的一些实施方式中，步骤S1中，所述有机溶液中铁锰摩尔比为(0.25-4):1，(Fe+Mn):P＝1:(1-1.05)。
在本发明的一些实施方式中，步骤S1中，所述锰源为乙酸锰或乳酸锰中的至少一种；所述铁源为乙酸铁或硝酸铁中的至少一种；所述磷源为磷酸二乙酯或磷酸三乙酯中的至少一种。
在本发明的一些实施方式中，步骤S1中，所述有机溶剂为乙醇或甘油中的至少一种。
在本发明的一些实施方式中，步骤S1中，所述锰源、铁源和磷源的混合料与所述有机溶剂的固液比为(30-50)g/100mL。
在本发明的一些实施方式中，步骤S2中，所述有机溶液、表面活性剂和助燃剂的用量比为(100-200)mL：(0.5-1.0)g：(1.0-2.0)g。
在本发明的一些实施方式中，步骤S2中，所述表面活性剂为月桂醇聚氧乙烯醚或 壬基酚聚氧乙烯醚中的至少一种。
在本发明的一些实施方式中，步骤S2中，所述助燃剂为烷基硝基茴香醚、硝基苯肼、烷氧基硝基苯胺或硝基二苯甲酮中的至少一种。
在本发明的一些实施方式中，步骤S3中，所述喷雾燃烧的温度为550-700℃，所用喷头的孔径为30-50μm，喷雾的压力为0.8-1.5MPa。进一步地，所述混合液经载气气流进入喷雾燃烧装置的燃烧室进行燃烧，载气气体为空气或氧气，载气流量为100-150L/h。
在本发明的一些实施方式中，步骤S4中，所述第一固体料与锂源、水混合后，加酸调节pH为2.5-4.0，再进行所述水热反应。
在本发明的一些实施方式中，步骤S4中，所述水的用量为所述第一固体料与锂源固体总质量的100％-200％。
在本发明的一些实施方式中，步骤S4中，所述第一固体料与锂源的配比按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)。
在本发明的一些实施方式中，步骤S4中，所述锂源为硝酸锂、醋酸锂、氢氧化锂或碳酸锂中的至少一种。
在本发明的一些实施方式中，步骤S4中，所述水热反应的温度为100-120℃。进一步地，所述水热反应的时间为2-4h。
在本发明的一些实施方式中，步骤S4中，所述碳源的用量为第一固体料中铁元素摩尔量的0.3-0.5倍。
在本发明的一些实施方式中，步骤S4中，所述碳源为葡萄糖、蔗糖或果糖中的至少一种。
在本发明的一些实施方式中，步骤S5中，所述煅烧的温度为600-850℃。进一步地，所述煅烧的时间为6-20h。
本发明还提供所述的方法在制备锂离子电池中的应用。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
1、本发明通过将锰源、铁源、磷源溶于有机溶剂，使磷铁锰混合均匀，再经喷雾 燃烧，利用铁、锰磷酸盐不同的稳定性，生成不同的铁与锰的磷酸盐，其中，铁以磷酸铁的形式存在，锰则以焦磷酸锰的形式稳定存在，得到磷酸铁与焦磷酸锰的混合物，并通过酸性条件下水热反应，使其中的焦磷酸锰进一步水热水解，预先使沉淀物中的焦磷酸锰形成磷酸锰锂，再添加碳源，经喷雾干燥后，烧结制备得到磷酸锰铁锂。其反应方程式如下：
喷雾燃烧反应(以乙酸铁、乙酸锰、磷酸三乙酯为例)：
Fe(CH3COO)3+PO4(CH3CH2)3+15O2→FePO4+12CO2+12H2O；
2Mn(CH3COO)2+2PO4(CH3CH2)3+26O2→Mn2P2O7+20CO2+21H2O；
水热反应：
H2O+2Li++Mn2P2O7→2LiMnPO4+2H+；
烧结反应：
C+Li2O+2FePO4→2LiFePO4+CO。
2、由于磷酸铁与磷酸锰的沉淀环境不同，难以达到共沉淀，本发明在喷雾燃烧过程中，首先通过有机溶剂溶解的方式将磷源、锰源、铁源混合溶解，避免磷酸锰铁沉淀物的生成，再经过喷雾燃烧反应，得到对应的磷酸铁和焦磷酸锰，一方面，使铁锰混合更均匀，利于后续制备磷酸锰铁锂，提高材料的比容量和循环性能。另一方面，保证了(Fe+Mn):P＝1:1，为下一步合成磷酸锰铁锂保证了充足的磷含量，避免了补加磷源的问题。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明实施例1制备的磷酸锰铁锂的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例利用喷雾燃烧制备了一种磷酸锰铁锂，具体过程为：
步骤1，按照摩尔比铁锰比为1:1且(Fe+Mn):P＝1:1，将乙酸锰、乙酸铁、磷酸三乙酯混合后，按照30g/100mL的比例将混合物溶于乙醇中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：月桂醇聚氧乙烯醚：烷基硝基茴香醚＝100mL:0.5g:1.0g，向有机溶液中加入月桂醇聚氧乙烯醚、烷基硝基茴香醚，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为30μm，喷雾压力为1.5MPa，载气气体为氧气，载气流量为100L/h，控制燃烧室温度为550℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与硝酸锂混合后，加入固体总质量100％的去离子水，并使用硝酸调节pH为2.5，在密闭反应釜中水热反应4h，反应温度为120℃；
步骤5，水热反应结束后，向反应釜内加入铁元素摩尔量0.3倍的葡萄糖，混合均匀后进行喷雾干燥，得到固体料；
步骤6，将步骤5所得固体料在惰性气体的保护下、750℃煅烧14h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
实施例2
本实施例利用喷雾燃烧制备了一种磷酸锰铁锂，具体过程为：
步骤1，按照摩尔比铁锰比为2:1且(Fe+Mn):P＝1:1，将乙酸锰、硝酸铁、磷酸三乙酯混合后，按照40g/100mL的比例将混合物溶于甘油中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：壬基酚聚氧乙烯醚：硝基苯肼＝150mL:0.8g:1.5g，向有机溶液中加入壬基酚聚氧乙烯醚、硝基苯肼，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为40μm，喷雾压力为1.2MPa，载气气体为空气，载气流量为120L/h，控制 燃烧室温度为600℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与醋酸锂混合后，加入固体总质量150％的去离子水，并使用硝酸调节pH为3.0，在密闭反应釜中水热反应3h，反应温度为110℃；
步骤5，水热反应结束后，向反应釜内加入铁元素摩尔量0.4倍的蔗糖，混合均匀后进行喷雾干燥，得到固体料；
步骤6，将步骤5所得固体料在惰性气体的保护下、600℃煅烧20h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
实施例3
本实施例利用喷雾燃烧制备了一种磷酸锰铁锂，具体过程为：
步骤1，按照摩尔比铁锰比为4:1且(Fe+Mn):P＝1:1，将乳酸锰、乙酸铁、磷酸二乙酯混合后，按照50g/100mL的比例将混合物溶于乙醇中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：月桂醇聚氧乙烯醚：硝基二苯甲酮＝200mL:1.0g:2.0g，向有机溶液中加入月桂醇聚氧乙烯醚、硝基二苯甲酮，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为50μm，喷雾压力为0.8MPa，载气气体为空气或氧气，载气流量为150L/h，控制燃烧室温度为700℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与氢氧化锂混合后，加入固体总质量200％的去离子水，并使用硝酸调节pH为4.0，在密闭反应釜中水热反应2h，反应温度为120℃；
步骤5，水热反应结束后，向反应釜内加入铁元素摩尔量0.5倍的果糖，混合均匀后进行喷雾干燥，得到固体料；
步骤6，将步骤5所得固体料在惰性气体的保护下、850℃煅烧6h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
对比例1
本对比例制备了一种磷酸锰铁锂，与实施例1的区别在于，未进行水热反应，具体过程为：
步骤1，按照摩尔比铁锰比为1:1且(Fe+Mn):P＝1:1，将乙酸锰、乙酸铁、磷酸三乙酯混合后，按照30g/100mL的比例将混合物溶于乙醇中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：月桂醇聚氧乙烯醚：烷基硝基茴香醚＝100mL:0.5g:1.0g，向有机溶液中加入月桂醇聚氧乙烯醚、烷基硝基茴香醚，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为30μm，喷雾压力为1.5MPa，载气气体为氧气，载气流量为100L/h，控制燃烧室温度为550℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与硝酸锂混合后，加入固体总质量100％的去离子水，并加入铁元素摩尔量0.3倍的葡萄糖，混合均匀后进行喷雾干燥，得到固体料；
步骤5，将步骤4所得固体料在惰性气体的保护下、750℃煅烧14h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
对比例2
本对比例制备了一种磷酸锰铁锂，与实施例2的区别在于，未进行水热反应，具体过程为：
步骤1，按照摩尔比铁锰比为2:1且(Fe+Mn):P＝1:1，将乙酸锰、硝酸铁、磷酸三乙酯混合后，按照40g/100mL的比例将混合物溶于甘油中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：壬基酚聚氧乙烯醚：硝基苯肼＝150mL:0.8g:1.5g，向有机溶液中加入壬基酚聚氧乙烯醚、硝基苯肼，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为40μm，喷雾压力为1.2MPa，载气气体为空气，载气流量为120L/h，控制燃烧室温度为600℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与醋酸锂混合后，加入固体总质量150％的去离子水，并加入铁元素摩尔量0.4倍的蔗糖，混合均匀后进行喷雾干燥，得到固体料；
步骤5，将步骤4所得固体料在惰性气体的保护下、600℃煅烧20h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
对比例3
本对比例制备了一种磷酸锰铁锂，与实施例3的区别在于，未进行水热反应，具体过程为：
步骤1，按照摩尔比铁锰比为4:1且(Fe+Mn):P＝1:1，将乳酸锰、乙酸铁、磷源为磷酸二乙酯混合后，按照50g/100mL的比例将混合物溶于乙醇中，得到磷铁锰的有机溶液；
步骤2，按照物料比为有机溶液：月桂醇聚氧乙烯醚：硝基二苯甲酮＝200mL:1.0g:2.0g，向有机溶液中加入月桂醇聚氧乙烯醚、硝基二苯甲酮，混合均匀，得到混合液；
步骤3，将混合液加入到喷雾燃烧装置中，经载气气流进入燃烧室燃烧；喷雾装置的喷头孔径为50μm，喷雾压力为0.8MPa，载气气体为空气或氧气，载气流量为150L/h，控制燃烧室温度为700℃；
步骤4，反应结束后，收集燃烧室内的固体料，按照摩尔比(Fe+Mn):Li＝1:(1.0-1.2)，将步骤3所得固体料与氢氧化锂混合后，加入固体总质量200％的去离子水，并加入铁元素摩尔量0.5倍的果糖，混合均匀后进行喷雾干燥，得到固体料；
步骤5，将步骤4所得固体料在惰性气体的保护下、850℃煅烧6h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。
试验例
以实施例和对比例得到的磷酸锰铁锂为正极材料，乙炔黑为导电剂，PVDF为粘结剂，按质量比8:1:1进行混合，并加入一定量的有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片。此过程中，发现对比例所得磷酸锰铁锂正极材料制得的浆料多为果冻状、难以涂覆，猜测残锂过多，焦磷酸锰与锂源难以进一步烧结制备磷锰类锂电正极材料，检 测实施例和对比例残锂含量，结果如表1所示；
以负极为金属锂片；隔膜为Celgard2400聚丙烯多孔膜；电解液中溶剂为EC、DMC和EMC按质量比1:1:1组成的溶液，溶质为LiPF6，LiPF6的浓度为1.0mol/L；在手套箱内组装2023型扣式电池。对电池进行充放电循环性能测试，在截止电压2.2-4.3V范围内，测试0.1C、1C放电比容量；测试电化学性能结果如表1所示。
表1磷酸锰铁锂的残锂含量及电化学性能
由表1可见，对比例的比容量都很低，这是由于焦磷酸锰未经过水热反应，与锂源喷雾干燥未能顺利转化成磷酸锰锂，无法制备合格的磷酸锰铁锂。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种喷雾燃烧制备磷酸锰铁锂正极材料的方法，其特征在于，包括以下步骤：
    S1：将锰源、铁源和磷源混合溶解于有机溶剂中，得到含磷铁锰的有机溶液；
    S2：向所述有机溶液中加入表面活性剂和助燃剂，得到混合液；
    S3：将所述混合液进行喷雾燃烧，得到第一固体料；
    S4：将所述第一固体料与锂源、水混合，在酸性条件下进行水热反应，反应结束后加入碳源混合，进行喷雾干燥，得到第二固体料；
    S5：所述第二固体料在惰性气氛下煅烧，即得所述磷酸锰铁锂。
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述锰源为乙酸锰或乳酸锰中的至少一种；所述铁源为乙酸铁或硝酸铁中的至少一种；所述磷源为磷酸二乙酯或磷酸三乙酯中的至少一种。
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述锰源、铁源和磷源的混合料与所述有机溶剂的固液比为(30-50)g/100mL。
  4. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述有机溶液、表面活性剂和助燃剂的用量比为(100-200)mL：(0.5-1.0)g：(1.0-2.0)g。
  5. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述表面活性剂为月桂醇聚氧乙烯醚或壬基酚聚氧乙烯醚中的至少一种。
  6. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述助燃剂为烷基硝基茴香醚、硝基苯肼、烷氧基硝基苯胺或硝基二苯甲酮中的至少一种。
  7. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述喷雾燃烧的温度为550-700℃，所用喷头的孔径为30-50μm，喷雾的压力为0.8-1.5MPa。
  8. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述第一固体料与锂源、水混合后，加酸调节pH为2.5-4.0，再进行所述水热反应。
  9. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述水热反应的温度为100-120℃。
  10. 如权利要求1-9任一项所述的方法在制备锂离子电池中的应用。
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