WO2024040903A1 - Method for preparing ferromanganese phosphate by coprecipitation and use thereof - Google Patents

Method for preparing ferromanganese phosphate by coprecipitation and use thereof Download PDF

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WO2024040903A1
WO2024040903A1 PCT/CN2023/079081 CN2023079081W WO2024040903A1 WO 2024040903 A1 WO2024040903 A1 WO 2024040903A1 CN 2023079081 W CN2023079081 W CN 2023079081W WO 2024040903 A1 WO2024040903 A1 WO 2024040903A1
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solution
manganese
ferricyanide
phosphate
iron
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PCT/CN2023/079081
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French (fr)
Chinese (zh)
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王涛
余海军
谢英豪
李爱霞
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 GBGB2309719.9A priority Critical patent/GB202309719D0/en
Publication of WO2024040903A1 publication Critical patent/WO2024040903A1/en

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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
    • H01M4/58—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
    • 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 material precursors, and specifically relates to a method for preparing ferromanganese phosphate by co-precipitation and its application.
  • Lithium iron phosphate has the disadvantages of low electronic conductivity, small lithium ion diffusion coefficient, and low material tap density in battery applications. Since manganese compounds have higher electrochemical reaction voltage and better electrolyte compatibility , currently, manganese compounds are introduced into lithium iron phosphate to broaden the application of lithium iron phosphate and form a solid solution of lithium iron manganese phosphate to obtain better capacitance and cycle effects.
  • the direct use of co-precipitation method to prepare ferromanganese phosphate also has the problem that ferromanganese is difficult to form co-precipitate.
  • the manganese in the synthesized ferromanganese phosphate mostly exists as divalent manganese, and during subsequent sintering with the lithium source, an additional phosphorus source needs to be added.
  • direct use of trivalent manganese is prone to disproportionation reactions in the solution, producing divalent manganese and tetravalent manganese, which affects the purity of the product.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
  • the present invention proposes a method for preparing ferromanganese phosphate by co-precipitation and its application. This process can slow down the precipitation rate of ferric phosphate, enable co-precipitation of iron and manganese, and the ferromanganese distribution in the prepared ferromanganese phosphate is relatively uniform.
  • a method for preparing ferric manganese phosphate by co-precipitation which includes the following steps:
  • the ferricyanide solution is a solution containing at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide.
  • the concentration of the ferricyanide solution is 0.1-1.0 mol/L.
  • the manganese salt in the manganese salt solution is selected from at least one of manganese nitrate and manganese sulfate.
  • step S1 the concentration of the manganese salt solution is 0.1-1.0 mol/L.
  • step S1 the molar ratio of phosphoric acid and perchloric acid in the mixed solution is 1: (0.9-3.5).
  • step S1 the total concentration of phosphoric acid and perchloric acid in the mixed solution is 0.5-1.0 mol/L.
  • step S2 the pH of the bottom liquid is 1.8-2.0.
  • step S2 the temperature of the reaction is controlled to be 50-70°C, and the pH is controlled to be 1.8-2.0.
  • the alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution.
  • the concentration of the alkali solution is 0.5-1.0 mol/L.
  • step S2 the reaction is carried out under stirring at a rotation speed of 150-300 r/min.
  • the target particle size D50 is 2-15 ⁇ m.
  • step S3 the drying is vacuum drying, and the drying temperature is 120-150°C, drying time is 2-4h.
  • the invention also provides the application of the method in preparing lithium iron manganese phosphate or lithium ion battery.
  • the present invention uses ferricyanide and manganese salt to carry out coprecipitation reaction in the medium of phosphoric acid and perchloric acid to generate manganese iron phosphate coprecipitate.
  • the reaction equation is as follows (taking sodium ferricyanide as an example): 4Na 3 [Fe(CN) 6 ]+15HClO 4 +4H 3 PO 4 ⁇ 24CO 2 ⁇ +12N 2 ⁇ +12NaCl+12H 2 O+4FePO 4 ⁇ +3HCl; 14Mn 2+ +14H 3 PO 4 +2HClO 4 ⁇ 14MnPO 4 ⁇ +Cl 2 ⁇ +8H 2 O+28H + .
  • iron and manganese co-precipitate with phosphate in a positive trivalent state to form ferromanganese phosphate, which avoids the subsequent shortage of phosphorus sources due to the precipitation of divalent cations and the need for additional additions.
  • the problem of phosphorus source avoids the problem of uneven distribution of phosphorus, manganese and iron; on the other hand, due to the large difference in Ksp between iron phosphate and manganese phosphate, it is difficult for iron to directly carry out co-precipitation reaction with manganese.
  • the present invention uses ferricyanide
  • the compound inhibits the direct precipitation of ferric ions, and uses perchloric acid and phosphoric acid to perform a cyanide-breaking reaction, which slows down the precipitation rate of iron phosphate, makes iron and manganese co-precipitate, improves the uniformity of iron and manganese mixing, and provides the basis for subsequent sintering of phosphoric acid Lithium iron manganese cathode materials lay the foundation for improving material specific capacity and cycle performance.
  • Figure 1 is a SEM image of ferric manganese phosphate prepared in Example 1 of the present invention.
  • a ferromanganese phosphate is prepared.
  • the specific process is:
  • Step 1 prepare a sodium ferricyanide solution with a concentration of 1.0 mol/L;
  • Step 2 prepare a manganese nitrate solution with a concentration of 1.0mol/L
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 10.5 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
  • a ferromanganese phosphate is prepared.
  • the specific process is:
  • Step 1 prepare a potassium ferricyanide solution with a concentration of 0.5mol/L;
  • Step 2 prepare a manganese sulfate solution with a concentration of 0.5mol/L;
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 0.5mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 2 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum dry the washed product at 120°C for 4 hours to obtain ferromanganese phosphate product.
  • a ferromanganese phosphate is prepared.
  • the specific process is:
  • Step 1 prepare a sodium ferrocyanide solution with a concentration of 0.1mol/L;
  • Step 2 prepare a manganese nitrate solution with a concentration of 0.1mol/L;
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 0.5mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 15 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum-dry the washed product at 150°C for 2 hours to obtain ferromanganese phosphate product.
  • This comparative example prepares a ferric manganese phosphate.
  • the difference from Example 1 is that ferric nitrate is used as the iron source.
  • the specific process is:
  • Step 1 prepare a ferric nitrate solution with a concentration of 1.0mol/L
  • Step 2 prepare a manganese nitrate solution with a concentration of 1.0mol/L
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 10.5 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
  • a ferric manganese phosphate was prepared.
  • the difference from Example 2 is that ferric sulfate is used as the iron source.
  • the specific process is:
  • Step 1 Prepare an iron sulfate solution with a concentration of 0.5 mol/L
  • Step 2 prepare a manganese sulfate solution with a concentration of 0.5mol/L;
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 0.5mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 2 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum dry the washed product at 120°C for 4 hours to obtain ferromanganese phosphate product.
  • This comparative example prepares a ferric manganese phosphate.
  • the difference from Example 3 is that ferrous nitrate is used as the iron source.
  • the specific process is:
  • Step 1 prepare a ferrous nitrate solution with a concentration of 0.1mol/L
  • Step 2 prepare a manganese nitrate solution with a concentration of 0.1mol/L;
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 0.5mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow, and control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 15 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum-dry the washed product at 150°C for 2 hours to obtain ferromanganese phosphate product.
  • This comparative example prepares a ferric manganese phosphate.
  • the difference from Example 1 is that ferric nitrate is used as the iron source and no perchloric acid is added.
  • the specific process is:
  • Step 1 prepare a ferric nitrate solution with a concentration of 1.0mol/L
  • Step 2 prepare a manganese nitrate solution with a concentration of 1.0mol/L
  • Step 3 Prepare a phosphoric acid solution with a concentration of 1.0 mol/L
  • Step 4 Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L
  • Step 5 Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid.
  • the bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
  • Step 6 Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle.
  • Step 7 When it is detected that the D50 of the material in the kettle reaches 10.5 ⁇ m, stop feeding and perform solid-liquid separation to obtain a precipitate;
  • Step 8 Wash the precipitate first with deionized water and then with absolute ethanol;
  • Step 9 Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
  • the ferromanganese phosphate products obtained in Examples 1-3 and Comparative Examples 1-4 were mixed with lithium hydroxide and glucose respectively, and then the total 25% deionized water by mass, mixed evenly and then spray-dried; calcined at 750°C for 16 hours under the protection of an inert gas, and naturally cooled to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
  • acetylene black is used as the conductive agent and PVDF is used as the binder.
  • the materials are mixed according to the mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, stirred and then coated.
  • the positive electrode sheet is made by covering it on aluminum foil, and the negative electrode is made of metallic lithium sheet;
  • the separator is 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, and the solute is LiPF 6 .
  • the concentration of LiPF 6 is 1.0mol/L; a 2023 button cell is assembled in the glove box.
  • the charge and discharge cycle performance of the battery was tested, and the discharge specific capacity of 0.2C and 1C was tested in the cut-off voltage range of 2.2 to 4.3V; the electrochemical performance results of the test are shown in Table 2.

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Abstract

Disclosed in the present invention are a method for preparing ferromanganese phosphate by coprecipitation and a use thereof. A ferricyanide solution, a manganese salt solution, and a mixed solution of a phosphoric acid and a perchloric acid are respectively prepared; the ferricyanide solution, the manganese salt solution, the mixed solution, and alkali liquor are concurrently added into a base solution for reaction; when a reaction material has a target particle size, solid-liquid separation is performed to obtain a precipitate; and washing and drying are carried out to obtain ferromanganese phosphate. According to the present invention, ferricyanide is used to inhibit the direct precipitation of ferric ions, and the perchloric acid and the phosphoric acid are used to carry out cyanide breaking reaction, so that the precipitation rate of iron phosphate is slowed down, thereby implementing coprecipitation of iron and manganese, and improving the homogeneity of mixing iron and manganese.

Description

共沉淀制备磷酸锰铁的方法及其应用Method for preparing ferromanganese phosphate by co-precipitation and its application 技术领域Technical field
本发明属于锂电池正极材料前驱体技术领域，具体涉及一种共沉淀制备磷酸锰铁的方法及其应用。The invention belongs to the technical field of lithium battery cathode material precursors, and specifically relates to a method for preparing ferromanganese phosphate by co-precipitation and its application.
背景技术Background technique
磷酸铁锂在电池应用中存在电子导电率较低，锂离子扩散系数较小，材料振实密度较低的缺点，由于锰系化合物具有较高的电化学反应电压和较佳的电解质相容性，目前采用在磷酸铁锂中引入锰系化合物来拓宽磷酸铁锂的应用，形成磷酸锰铁锂固溶体，以获得较佳的电容量以及循环效果。Lithium iron phosphate has the disadvantages of low electronic conductivity, small lithium ion diffusion coefficient, and low material tap density in battery applications. Since manganese compounds have higher electrochemical reaction voltage and better electrolyte compatibility , currently, manganese compounds are introduced into lithium iron phosphate to broaden the application of lithium iron phosphate and form a solid solution of lithium iron manganese phosphate to obtain better capacitance and cycle effects.
磷酸锰铁锂的合成方法有很多，基本类似磷酸铁锂的合成。有纯固相法，包括直接使用磷源、铁源、锰源、锂源等原料烧结得到磷酸锰铁锂，也有先合成磷酸锰作为锰源和部分磷源，再将磷酸锰、铁源、锂源混合，烧结得到磷酸亚锰铁锂。其缺点在于不能实现锰、铁在原子层面的均匀混合，制备出来的磷酸锰铁锂的充电恒压段和倍率放电性能较差。由于磷酸锰与磷酸铁的Ksp不同，沉淀速率与pH不同，直接采用共沉淀法制取磷酸锰铁还存在锰铁难以形成共沉淀物的问题。此外，合成的磷酸锰铁中的锰多以二价锰存在，在后续与锂源烧结时，还需要另外补加磷源。而直接使用三价锰在溶液中易发生歧化反应，生成二价锰和四价锰，影响产品纯度。There are many methods for synthesizing lithium iron manganese phosphate, which are basically similar to the synthesis of lithium iron phosphate. There is a pure solid-phase method, which involves directly sintering phosphorus source, iron source, manganese source, lithium source and other raw materials to obtain lithium manganese iron phosphate. There is also a method that first synthesizes manganese phosphate as a manganese source and part of the phosphorus source, and then combines manganese phosphate, iron source, Lithium sources are mixed and sintered to obtain lithium iron manganese phosphate. Its disadvantage is that it cannot achieve uniform mixing of manganese and iron at the atomic level, and the prepared lithium manganese iron phosphate has poor charging constant voltage section and rate discharge performance. Since the Ksp of manganese phosphate and iron phosphate are different, and the precipitation rate and pH are different, the direct use of co-precipitation method to prepare ferromanganese phosphate also has the problem that ferromanganese is difficult to form co-precipitate. In addition, the manganese in the synthesized ferromanganese phosphate mostly exists as divalent manganese, and during subsequent sintering with the lithium source, an additional phosphorus source needs to be added. However, direct use of trivalent manganese is prone to disproportionation reactions in the solution, producing divalent manganese and tetravalent manganese, which affects the purity of the product.
发明内容Contents of the invention
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，本发明提出一种共沉淀制备磷酸锰铁的方法及其应用，该工艺能够减缓磷酸铁的沉淀速率，使铁锰达到共沉淀，制备得到的磷酸锰铁中锰铁分布较为均匀。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for preparing ferromanganese phosphate by co-precipitation and its application. This process can slow down the precipitation rate of ferric phosphate, enable co-precipitation of iron and manganese, and the ferromanganese distribution in the prepared ferromanganese phosphate is relatively uniform.
根据本发明的一个方面，提出了一种共沉淀制备磷酸锰铁的方法，包括以下步骤：According to one aspect of the present invention, a method for preparing ferric manganese phosphate by co-precipitation is proposed, which includes the following steps:
S1：分别配制铁氰化物溶液、锰盐溶液以及磷酸和高氯酸的混合溶液；S1: Prepare ferricyanide solution, manganese salt solution and mixed solution of phosphoric acid and perchloric acid respectively;
S2：将所述混合溶液与碱液混合作为底液，向所述底液中并流加入所述铁氰化物溶 液、锰盐溶液、混合溶液和碱液进行反应，当反应物料达到目标粒径，进行固液分离，得到沉淀物；S2: Mix the mixed solution and alkali solution as the bottom liquid, and add the ferricyanide solution to the bottom liquid in parallel flow. Liquid, manganese salt solution, mixed solution and alkali solution are reacted. When the reaction material reaches the target particle size, solid-liquid separation is performed to obtain a precipitate;
S3：所述沉淀物经洗涤和干燥，即得所述磷酸锰铁。S3: The precipitate is washed and dried to obtain the ferric manganese phosphate.
在本发明的一些实施方式中，步骤S1中，所述铁氰化物溶液为包含亚铁氰化钠、亚铁氰化钾、铁氰化钠或铁氰化钾中的至少一种的溶液。In some embodiments of the present invention, in step S1, the ferricyanide solution is a solution containing at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide.
在本发明的一些实施方式中，步骤S1中，所述铁氰化物溶液的浓度为0.1-1.0mol/L。In some embodiments of the present invention, in step S1, the concentration of the ferricyanide solution is 0.1-1.0 mol/L.
在本发明的一些实施方式中，步骤S1中，所述锰盐溶液中的锰盐选自硝酸锰、硫酸锰中的至少一种。In some embodiments of the present invention, in step S1, the manganese salt in the manganese salt solution is selected from at least one of manganese nitrate and manganese sulfate.
在本发明的一些实施方式中，步骤S1中，所述锰盐溶液的浓度为0.1-1.0mol/L。In some embodiments of the present invention, in step S1, the concentration of the manganese salt solution is 0.1-1.0 mol/L.
在本发明的一些实施方式中，步骤S1中，所述混合溶液中磷酸和高氯酸的摩尔比为1：(0.9-3.5)。In some embodiments of the present invention, in step S1, the molar ratio of phosphoric acid and perchloric acid in the mixed solution is 1: (0.9-3.5).
在本发明的一些实施方式中，步骤S1中，所述混合溶液中磷酸和高氯酸的总浓度为0.5-1.0mol/L。In some embodiments of the present invention, in step S1, the total concentration of phosphoric acid and perchloric acid in the mixed solution is 0.5-1.0 mol/L.
在本发明的一些实施方式中，步骤S2中，所述底液的pH为1.8-2.0。In some embodiments of the present invention, in step S2, the pH of the bottom liquid is 1.8-2.0.
在本发明的一些实施方式中，步骤S2中，控制所述反应的温度为50-70℃，pH为1.8-2.0。In some embodiments of the present invention, in step S2, the temperature of the reaction is controlled to be 50-70°C, and the pH is controlled to be 1.8-2.0.
在本发明的一些实施方式中，步骤S2中，控制铁氰化物溶液、锰盐溶液和混合溶液三者进料的摩尔比满足：铁锰比＝(0.25-4)：1，(Fe+Mn)：H3PO4＝1：(1.02-1.05)。In some embodiments of the present invention, in step S2, the molar ratio of the three feeds of ferricyanide solution, manganese salt solution and mixed solution is controlled to satisfy: iron-manganese ratio = (0.25-4): 1, (Fe+Mn ): H 3 PO 4 =1: (1.02-1.05).
在本发明的一些实施方式中，步骤S2中，所述碱液为氢氧化钠溶液或氢氧化钾溶液中的至少一种。In some embodiments of the present invention, in step S2, the alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution.
在本发明的一些实施方式中，步骤S2中，所述碱液的浓度为0.5-1.0mol/L。In some embodiments of the present invention, in step S2, the concentration of the alkali solution is 0.5-1.0 mol/L.
在本发明的一些实施方式中，步骤S2中，所述反应在转速为150-300r/min的搅拌下进行。In some embodiments of the present invention, in step S2, the reaction is carried out under stirring at a rotation speed of 150-300 r/min.
在本发明的一些实施方式中，步骤S2中，所述目标粒径D50为2-15μm。In some embodiments of the present invention, in step S2, the target particle size D50 is 2-15 μm.
在本发明的一些实施方式中，步骤S3中，所述干燥为真空干燥，干燥的温度为 120-150℃，干燥的时间为2-4h。In some embodiments of the present invention, in step S3, the drying is vacuum drying, and the drying temperature is 120-150℃, drying time is 2-4h.
本发明还提供所述的方法在制备磷酸锰铁锂或锂离子电池中的应用。The invention also provides the application of the method in preparing lithium iron manganese phosphate or lithium ion battery.
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：According to a preferred embodiment of the present invention, it has at least the following beneficial effects:
1、本发明通过利用铁氰化物与锰盐在磷酸与高氯酸的介质中进行共沉淀反应，以生成磷酸锰铁共沉淀物。其反应方程式如下(以铁氰化钠为例)：
4Na3[Fe(CN)6]+15HClO4+4H3PO4→24CO2↑+12N2↑+12NaCl+12H2O+4FePO4↓+3HCl；
14Mn2++14H3PO4+2HClO4→14MnPO4↓+Cl2↑+8H2O+28H+。1. The present invention uses ferricyanide and manganese salt to carry out coprecipitation reaction in the medium of phosphoric acid and perchloric acid to generate manganese iron phosphate coprecipitate. The reaction equation is as follows (taking sodium ferricyanide as an example):
4Na 3 [Fe(CN) 6 ]+15HClO 4 +4H 3 PO 4 →24CO 2 ↑+12N 2 ↑+12NaCl+12H 2 O+4FePO 4 ↓+3HCl;
14Mn 2+ +14H 3 PO 4 +2HClO 4 →14MnPO 4 ↓+Cl 2 ↑+8H 2 O+28H + .
2、本发明在制备磷酸锰铁时，一方面，铁和锰均以正三价态与磷酸根共沉淀，形成磷酸锰铁，避免了后续由于二价阳离子沉淀导致磷源不足，需另外补加磷源的问题，避免了磷锰铁三者分布不均的问题；另一方面，由于磷酸铁与磷酸锰的Ksp差别较大，铁难以与锰直接进行共沉淀反应，本发明通过利用铁氰化物抑制了三价铁离子的直接沉淀，采用高氯酸与磷酸进行破氰反应，减缓了磷酸铁的沉淀速率，使铁锰达到共沉淀，提高了铁锰混合的均匀性，为后续烧结磷酸锰铁锂正极材料提高材料比容量及循环性能奠定了基础。2. When preparing ferromanganese phosphate in the present invention, on the one hand, iron and manganese co-precipitate with phosphate in a positive trivalent state to form ferromanganese phosphate, which avoids the subsequent shortage of phosphorus sources due to the precipitation of divalent cations and the need for additional additions. The problem of phosphorus source avoids the problem of uneven distribution of phosphorus, manganese and iron; on the other hand, due to the large difference in Ksp between iron phosphate and manganese phosphate, it is difficult for iron to directly carry out co-precipitation reaction with manganese. The present invention uses ferricyanide The compound inhibits the direct precipitation of ferric ions, and uses perchloric acid and phosphoric acid to perform a cyanide-breaking reaction, which slows down the precipitation rate of iron phosphate, makes iron and manganese co-precipitate, improves the uniformity of iron and manganese mixing, and provides the basis for subsequent sintering of phosphoric acid Lithium iron manganese cathode materials lay the foundation for improving material specific capacity and cycle performance.
附图说明Description of drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and examples, wherein:
图1为本发明实施例1制备的磷酸锰铁SEM图。Figure 1 is a SEM image of ferric manganese phosphate prepared in Example 1 of the present invention.
具体实施方式Detailed ways
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。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without exerting creative efforts are all protection scope of the present invention.
实施例1Example 1
本实施例制备了一种磷酸锰铁，具体过程为：In this embodiment, a ferromanganese phosphate is prepared. The specific process is:
步骤1，配制浓度为1.0mol/L的铁氰化钠溶液； Step 1, prepare a sodium ferricyanide solution with a concentration of 1.0 mol/L;
步骤2，配制浓度为1.0mol/L的硝酸锰溶液；Step 2, prepare a manganese nitrate solution with a concentration of 1.0mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:2，配制总浓度为1.0mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:2;
步骤4，配制浓度为1.0mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为1:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速250r/min，反应温度为70℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 1:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 250r/min, and the reaction temperature to 70°C;
步骤7，当检测到釜内物料D50达到10.5μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 10.5 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于135℃下真空干燥3h，即得磷酸锰铁产品。Step 9: Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
实施例2Example 2
本实施例制备了一种磷酸锰铁，具体过程为：In this embodiment, a ferromanganese phosphate is prepared. The specific process is:
步骤1，配制浓度为0.5mol/L的铁氰化钾溶液；Step 1, prepare a potassium ferricyanide solution with a concentration of 0.5mol/L;
步骤2，配制浓度为0.5mol/L的硫酸锰溶液；Step 2, prepare a manganese sulfate solution with a concentration of 0.5mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:0.9，配制总浓度为1.0mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:0.9;
步骤4，配制浓度为0.5mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 0.5mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为0.25:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速300r/min，反应温度为60℃； Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 0.25:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 300r/min, and the reaction temperature to 60°C;
步骤7，当检测到釜内物料D50达到2μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 2 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于120℃下真空干燥4h，即得磷酸锰铁产品。Step 9: Vacuum dry the washed product at 120°C for 4 hours to obtain ferromanganese phosphate product.
实施例3Example 3
本实施例制备了一种磷酸锰铁，具体过程为：In this embodiment, a ferromanganese phosphate is prepared. The specific process is:
步骤1，配制浓度为0.1mol/L的亚铁氰化钠溶液；Step 1, prepare a sodium ferrocyanide solution with a concentration of 0.1mol/L;
步骤2，配制浓度为0.1mol/L的硝酸锰溶液；Step 2, prepare a manganese nitrate solution with a concentration of 0.1mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:3.5，配制总浓度为0.5mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 0.5 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:3.5;
步骤4，配制浓度为0.5mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 0.5mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为1:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速150r/min，反应温度为50℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 1:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 150r/min, and the reaction temperature to 50°C;
步骤7，当检测到釜内物料D50达到15μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 15 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于150℃下真空干燥2h，即得磷酸锰铁产品。Step 9: Vacuum-dry the washed product at 150°C for 2 hours to obtain ferromanganese phosphate product.
对比例1Comparative example 1
本对比例制备了一种磷酸锰铁，与实施例1的区别在于，铁源采用硝酸铁，具体过程为：This comparative example prepares a ferric manganese phosphate. The difference from Example 1 is that ferric nitrate is used as the iron source. The specific process is:
步骤1，配制浓度为1.0mol/L的硝酸铁溶液； Step 1, prepare a ferric nitrate solution with a concentration of 1.0mol/L;
步骤2，配制浓度为1.0mol/L的硝酸锰溶液；Step 2, prepare a manganese nitrate solution with a concentration of 1.0mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:2，配制总浓度为1.0mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:2;
步骤4，配制浓度为1.0mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为1:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速250r/min，反应温度为70℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 1:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 250r/min, and the reaction temperature to 70°C;
步骤7，当检测到釜内物料D50达到10.5μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 10.5 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于135℃下真空干燥3h，即得磷酸锰铁产品。Step 9: Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
对比例2Comparative example 2
本对比例制备了一种磷酸锰铁，与实施例2的区别在于，铁源采用硫酸铁，具体过程为：In this comparative example, a ferric manganese phosphate was prepared. The difference from Example 2 is that ferric sulfate is used as the iron source. The specific process is:
步骤1，配制浓度为0.5mol/L的硫酸铁溶液；Step 1: Prepare an iron sulfate solution with a concentration of 0.5 mol/L;
步骤2，配制浓度为0.5mol/L的硫酸锰溶液；Step 2, prepare a manganese sulfate solution with a concentration of 0.5mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:0.9，配制总浓度为1.0mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:0.9;
步骤4，配制浓度为0.5mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 0.5mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为0.25:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH 为1.8-2.0、搅拌转速300r/min，反应温度为60℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 0.25:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reactor is 1.8-2.0, the stirring speed is 300r/min, and the reaction temperature is 60°C;
步骤7，当检测到釜内物料D50达到2μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 2 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于120℃下真空干燥4h，即得磷酸锰铁产品。Step 9: Vacuum dry the washed product at 120°C for 4 hours to obtain ferromanganese phosphate product.
对比例3Comparative example 3
本对比例制备了一种磷酸锰铁，与实施例3的区别在于，铁源采用硝酸亚铁，具体过程为：This comparative example prepares a ferric manganese phosphate. The difference from Example 3 is that ferrous nitrate is used as the iron source. The specific process is:
步骤1，配制浓度为0.1mol/L的硝酸亚铁溶液；Step 1, prepare a ferrous nitrate solution with a concentration of 0.1mol/L;
步骤2，配制浓度为0.1mol/L的硝酸锰溶液；Step 2, prepare a manganese nitrate solution with a concentration of 0.1mol/L;
步骤3，按照摩尔比磷酸:高氯酸＝1:3.5，配制总浓度为0.5mol/L的磷酸与高氯酸的混合溶液；Step 3: Prepare a mixed solution of phosphoric acid and perchloric acid with a total concentration of 0.5 mol/L according to the molar ratio of phosphoric acid: perchloric acid = 1:3.5;
步骤4，配制浓度为0.5mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 0.5mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为4:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速150r/min，反应温度为50℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow, and control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 4:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 150r/min, and the reaction temperature to 50°C;
步骤7，当检测到釜内物料D50达到15μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 15 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于150℃下真空干燥2h，即得磷酸锰铁产品。Step 9: Vacuum-dry the washed product at 150°C for 2 hours to obtain ferromanganese phosphate product.
对比例4Comparative example 4
本对比例制备了一种磷酸锰铁，与实施例1的区别在于，铁源采用硝酸铁，且不加入高氯酸，具体过程为： This comparative example prepares a ferric manganese phosphate. The difference from Example 1 is that ferric nitrate is used as the iron source and no perchloric acid is added. The specific process is:
步骤1，配制浓度为1.0mol/L的硝酸铁溶液；Step 1, prepare a ferric nitrate solution with a concentration of 1.0mol/L;
步骤2，配制浓度为1.0mol/L的硝酸锰溶液；Step 2, prepare a manganese nitrate solution with a concentration of 1.0mol/L;
步骤3，配制浓度为1.0mol/L的磷酸溶液；Step 3: Prepare a phosphoric acid solution with a concentration of 1.0 mol/L;
步骤4，配制浓度为1.0mol/L的氢氧化钠溶液；Step 4: Prepare a sodium hydroxide solution with a concentration of 1.0 mol/L;
步骤5，将步骤3和步骤4配制的溶液加入至反应釜中作为底液，底液漫过底层搅拌桨，底液pH为1.8-2.0；Step 5: Add the solution prepared in Steps 3 and 4 into the reaction kettle as the bottom liquid. The bottom liquid flows through the bottom stirring paddle, and the pH of the bottom liquid is 1.8-2.0;
步骤6，将步骤1、步骤2、步骤3和步骤4配制的溶液并流加入到反应釜内，控制反应釜进料各物料摩尔比，铁锰比为1:1且(Fe+Mn):H3PO4＝1:1，并控制反应釜内pH为1.8-2.0、搅拌转速250r/min，反应温度为70℃；Step 6: Add the solutions prepared in Step 1, Step 2, Step 3 and Step 4 into the reaction kettle in parallel flow. Control the molar ratio of the materials fed to the reaction kettle. The iron-manganese ratio is 1:1 and (Fe+Mn): H 3 PO 4 =1:1, and control the pH in the reaction kettle to 1.8-2.0, the stirring speed to 250r/min, and the reaction temperature to 70°C;
步骤7，当检测到釜内物料D50达到10.5μm时，停止进料，并进行固液分离，得到沉淀物；Step 7: When it is detected that the D50 of the material in the kettle reaches 10.5 μm, stop feeding and perform solid-liquid separation to obtain a precipitate;
步骤8，沉淀物先用去离子水洗涤，再用无水乙醇洗涤；Step 8: Wash the precipitate first with deionized water and then with absolute ethanol;
步骤9，将洗涤后的产物，置于135℃下真空干燥3h，即得磷酸锰铁产品。Step 9: Vacuum dry the washed product at 135°C for 3 hours to obtain ferromanganese phosphate product.
对实施例1-3和对比例1-4所得磷酸锰铁产品进行ICP检测，结果如表1所示。The ferromanganese phosphate products obtained in Examples 1-3 and Comparative Examples 1-4 were subjected to ICP detection, and the results are shown in Table 1.
表1
Table 1
由表1的检测结果可知，各对比例中锰的沉淀量极少，即使增加锰至最大量，锰的沉淀量仍然很少，无法得到需要的磷酸锰铁目标产品。 It can be seen from the test results in Table 1 that the amount of manganese precipitated in each comparative example is very small. Even if the manganese is increased to the maximum amount, the amount of manganese precipitated is still very small, and the required target product of ferromanganese phosphate cannot be obtained.
试验例Test example
按照摩尔比(Fe+Mn):Li:碳源＝1:1.1:0.4，将实施例1-3和对比例1-4所得磷酸锰铁产品分别与氢氧化锂、葡萄糖混合后，并加入总质量25％的去离子水，混合均匀后进行喷雾干燥；在惰性气体的保护下、750℃煅烧16h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。According to the molar ratio (Fe+Mn): Li: carbon source = 1:1.1:0.4, the ferromanganese phosphate products obtained in Examples 1-3 and Comparative Examples 1-4 were mixed with lithium hydroxide and glucose respectively, and then the total 25% deionized water by mass, mixed evenly and then spray-dried; calcined at 750°C for 16 hours under the protection of an inert gas, and naturally cooled to room temperature to obtain the finished lithium iron manganese phosphate cathode material.
以实施例和对比例得到的磷酸锰铁锂正极材料，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，负极采用金属锂片；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0.2C、1C放电比容量；测试电化学性能结果如表2所示。For the lithium iron manganese phosphate cathode material obtained in the Examples and Comparative Examples, acetylene black is used as the conductive agent and PVDF is used as the binder. The materials are mixed according to the mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, stirred and then coated. The positive electrode sheet is made by covering it on aluminum foil, and the negative electrode is made of metallic lithium sheet; the separator is 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, and the solute is LiPF 6 . The concentration of LiPF 6 is 1.0mol/L; a 2023 button cell is assembled in the glove box. The charge and discharge cycle performance of the battery was tested, and the discharge specific capacity of 0.2C and 1C was tested in the cut-off voltage range of 2.2 to 4.3V; the electrochemical performance results of the test are shown in Table 2.
表2
Table 2
由表2可见实施例的电化学性能明显优于对比例，表明本发明制备的磷酸锰铁烧结得到的磷酸锰铁锂具有更高的比容量和循环性能。It can be seen from Table 2 that the electrochemical properties of the embodiments are significantly better than those of the comparative examples, indicating that the lithium iron manganese phosphate obtained by sintering the ferromanganese phosphate prepared in the present invention has higher specific capacity and cycle performance.
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。 The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种共沉淀制备磷酸锰铁的方法，其特征在于，包括以下步骤：A method for preparing ferric manganese phosphate by co-precipitation, which is characterized in that it includes the following steps:
    S1：分别配制铁氰化物溶液、锰盐溶液以及磷酸和高氯酸的混合溶液；S1: Prepare ferricyanide solution, manganese salt solution and mixed solution of phosphoric acid and perchloric acid respectively;
    S2：将所述混合溶液与碱液混合作为底液，向所述底液中并流加入所述铁氰化物溶液、锰盐溶液、混合溶液和碱液进行反应，当反应物料达到目标粒径，进行固液分离，得到沉淀物；S2: Mix the mixed solution and alkali liquid as the bottom liquid, add the ferricyanide solution, manganese salt solution, mixed solution and alkali liquid into the bottom liquid in parallel flow for reaction. When the reaction material reaches the target particle size , perform solid-liquid separation to obtain a precipitate;
    S3：所述沉淀物经洗涤和干燥，得到所述磷酸锰铁。S3: The precipitate is washed and dried to obtain the ferric manganese phosphate.
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述铁氰化物溶液为包含亚铁氰化钠、亚铁氰化钾、铁氰化钠或铁氰化钾中的至少一种的溶液。The method according to claim 1, wherein in step S1, the ferricyanide solution contains at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide. seed solution.
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述铁氰化物溶液的浓度为0.1-1.0mol/L。The method according to claim 1, characterized in that in step S1, the concentration of the ferricyanide solution is 0.1-1.0 mol/L.
  4. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述锰盐溶液中的锰盐选自硝酸锰、硫酸锰中的至少一种。The method according to claim 1, characterized in that in step S1, the manganese salt in the manganese salt solution is selected from at least one of manganese nitrate and manganese sulfate.
  5. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述混合溶液中磷酸和高氯酸的摩尔比为1：(0.9-3.5)。The method according to claim 1, characterized in that, in step S1, the molar ratio of phosphoric acid and perchloric acid in the mixed solution is 1: (0.9-3.5).
  6. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述底液的pH为1.8-2.0。The method according to claim 1, characterized in that, in step S2, the pH of the bottom liquid is 1.8-2.0.
  7. 根据权利要求1所述的方法，其特征在于，步骤S2中，控制所述反应的温度为50-70℃，pH为1.8-2.0。The method according to claim 1, characterized in that in step S2, the temperature of the reaction is controlled to be 50-70°C and the pH is 1.8-2.0.
  8. 根据权利要求1所述的方法，其特征在于，步骤S2中，控制铁氰化物溶液、锰盐溶液和混合溶液三者进料的摩尔比满足：铁锰比＝(0.25-4)：1，(Fe+Mn)：H3PO4＝1：(1.02-1.05)。The method according to claim 1, characterized in that, in step S2, the molar ratio of the three feeds of ferricyanide solution, manganese salt solution and mixed solution is controlled to satisfy: iron-manganese ratio = (0.25-4): 1, (Fe+Mn): H 3 PO 4 =1: (1.02-1.05).
  9. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述碱液为氢氧化钠溶液或氢氧化钾溶液中的至少一种。The method of claim 1, wherein in step S2, the alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution.
  10. 如权利要求1-9任一项所述的方法在制备磷酸锰铁锂或锂离子电池中的应用。 Application of the method according to any one of claims 1 to 9 in preparing lithium iron manganese phosphate or lithium ion battery.
PCT/CN2023/079081 2022-08-25 2023-03-01 Method for preparing ferromanganese phosphate by coprecipitation and use thereof WO2024040903A1 (en)

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