WO2024040903A1 - Méthode de préparation de phosphate de ferromanganèse par coprécipitation et son utilisation - Google Patents

Méthode de préparation de phosphate de ferromanganèse par coprécipitation et son utilisation Download PDF

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Publication number
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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English (en)
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/fr

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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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une méthode de préparation de phosphate de ferromanganèse par coprécipitation et son utilisation. Une solution de ferricyanure, une solution de sel de manganèse, et une solution mixte d'un acide phosphorique et d'un acide perchlorique sont respectivement préparées ; la solution de ferricyanure, la solution de sel de manganèse, la solution mixte et la liqueur alcaline sont ajoutées simultanément dans une solution de base pour réaction ; lorsqu'un matériau de réaction a une taille de particule cible, une séparation solide-liquide est effectuée pour obtenir un précipité ; et un lavage et un séchage sont effectués pour obtenir du phosphate de ferromanganèse. Selon la présente invention, le ferricyanure est utilisé pour inhiber la précipitation directe d'ions ferriques, et l'acide perchlorique et l'acide phosphorique sont utilisés pour effectuer une réaction de rupture de cyanure, de telle sorte que le taux de précipitation du phosphate de fer est ralenti, ce qui permet de mettre en œuvre une coprécipitation de fer et de manganèse, et d'améliorer l'homogénéité du mélange de fer et de manganèse.
PCT/CN2023/079081 2022-08-25 2023-03-01 Méthode de préparation de phosphate de ferromanganèse par coprécipitation et son utilisation WO2024040903A1 (fr)

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CN115321507B (zh) * 2022-08-25 2023-07-07 广东邦普循环科技有限公司 共沉淀制备磷酸锰铁的方法及其应用
CN116062726A (zh) * 2023-03-09 2023-05-05 金驰能源材料有限公司 磷酸铁锂及其连续式生产方法

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JP2011100592A (ja) * 2009-11-05 2011-05-19 Tayca Corp 炭素−オリビン型リン酸マンガン鉄リチウム複合体の製造方法、およびリチウムイオン電池用正極材料
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