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WO2025232043A1 - Matériau d'électrode positive à base de phosphate composite, et procédé de préparation et utilisation associés - Google Patents

Matériau d'électrode positive à base de phosphate composite, et procédé de préparation et utilisation associés

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Publication number
WO2025232043A1
WO2025232043A1 PCT/CN2024/115724 CN2024115724W WO2025232043A1 WO 2025232043 A1 WO2025232043 A1 WO 2025232043A1 CN 2024115724 W CN2024115724 W CN 2024115724W WO 2025232043 A1 WO2025232043 A1 WO 2025232043A1
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Prior art keywords
nitrogen
phosphate
coating layer
cathode material
composite phosphate
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PCT/CN2024/115724
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English (en)
Chinese (zh)
Inventor
唐杰
王鹏
孔令涌
冯泽
杭静
饶一楠
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SHENZHEN DYNANONIC CO Ltd
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SHENZHEN DYNANONIC CO Ltd
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Publication of WO2025232043A1 publication Critical patent/WO2025232043A1/fr
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    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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

  • This application relates to the field of battery materials technology, and in particular to a composite phosphate-based cathode material, its preparation method, and its application.
  • Lithium manganese iron phosphate (LMFP) batteries are a new type of power battery. Compared with traditional ternary lithium batteries and lithium iron phosphate (LFP) batteries, they have better safety performance and higher energy density.
  • LMFP lithium manganese iron phosphate
  • phosphate-based cathode materials with the same olivine structure lithium manganese iron phosphate (LMFP) and other phosphate-based cathode materials are solid solution cathode materials formed by combining the high energy density of lithium manganese phosphate, lithium manganese iron phosphate, and lithium iron phosphate.
  • a method for preparing a composite phosphate-based cathode material comprising the following steps:
  • the primary crystallization product is mixed with a second carbon source, a nitrogen source and a solvent, dried and pulverized, and then subjected to a second sintering process to form a nitrogen-doped carbon coating layer on the surface of the carbon coating layer, thereby obtaining a secondary crystallization product.
  • the secondary crystallization product is dispersed in a nitrogen, phosphorus and carbon-containing hydrogel and subjected to a third sintering treatment to form a nitrogen-phosphorus co-doped carbon coating layer on the surface of the nitrogen-doped carbon coating layer, thereby obtaining a composite phosphate-based cathode material.
  • a positive electrode sheet comprising a current collector and a positive electrode active layer formed on the surface of the current collector, wherein the positive electrode active layer contains the aforementioned composite phosphate-based positive electrode material.
  • a secondary battery which includes the aforementioned positive electrode plate.
  • the beneficial effects of the composite phosphate-based cathode material provided in this application embodiment are as follows: it includes a phosphate-based active core, and a carbon coating layer, a nitrogen-doped carbon coating layer, and a nitrogen-phosphorus co-doped carbon coating layer sequentially coated on the outer surface of the phosphate-based active core.
  • the carbon coating layer directly coated on the outer surface of the phosphate-based active core can improve the electronic and ionic conductivity of the composite cathode material, and optimize the particle size and morphology of the composite cathode material, which is beneficial for obtaining a composite phosphate-based cathode material with small particle size, high uniformity, and complete morphology.
  • the nitrogen-doped carbon coating layer coated on the outer surface of the carbon coating layer can not only increase the uniformity and integrity of the coating, but also enhance the electronic conductivity and lithium-ion diffusion of the carbon coating layer through non-metallic atom doping of carbon. Furthermore, the nitrogen-doped carbon coating layer also helps to increase the contact density with the nitrogen-phosphorus co-doped carbon coating layer.
  • a C-N-C-N-P-C-like conductive network is formed between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon layer, ensuring the stability of the three coating layers and further improving the electrochemical performance of the composite cathode material.
  • the electron-rich clouds of the doped P and N atoms provide a rich conductive network.
  • the nitrogen-phosphorus co-doped carbon coating layer can form mutual contacts between different composite phosphate-based cathode material particles, acting as a series network between them, providing continuous electron channels and layered porous channels for Li ion transport.
  • phosphorus (P) can enhance the connection between phosphate-based active materials and carbon coating layers, improve the coating effect of the three types of carbon coating layers, promote interfacial electron transport in composite phosphate-based cathode materials during charging and discharging, and improve the cycle and rate performance of composite phosphate-based cathode materials during charging and discharging.
  • the beneficial effects of the method for preparing composite phosphate-based cathode materials provided in this application are as follows: After preparing a phosphate-based solid-phase precursor material containing a first carbon source, a first sintering treatment is performed to allow the phosphate-based precursor material in the solid-phase precursor material to undergo primary crystallization to form a phosphate-based active material.
  • the carbon material generated by the first carbon source is in situ coated on the outer surface of the phosphate-based active core, optimizing the particle size and morphology of the active core, and obtaining a core-shell primary crystallization product.
  • the second carbon source is mixed with a second carbon source, a nitrogen source, and a solvent, dried, and pulverized to allow the second carbon source and nitrogen source to coat the surface of the primary crystallization product.
  • a second sintering treatment is then performed to optimize the crystal structure in the phosphate-based active core, and the second carbon source and nitrogen source react at high temperature to form a nitrogen-doped carbon coating layer in situ on the surface of the carbon coating layer, increasing the uniformity and integrity of the coating.
  • the electronic conductivity and lithium-ion diffusion of the carbon coating layer are enhanced by nitrogen atom doping of carbon.
  • the secondary crystallization product After obtaining the secondary crystallization product, it is dispersed in a nitrogen-, phosphorus-, and carbon-containing hydrogel and subjected to a third sintering treatment. This process dehydrates and carbonizes the hydrogel on the surface of the nitrogen-doped carbon coating layer, forming a nitrogen-phosphorus co-doped carbon coating layer. High-temperature sintering then creates a C-N-C-N-P-C-like conductive network between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon layer.
  • the electron-rich clouds of the P and N atoms in the nitrogen-phosphorus co-doped carbon coating layer provide a rich conductive network, forming interconnected series networks between different composite phosphate-based cathode material particles.
  • This provides continuous electron channels and layered porous channels for Li ion transport. Furthermore, it enhances the connection between the phosphate-based active material and the carbon coating layer, improves the coating effect of the three carbon coating layers, and enhances the cycle and rate performance of the composite cathode material during charge and discharge.
  • the beneficial effects of the positive electrode sheet provided in this application embodiment are as follows: Since the positive electrode active layer adopts the above-mentioned composite phosphate-based positive electrode material, which includes three coating layers: carbon coating layer, nitrogen-doped carbon coating layer, and nitrogen-phosphorus co-doped carbon coating layer, the ionic conductivity and electronic conductivity of the composite phosphate-based positive electrode material are significantly improved. At the same time, it has the characteristics of good structural stability, high capacity, and excellent conductivity. Therefore, the stability, energy density, rate performance, cycle performance and other electrochemical performance of the positive electrode sheet are improved.
  • the beneficial effects of the secondary battery provided in this application embodiment are as follows: because it contains a positive electrode sheet with excellent electrochemical performance such as good stability, high energy density, good rate performance, and good cycle stability, the energy density, cycle stability, and other electrochemical performance of the secondary battery are improved.
  • Figure 1 is a schematic flowchart of the preparation method of the composite phosphate-based cathode material provided in the embodiments of this application;
  • Figure 2 is a schematic flowchart of the preparation method of the composite phosphate-based cathode material provided in Example 1 of this application;
  • Figure 3 shows the XRD patterns of C@LMFP-Ti (labeled a) and N/P-C@N-C@C@LMFP-Ti (labeled b) in the composite phosphate cathode material provided in Example 1 of this application;
  • Figure 4 is a TEM image of the composite phosphate-based cathode material C@LMFP-Ti (labeled (a)) and the composite phosphate-based cathode material N/P-C@N-C@C@LMFP-Ti (labeled (b)) provided in Embodiment 1 of this application;
  • Figure 5 is a SEM image of the composite phosphate cathode material C@LMFP-Ti (labeled as (a)) and the composite phosphate cathode material N/P-C@N-C@C@LMFP-Ti (labeled as (b)) provided in Embodiment 1 of this application;
  • Figure 6 is an EDS diagram of the composite phosphate cathode material C@LMFP-Ti (labeled as (a)) and the composite phosphate cathode material N/P-C@N-C@C@LMFP-Ti (labeled as (b)) provided in Embodiment 1 of this application.
  • the first aspect of this application provides a composite phosphate-based cathode material, including a phosphate-based active core, on the outer surface of which a carbon coating layer, a nitrogen-doped carbon coating layer, and a nitrogen-phosphorus co-doped carbon coating layer are sequentially coated from the inside to the outside.
  • the first aspect of this application provides a composite phosphate-based cathode material, comprising a phosphate-based active core and, from the inside out, a carbon coating layer, a nitrogen-doped carbon coating layer, and a nitrogen-phosphorus co-doped carbon coating layer sequentially coated on the outer surface of the phosphate-based active core.
  • the carbon coating layer directly coated on the outer surface of the phosphate-based active core improves the electronic and ionic conductivity of the composite cathode material and optimizes its particle size and morphology, resulting in a composite phosphate-based cathode material with small particle size, high uniformity, and complete morphology.
  • the nitrogen-doped carbon coating layer on the outer surface of the carbon coating layer not only increases the uniformity and integrity of the coating but also enhances the electronic conductivity and lithium-ion diffusion of the carbon coating layer through non-metallic atom doping of carbon. Furthermore, the nitrogen-doped carbon coating layer also helps to increase the contact density with the nitrogen-phosphorus co-doped carbon coating layer.
  • a C-N-C-N-P-C-like conductive network is formed between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon layer, ensuring the stability of the three coating layers and further improving the electrochemical performance of the composite cathode material.
  • the electron-rich clouds of the doped P and N atoms provide a rich conductive network.
  • the nitrogen-phosphorus co-doped carbon coating layer can form mutual contacts between different composite phosphate-based cathode material particles, acting as a series network between them, providing continuous electron channels and layered porous channels for Li ion transport.
  • the mass percentage of carbon in the carbon coating layer can be any typical but non-limiting point value or an interval between any two point values, such as 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%.
  • the nitrogen-doped carbon coating layer contains 0.3% to 0.8% carbon and 1.5% to 3.0% nitrogen by mass.
  • the electron-rich cloud of N atoms provides a rich conductive network, which is beneficial for enhancing the electronic conductivity and ion diffusion performance of the carbon layer.
  • this doping level ensures the graphitization degree of the nitrogen-doped carbon coating layer, thus ensuring its electronic and ionic conductivity.
  • the mass percentage of carbon in the nitrogen-doped carbon coating layer can be any typical but non-limiting point value or a range between any two point values, such as 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, and 0.8%; the mass percentage of nitrogen can be any typical but non-limiting point value or a range between any two point values, such as 1.5%, 1.8%, 2.0%, 2.5%, 2.8%, and 3.0%.
  • nitrogen elements in the nitrogen-doped carbon coating layer form chemical bonds with carbon elements and/or are doped in a free form.
  • nitrogen elements can be doped into the carbon coating layer in a free form; or they can form chemical bonds with the carbon material, with nitrogen elements suspended on the outer surface of the nitrogen-doped carbon coating layer. This is beneficial for improving the electronic and ionic conductivity of the composite phosphate-based cathode material, and also for increasing the contact density between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped material.
  • the nitrogen-phosphorus co-doped carbon coating layer contains 0.3%–0.8% carbon, 0.6%–1.5% nitrogen, and 1.2%–3.2% phosphorus by mass.
  • the nitrogen and phosphorus doping content in the nitrogen-phosphorus co-doped carbon coating layer of this application provides a rich electron cloud, offering an abundant conductive network. This facilitates the formation of interconnected series network structures between different composite phosphate-based cathode material particles, providing continuous and abundant electron channels for ion transport.
  • this doping content also enhances the connection between the phosphate-based active material and the carbon coating layer, improves the coating effect of the three carbon coating layers, promotes interfacial electron transport, and enhances the cycle and rate performance of the composite phosphate-based cathode material during charge and discharge.
  • the mass percentage of carbon in the nitrogen-phosphorus co-doped carbon coating layer can be any typical but non-limiting value or a range between any two values, such as 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, and 0.8%;
  • the mass percentage of nitrogen can be any typical but non-limiting value or a range between any two values, such as 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, and 1.6%;
  • the mass percentage of phosphorus can be any typical but non-limiting value or a range between any two values, such as 1.2%, 1.5%, 2.0%, 2.5%, 3.0%, and 3.2%.
  • the nitrogen-phosphorus co-doped carbon coating is prepared by sintering a nitrogen-, phosphorus-, and carbon-containing hydrogel, resulting in a three-dimensional porous network structure.
  • the nitrogen-phosphorus co-doped carbon coating is prepared by sintering a nitrogen-, phosphorus-, and carbon-containing hydrogel.
  • the hydrogel possesses a three-dimensional network structure that retains its loose three-dimensional porous network structure even after losing moisture and carbonizing during the drying sintering process.
  • the phosphate-based cathode material included in the phosphate-based active core of this application can be lithium manganese iron phosphate, lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate-based materials doped with other metal elements, lithium iron phosphate-based materials doped with other metal elements, lithium manganese phosphate-based materials doped with other metal elements, etc. Doping with metal elements can improve the electrochemical performance of the phosphate-based cathode material.
  • the phosphate-based active core of this application has broad selectivity for phosphate-based cathode materials, strong practicality, and can meet different application requirements.
  • the coating layer of the composite phosphate-based cathode material contains 0.9%–2.4% carbon, 2.1%–4.5% nitrogen, and 1.2%–3.2% phosphorus by mass.
  • the total carbon, total nitrogen, and total phosphorus content in the coating layer of the composite phosphate-based cathode material ensures both the capacity and other electrochemical properties of the composite phosphate-based cathode material, while also improving its ionic and electronic conductivity. This, in turn, enhances the cycle stability, rate performance, and other electrochemical properties of the composite phosphate-based cathode material during charge and discharge processes.
  • the total thickness of the carbon coating layer, nitrogen-doped carbon coating layer, and nitrogen-phosphorus co-doped carbon coating layer in the composite phosphate-based cathode material is 1 nm to 9 nm.
  • the overall coating layer on the outer surface of the phosphate-based active core can effectively improve the electronic and ionic conductivity of the composite cathode material, promote interfacial electron transport during charge and discharge, and enhance the cycle and rate performance of the composite phosphate-based cathode material during charge and discharge.
  • the total thickness of the carbon coating layer, nitrogen-doped carbon coating layer, and nitrogen-phosphorus co-doped carbon coating layer in the composite phosphate-based cathode material can be any typical but non-limiting value such as 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, or 9 nm, or a range between any two values.
  • the total thickness of the carbon coating layer, nitrogen-doped carbon coating layer, and nitrogen-phosphorus co-doped carbon coating layer in the composite phosphate-based cathode material is 2 nm to 3 nm.
  • embodiments of this application provide a method for preparing a composite phosphate-based cathode material, as shown in Figure 1, including the following steps:
  • the secondary crystallization product is dispersed into a hydrogel containing nitrogen, phosphorus and carbon, and a third sintering treatment is performed to form a nitrogen-phosphorus co-doped carbon coating layer on the surface of the nitrogen-doped carbon coating layer, thereby obtaining a composite phosphate-based cathode material.
  • After obtaining the secondary crystallization product it is dispersed in a nitrogen-, phosphorus-, and carbon-containing hydrogel and subjected to a third sintering treatment.
  • This process dehydrates the hydrogel and carbonizes it onto the surface of the nitrogen-doped carbon coating layer, forming a nitrogen-phosphorus co-doped carbon coating layer.
  • High-temperature sintering then creates a C-N-C-N-P-C-like conductive network between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon layer.
  • the electron-rich clouds of the P and N atoms in the nitrogen-phosphorus co-doped carbon coating layer provide a rich conductive network, forming interconnected series networks between different composite phosphate-based cathode material particles. This provides continuous electron channels and layered porous channels for Li ion transport. Furthermore, it enhances the connection between the phosphate-based active material and the carbon coating layer, improves the coating effect of the three carbon coating layers, and enhances the cycle and rate performance of the composite cathode material during charge and discharge.
  • the ratio of each raw material component conforms to the stoichiometric ratio of the Li ⁇ sub>m ⁇ /sub>Mn ⁇ sub> x ⁇ /sub> Fe ⁇ sub>y ⁇ /sub>An ⁇ sub>p ⁇ /sub> PO ⁇ sub>4 ⁇ /sub> active material, avoiding the generation of a large number of impurity phases due to incompatible ratios, while ensuring the electrochemical performance of the Li ⁇ sub> m ⁇ /sub>Mn ⁇ sub> x ⁇ /sub> Fe ⁇ sub>y ⁇ /sub>An ⁇ sub>p ⁇ /sub> PO ⁇ sub> 4 ⁇ /sub> active material.
  • the phosphate-based cathode material contained in the phosphate-based active core can be lithium manganese iron phosphate, lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate-based material doped with other metal elements, lithium iron phosphate-based material doped with other metal elements, lithium manganese phosphate-based material doped with other metal elements, etc.
  • the conditions for the first sintering treatment include: heating to 300°C-400°C in an inert atmosphere at a heating rate of 1°C/min-5°C/min, followed by holding at that temperature for 5h-10h.
  • the phosphate-based precursor material in the solid-phase precursor material can undergo primary crystallization to form a phosphate-based active material.
  • the carbon material generated from the first carbon source is in situ coated on the outer surface of the phosphate-based active core, optimizing the particle size and morphology of the active core, resulting in a core-shell primary crystallization product.
  • the inert atmosphere can be at least one of nitrogen, argon, helium, etc.;
  • the specific heating rate can be any typical but non-limiting point value or a range between any two point values, such as 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min;
  • the sintering temperature can be any typical but non-limiting point value or a range between any two point values, such as 300°C, 320°C, 350°C, 380°C, 400°C;
  • the holding time can be any typical but non-limiting point value or a range between any two point values, such as 5h, 6h, 7h, 8h, 9h, 10h.
  • the amount of the first carbon source added is 2 wt% to 8 wt% of the theoretical yield of the composite phosphate-based cathode material.
  • the addition of the first carbon source can form a carbon coating layer in situ on the outer surface of the phosphate-based active core during sintering, thereby optimizing the shape and size of the phosphate-based active core particles.
  • the amount of the first carbon source added can be any typical but non-limiting value, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 8%, or a range between any two values, representing the theoretical yield of the composite phosphate-based cathode material.
  • the first carbon source includes one or more of glucose, sucrose, citric acid, and fructose.
  • These organic carbon sources can be carbonized during high-temperature sintering in an inert atmosphere to form amorphous carbon, which is then deposited in situ onto the outer surface of the phosphate-based active core, forming a carbon coating layer.
  • the lithium source includes one or more of lithium carbonate, lithium oxalate, and lithium acetate.
  • the phosphorus source includes one or more of phosphoric acid, ammonium phosphate, and ammonium dihydrogen phosphate.
  • the manganese source includes one or more of manganese carbonate, manganese oxalate, and manganese acetate.
  • the iron source includes one or more of ferrous oxalate, ferrous acetate, ferric phosphate, and ferric nitrate.
  • the raw material components used in the above embodiments of this application all have a purity of ⁇ 99%, and all of the above raw material components have good solubility, which is beneficial for the preparation of phosphate-based active materials.
  • step S20 above:
  • the amount of the second carbon source added is 2 wt% to 5 wt% of the theoretical yield of the composite phosphate-based cathode material.
  • the amount of the nitrogen source added is 1 wt% to 10 wt% of the theoretical yield of the composite phosphate-based cathode material.
  • the ratio of carbon and nitrogen sources is beneficial for mutual doping of the carbon and nitrogen sources during high-temperature sintering, forming a nitrogen-doped carbon coating layer, optimizing the consistency and integrity of the carbon coating layer, improving the electronic and ionic conductivity of the carbon coating layer, and ensuring that the carbon material has high graphitization performance, thus ensuring its conductivity.
  • the amount of the second carbon source added can be any typical but non-limiting point value or an interval between any two point values, such as 2wt%, 3wt%, 4wt%, 5wt%, etc., which is the theoretical yield of the composite phosphate-based cathode material.
  • the amount of nitrogen source added can be any typical but non-limiting point value or an interval between any two point values, such as 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 10wt%, etc., which is the theoretical yield of composite phosphate-based cathode materials.
  • the conditions for the second sintering process include: heating to 400°C-500°C in an inert atmosphere at a heating rate of 1°C/min-5°C/min, followed by holding at that temperature for 2h-3h.
  • the crystal structure of the phosphate-based active core can be optimized, allowing the second carbon source and nitrogen source to react at high temperatures to form a nitrogen-doped carbon coating layer in situ on the surface of the carbon coating layer. This increases the uniformity and integrity of the coating, and the nitrogen atom doping of carbon enhances the electronic conductivity and lithium-ion diffusion of the carbon coating layer, resulting in a secondary crystallization product.
  • the inert atmosphere can be at least one of nitrogen, argon, helium, etc.
  • the specific heating rate can be any typical but non-limiting point value or a range between any two point values, such as 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min, etc.
  • the sintering temperature can be any typical but non-limiting point value or a range between any two point values, such as 300°C, 420°C, 450°C, 480°C, 500°C, etc.
  • the holding time can be any typical but non-limiting point value or a range between any two point values, such as 2h, 2.5h, 3h, etc.
  • the second carbon source includes one or more of glucose, sucrose, citric acid, and fructose; these organic carbon sources can be carbonized during high-temperature sintering in an inert atmosphere and react with the nitrogen source to generate carbon-nitrogen bonds and/or nitrogen atoms are doped into the carbon coating layer in a free form, forming a nitrogen-doped carbon coating layer on the surface of the carbon coating layer in situ.
  • the nitrogen source includes one or more of amino acids, urea, acetonitrile, trimethylamine, methylimine, and melamine; these nitrogen sources can react with the carbon source or be directly doped into the carbon coating layer in a free form as nitrogen atoms during high-temperature sintering in an inert atmosphere, thereby enhancing the electronic conductivity and lithium-ion diffusion of the carbon coating layer through nitrogen atom doping of carbon.
  • the solvent includes one or more of deionized water and anhydrous ethanol; these solvents have good solubility for carbon and nitrogen sources and good dispersibility for the primary crystallization product.
  • the second carbon source and nitrogen source can coat the surface of the primary crystallization product.
  • the amount of solvent can be 5-10 times the weight of the finished phosphate-based cathode material.
  • the method of mixing the primary crystallization product with the second carbon source, nitrogen source and solvent can be wet ball milling, such as ball milling in a ball mill for 4 to 10 hours, to ensure that the components are fully mixed and uniform, and after drying, the second carbon source and nitrogen source are coated on the surface of the primary crystallization product.
  • an initiator is used to promote the cross-linking polymerization of phytic acid and aniline to form a three-dimensional network structure hydrogel, while simultaneously encapsulating the secondary crystallization product in situ within the hydrogel.
  • the polymerization reaction is carried out under ice bath conditions of -20°C to -5°C. Adding an initiator under these conditions helps to avoid safety issues caused by the subsequent large exothermic reaction.
  • the mixed solution contains 10%–20% phytic acid by mass, 0.1 mol/L–0.2 mol/L aniline, and 0.2 g/mL–0.6 g/mL of the secondary crystallization product.
  • concentration of the secondary crystallization product ensures its stability in the polymer product, while the concentrations of phytic acid and aniline ensure sufficient cross-linking polymerization between them via subsequent initiator catalysis, forming a nitrogen-, phosphorus-, and carbon-containing hydrogel coating the secondary crystallization product.
  • the mass fraction of phytic acid is any typical but non-limiting point value or any range between any two point values, such as 10%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%;
  • the concentration of aniline is any typical but non-limiting point value or any range between any two point values, such as 0.1mol/L, 0.12mol/L, 0.13mol/L, 0.15mol/L, 0.16mol/L, 0.18mol/L, 0.20mol/L;
  • the concentration of the secondary crystallization product is any typical but non-limiting point value or any range between any two point values, such as 0.2g/mL, 0.3g/mL, 0.4g/mL, 0.5g/mL, 0.6g/mL.
  • the concentration of the initiator solution is 0.05 mol/L to 0.15 mol/L; under this concentration condition, the crosslinking polymerization reaction between phytic acid and aniline can be initiated well.
  • the concentration of the initiator solution can be any typical but non-limiting point value or a range between any two point values, such as 0.05 mol/L, 0.06 mol/L, 0.07 mol/L, 0.09 mol/L, 0.1 mol/L, 0.12 mol/L, 0.13 mol/L, and 0.15 mol/L.
  • the initiator solution contains one or more of ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide, and azobisisobutyronitrile. These initiators can all initiate cross-linking polymerization of aniline and phytic acid to form a nitrogen-, phosphorus-, and carbon-containing hydrogel.
  • a C-N-C-N-P-C-like conductive network is formed between the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon layer.
  • the secondary crystallization product is in situ coated within the nitrogen-phosphorus co-doped carbon coating layer, which has a three-dimensional porous network structure.
  • the electron-rich clouds of the P and N atoms doped in the nitrogen-phosphorus co-doped carbon coating layer provide abundant conductive networks, forming interconnected series networks between different composite phosphate-based cathode material particles, providing continuous electron channels and layered porous channels for the transport of Li ions. It also enhances the connection between phosphate-based active materials and carbon coating layers, improves the coating effect of the three types of carbon coating layers, and improves the cycle and rate performance of composite cathode materials during charge and discharge processes.
  • the inert atmosphere can be at least one of nitrogen, argon, helium, etc.;
  • the specific heating rate can be any typical but non-limiting point value or a range between any two point values, such as 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min;
  • the sintering temperature can be any typical but non-limiting point value or a range between any two point values, such as 650°C, 700°C, 850°C;
  • the holding time can be any typical but non-limiting point value or a range between any two point values, such as 5h, 6h, 7h, 8h, 9h, 10h;
  • the temperature can be lowered to any typical but non-limiting point value or a range between any two point values, such as 400°C, 450°C, 500°C; and the annealing can be performed for 2h or 3h, which are typical but non-limiting point values or a range between any two point values.
  • embodiments of this application provide a positive electrode sheet, including a current collector and a positive electrode active layer formed on the surface of the current collector, wherein the positive electrode active layer contains the aforementioned composite phosphate-based positive electrode material.
  • the preparation of the positive electrode active layer includes the following steps: mixing the above-mentioned composite phosphate-based positive electrode material, conductive agent and binder to form an electrode slurry, coating the electrode slurry onto the current collector, and then preparing the positive electrode sheet through steps such as drying, rolling and die cutting.
  • the mass percentage of the composite phosphate-based cathode material in the cathode active layer of the cathode sheet is 90% to 95%.
  • the mass percentage of the composite phosphate-based cathode material in the cathode active material layer can be 90%, 91%, 92%, 93%, 94%, 95%, etc.
  • the current collector of the positive electrode includes, but is not limited to, any one of copper foil or aluminum foil.
  • the binder content in the positive electrode active material layer is 2wt% to 5wt%.
  • the binder content can be typical but not limited to 2wt%, 3wt%, 4wt%, 5wt%, etc.
  • the binder includes one or more of the following: polyvinylidene chloride, soluble polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropyl methylcellulose, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives.
  • the conductive agent content in the positive electrode active material layer is 1 wt% to 5 wt%.
  • the conductive agent content can be a typical but not limited content such as 3 wt%, 4 wt%, or 5 wt%.
  • the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60 , and carbon nanotubes.
  • embodiments of this application provide a secondary battery, which includes the aforementioned positive electrode sheet.
  • the secondary battery provided in this application embodiment has improved the energy density, cycle stability and other electrochemical performance of the secondary battery because it contains a positive electrode sheet with excellent electrochemical performance such as good stability, high energy density, good rate performance and good cycle stability.
  • This application does not specifically limit the negative electrode, electrolyte, separator, etc. in the secondary battery of the embodiments, and can be applied to any battery system.
  • the negative electrode active material of the secondary battery includes, but is not limited to, carbon materials such as graphite, soft carbon (e.g., coke), and hard carbon, or nitrides, tin-based oxides, tin alloys, and nano-anode materials.
  • the current collector includes, but is not limited to, any one of copper foil and aluminum foil.
  • the steps for making the negative electrode sheet include: mixing the negative electrode active material with conductive agents such as conductive carbon black, binders such as carboxymethyl cellulose and styrene-butadiene rubber, and solvents such as water in a mass ratio of (80-99):(1-5):(2-10):100 to make a positive electrode mixed slurry, then degassing under vacuum, discharging the material, coating it on a coating machine, and obtaining the negative electrode sheet after rolling, slitting, and die-cutting.
  • conductive agents such as conductive carbon black
  • binders such as carboxymethyl cellulose and styrene-butadiene rubber
  • solvents such as water in a mass ratio of (80-99):(1-5):(2-10):100
  • the membrane is capable of blocking electrons while allowing ions to pass through.
  • exemplary membranes include, but are not limited to, at least one material selected from polypropylene fibers, polyacrylonitrile fibers, polyvinyl formal fibers, poly(ethylene glycol terephthalate), polyethylene terephthalate, polyamide fibers, and poly(p-phenylene terephthalamide).
  • the electrolyte includes at least one soluble metal salt.
  • the metal salt includes at least one of LiClO4 , LiBF4 , LiPF6 , LiAsF6 , LiCF3SO3 , LiTDI, Li[( CF3SO2 ) 2N ] , Li[( FSO2 ) 2N ], and Li[( CmF2m + 1SO2 )( CnF2n + 1SO2 )N], where m and n are natural numbers.
  • These electrolyte salts can ensure high ionic conductivity of the electrolyte and do not undergo harmful side reactions with electrode materials, electrolyte, or separator, exhibiting good chemical stability.
  • the secondary battery includes at least one of a battery cell, a battery module, and a battery pack.
  • the battery cell types include lithium-ion batteries, as well as novel batteries such as lithium-air batteries and lithium metal batteries.
  • the battery cells of this application can be assembled into a battery module.
  • the battery module can contain multiple battery cells, the specific number of which can be adjusted according to the application and capacity of the battery module.
  • the battery module may also include a housing with a receiving space in which multiple battery cells are received.
  • battery cells and/or battery modules can also be assembled into a battery pack, and the number of battery cells or battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • a composite phosphate-based cathode material includes the following steps:
  • the precursor was placed in a sintering furnace and heated to 320°C in a nitrogen atmosphere at a heating rate of 3°C/min for 6 hours. After cooling to room temperature, the primary crystallization product C@LMFP-Ti material was obtained.
  • the above primary crystallization product (theoretical weight of 1 mol lithium manganese iron phosphate), 4.7 g glucose (3% of the theoretical weight of 1 mol lithium manganese iron phosphate), 6 g urea (1.78% of the theoretical weight of 1 mol lithium manganese iron phosphate), and 1000 mL water are mixed in a certain proportion and ball-milled in a ball mill for 6 hours. After drying and pulverizing, the mixture is carbonized by heating to 480°C at 3°C/min and holding at that temperature for 2.5 hours. The resulting sample is then ground to obtain the secondary crystallization product N-C@C@LMFP-Ti material.
  • step 6 lithium manganese iron phosphate encapsulated by phytic acid-doped polyaniline hydrogel
  • a sintering furnace is placed in a sintering furnace and heated to 740°C for 8 hours under a nitrogen atmosphere at a heating rate of 2°C/min. Then, it is cooled to 420°C for annealing for 2 hours and finally cooled to room temperature to obtain the composite phosphate-based cathode material N/P-C@N-C@C@LMFP-Ti.
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that the doping element in step 1 is changed to cobalt nitrate.
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that the amount of urea added in step 3 is changed to 10.12g (content is about 3.0%).
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that the amount of urea added in step 3 is 20g (content is about 5.93%).
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that the amount of aniline added in step 4 is 500 mL of 0.5 mol/L (content is about 2.22%).
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that: in step 4, ammonium persulfate, an initiator, is not added for polymerization, and phytic acid and aniline only form a mixture.
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that urea is not added in step 3.
  • a composite phosphate-based cathode material comprising the following steps:
  • the precursor was placed in a sintering furnace and heated to 320°C in a nitrogen atmosphere at a heating rate of 3°C/min for 6 hours. After cooling to room temperature, the primary crystallization product C@LMFP-Ti material was obtained.
  • the phytic acid-doped polyaniline hydrogel obtained in step 4 is placed in a sintering furnace and heated to 740°C for 8 hours under a nitrogen atmosphere at a heating rate of 2°C/min. Then, it is cooled to 420°C for annealing for 2 hours and finally cooled to room temperature to obtain the secondary crystallized product N/P-C@C@LMFP-Ti.
  • the above-mentioned secondary crystallized product N/P-C@C@LMFP-Ti (theoretical weight of 1 mol lithium manganese iron phosphate), 4.7 g glucose (3% of the theoretical weight of 1 mol lithium manganese iron phosphate), 6 g urea (1.78% of the theoretical weight of 1 mol lithium manganese iron phosphate), and 1000 mL of water are mixed in a certain proportion, ball-milled in a ball mill for 6 hours, dried and pulverized, and then carbonized by heating to 480°C at 3°C/min and holding at that temperature for 2.5 hours; the obtained sample is then ground to obtain the secondary crystallized product N-C@N/P-C@C@LMFP-Ti material.
  • a composite phosphate-based cathode material is prepared differently from that in Example 1 in that glucose is not added in step 1.
  • X-ray diffraction (XRD) analysis was performed on the primary crystallization product C@LMFP-Ti (labeled a) and the composite phosphate-based cathode material N/P-C@N-C@C@LMFP-Ti (labeled b) obtained in Example 1, as shown in Figure 3.
  • the test results show that the composite phosphate-based cathode material obtained in this application is doped with nitrogen and phosphorus elements.
  • LFP/LMP are the standard peaks of lithium iron phosphate and lithium manganese phosphate, respectively. Since lithium manganese iron phosphate (LMFP) does not have its own characteristic XRD crystal diffraction peaks, its peaks are mainly between those of lithium manganese phosphate (LMP) and lithium iron phosphate (LFP).
  • the primary crystallization product C@LMFP-Ti (labeled as (a)) and the composite phosphate cathode material N/P-C@N-C@C@LMFP-Ti (labeled as (b)) prepared in Example 1 were subjected to transmission electron microscopy (TEM) and scanning electron microscopy (SEM) tests, respectively.
  • TEM transmission electron microscopy
  • SEM scanning electron microscopy
  • the TEM image is shown in Figure 4
  • the test results show that after the nitrogen-doped carbon coating layer and the nitrogen-phosphorus co-doped carbon coating layer are applied, the particle surface and the particles of the composite phosphate cathode material have flocculent material.
  • the flocculent material is a coating layer with a three-dimensional porous network structure.
  • the battery assembly process is as follows: The prepared positive electrode sheet is attached to the positive electrode metal shell with conductive adhesive and then dried; a lithium metal sheet is used as the negative electrode, a Celgard2400 microporous membrane is used as the battery separator, and a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) containing 1.0M LiPF6 is used as the electrolyte (EC/DEC volume ratio is 1:1).
  • the coin cell is assembled in a glove box to obtain a lithium-ion coin cell.
  • the testing equipment involved in the above-mentioned tests includes the following:
  • ICP-OES Inductively coupled plasma optical emission spectrometer
  • Discharge rate capacity At room temperature, the charge/discharge rate of the coin cell battery is 0.1C/1C/2C/3C.
  • Cyclic performance At room temperature, the specific capacity of a button cell after 500 cycles of 1C charge/1C discharge is equal to the initial specific capacity of the first cycle multiplied by 100%.
  • the phosphate-based cathode material prepared in this application embodiment includes a phosphate-based active core and carbon coating layers, nitrogen-doped carbon coating layers and nitrogen-phosphorus co-doped carbon coating layers that are sequentially coated from the inside out. All of these materials exhibit better electronic conductivity, cycle stability and rate performance.
  • the nitrogen-phosphorus co-doped carbon coating layer prepared by nitrogen, phosphorus and carbon hydrogel has a three-dimensional porous structure. During lithium ion insertion and extraction, it can quickly conduct electrons to conduct electricity, thereby reducing polarization and improving the diffusion kinetics of lithium manganese iron phosphate.
  • Example 1 Comparing Example 1 with Comparative Examples 1-4, it can be seen that the doping of nitrogen and phosphorus elements at different positions affects the electronic conductivity, cycle stability, and rate performance of the composite material.

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Abstract

La présente invention appartient au domaine technique des matériaux de batterie, et concerne en particulier un matériau d'électrode positive à base de phosphate composite, un procédé de préparation et une utilisation associés. Le matériau d'électrode positive à base de phosphate composite comprend un noyau actif à base de phosphate, la surface externe du noyau actif à base de phosphate étant séquentiellement revêtue d'une couche de revêtement de carbone, d'une couche de revêtement de carbone dopée à l'azote et d'une couche de revêtement de carbone co-dopé azote-phosphore de l'intérieur vers l'extérieur, la couche de revêtement de carbone pouvant améliorer la conductivité électronique et ionique du matériau d'électrode positive composite, et optimiser la taille et la morphologie de particule du matériau d'électrode positive composite. La couche de revêtement en carbone dopé à l'azote améliore la cohérence et l'intégrité du revêtement ; et du carbone dopé à l'atome d'azote améliore en outre la conductivité électronique et la diffusion lithium-ion de la couche de revêtement en carbone. Des nuages riches en électrons d'atomes de P et de N dans la couche de revêtement de carbone co-dopé azote-phosphore peuvent fournir un réseau conducteur riche, un contact mutuel est formé parmi différentes particules pour former un réseau en série, favorisant ainsi le transport d'électrons interfaciaux du matériau composite pendant un processus de charge et de décharge, et améliorant les performances de cyclage et de vitesse du matériau d'électrode positive à base de phosphate composite pendant le processus de charge et de décharge.
PCT/CN2024/115724 2024-05-06 2024-08-30 Matériau d'électrode positive à base de phosphate composite, et procédé de préparation et utilisation associés Pending WO2025232043A1 (fr)

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