WO2023179788A1 - 一种复合正极材料及其制备方法与应用 - Google Patents

一种复合正极材料及其制备方法与应用 Download PDF

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Publication number
WO2023179788A1
WO2023179788A1 PCT/CN2023/083886 CN2023083886W WO2023179788A1 WO 2023179788 A1 WO2023179788 A1 WO 2023179788A1 CN 2023083886 W CN2023083886 W CN 2023083886W WO 2023179788 A1 WO2023179788 A1 WO 2023179788A1
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Prior art keywords
lfp
lmfp
particle size
composite cathode
cathode material
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PCT/CN2023/083886
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English (en)
French (fr)
Inventor
李咏军
赵璐涵
赵平
石忠洋
温圣耀
刘范芬
张伟康
苑丁丁
吕正中
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Eve Power Co Ltd
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Eve Power Co Ltd
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Priority to EP23774031.1A priority Critical patent/EP4485569A4/en
Priority to HU2400494A priority patent/HUP2400494A1/hu
Publication of WO2023179788A1 publication Critical patent/WO2023179788A1/zh
Priority to US18/893,988 priority patent/US20250015265A1/en
Anticipated expiration legal-status Critical
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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
    • H01M4/58—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative electrodes
    • 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 present application belongs to the field of lithium-ion batteries and relates to a cathode material, in particular to a composite cathode material and its preparation method and application.
  • the theoretical gram capacity of LFP material is 170mAh/g, and the operating voltage platform is 3.22V.
  • the current commercial LFP material gram capacity can reach 160mAh/g, which is close to the theoretical limit. Therefore, the direction of improving the energy density of LFP batteries is mainly to improve the compaction of the material. density.
  • the highest compacted density of currently used LFP materials is lower than 2.65g/cm 3 , making it difficult for the energy density of a single cell to exceed 190Wh/kg.
  • the main reason why ternary materials have higher energy density than LFP is that they have a higher operating voltage of 3.8V. Therefore, increasing the operating voltage of the material can effectively increase the energy density of LFP batteries.
  • LMFP lithium iron manganese phosphate
  • the theoretical gram capacity of lithium iron manganese phosphate (LMFP) material is the same as that of LFP, but its electrode potential relative to Li + /Li is 4.1V. At the same capacity, LMFP has 15% higher energy density than LFP, and the energy density of the battery core can Breaking through 200Wh/kg.
  • lithium iron manganese phosphate does not contain precious metal elements, has low raw material cost and is environmentally friendly. It has obvious advantages over ternary materials and is a technical direction for high-energy-density batteries.
  • the existing technology discloses a method for improving the safety performance of ternary batteries, which includes the following steps: 1) Mixing common cathode materials with ternary cathode materials and lithium iron phosphate or lithium manganese iron phosphate to obtain cathode materials; 2) Mixing the cathode materials
  • the positive electrode of the ternary battery is prepared according to the conventional lithium ion battery positive electrode sheet manufacturing process; 3)
  • the graphite and lithium titanate materials are mixed and then the ternary battery negative electrode is prepared according to the conventional lithium ion battery negative electrode sheet manufacturing process; 4 ) are prepared into ternary batteries according to conventional lithium-ion battery assembly processes and formation processes.
  • LMPF is only used as an additive to improve the safety performance of NCM batteries, that is, LMFP materials are mixed with NCM materials for use.
  • the cathode active material is mainly NCM materials, ignoring the role of LMFP as a cathode active material. potential.
  • the composite cathode material includes LMFP. Compared with the conventional LFP cathode material, it has a higher discharge platform voltage and greatly improves the energy density of the battery. Compared with Compared with conventional NCM cathode materials, it has better safety and stability performance.
  • the purpose of this application is to provide a composite cathode material and its preparation method and application.
  • the composite cathode material uses LMFP and LFP materials in a variety of particle size ranges to achieve adjustable operating voltage, thereby increasing the energy density of the battery. and safety performance.
  • this application provides a composite cathode material, which includes LMFP and LFP;
  • the primary particle size range of the LMFP is selected from 20-200nm;
  • the primary particle size range of the LFP is selected from a combination of at least two ranges of 100-200nm, 200-350nm, 350-500nm, and 500-1000nm;
  • the primary particle size of LFP is larger than the primary particle size of LMFP.
  • the gaps between small particles of LMFP are evenly filled with large particles of LFP material, where LFP is a combination of different particle size types, which can achieve a primary particle size of LMFP ranging from 20 to 200 nm.
  • LFP can be filled between smaller and larger LMFPs to achieve uniform filling of large particles of LFP, thereby increasing the overall compaction density of the material, increasing the energy density of the battery, and improving the cycle performance of the battery; and, LFP Using different particle size types in combination with LMFP, the voltage can be adjusted.
  • the primary particle size range of LMFP is selected from 20-200nm, which means that the minimum value of the primary particle size of LMFP is above 20nm, for example, it can be 20nm, 22nm, 24nm, 26nm, 28nm or 30nm.
  • the primary particle size of LMFP The maximum value of the diameter is below 200nm, for example, it can be 200nm, 190nm, 180nm, 170nm, 160nm or 150nm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the primary particle size range of the LFP is selected from a combination of at least two ranges of 100-200nm, 200-350nm, 350-500nm, and 500-1000nm. Typical but non-limiting combinations include 200-350nm and 350-500nm. Combination of particle size ranges, combination of two particle size ranges of 500-1000nm and 350-500nm, combination of two particle size ranges of 500-1000nm and 100-200nm, three particles of 200-350nm, 350-500nm and 500-1000nm A combination of particle size ranges, or a combination of the four particle size ranges of 200-350nm, 350-500nm, 500-1000nm and 100-200nm.
  • the primary particle size range of LFP is selected from 200-350nm, which means that the minimum particle size of the primary particles of the LFP material in this particle size range is above 200nm, for example, it can be 200nm, 210nm, 220nm, 230nm, 240nm or 250nm,
  • the maximum particle diameter of the primary particles of LFP is below 350nm, for example, it can be 350nm, 340nm, 330nm, 320nm, 310nm or 300nm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the primary particle size range of LFP is selected from 150-500nm, which means that the minimum particle size of the primary particles of the LFP material in this particle size range is above 150nm, for example, it can be 150nm, 160nm, 170nm, 180nm, 190nm or 200nm,
  • the maximum particle diameter of the primary particles of LFP is below 500nm, for example, it can be 500nm, 490nm, 480nm, 470nm, 460nm or 450nm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the primary particle size range of LFP is selected from 100-1000nm, which means that the minimum particle size of the primary particles of the LFP material in this particle size range is above 100nm, for example, it can be 100nm, 110nm, 120nm, 130nm, 140nm or 150nm,
  • the maximum particle diameter of the primary particles of LFP is below 1000nm, for example, it can be 1000nm, 990nm, 980nm, 970nm, 960nm or 950nm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the primary particle size range of LFP is selected from 350-1000nm, which means that the minimum particle size of the primary particles of the LFP material in this particle size range is above 350nm, for example, it can be 350nm, 360nm, 370nm, 380nm, 390nm or 400nm,
  • the maximum particle diameter of the primary particles of LFP is below 1000nm, for example, it can be 1000nm, 990nm, 980nm, 970nm, 960nm or 950nm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the mass ratio of the LMFP to LFP is (5-9):(1-5), for example, it can be 5:5, 6:4, 7:3, 8:2 or 9:1, but is not limited to For the numerical values listed, other non-listed values within the numerical range are equally applicable.
  • the particle diameter D 50 of the LMFP secondary particles is 0.5-10 ⁇ m, for example, it can be 0.5 ⁇ m, 1 ⁇ m, 3 ⁇ m, 5 ⁇ m, 7 ⁇ m, 9 ⁇ m or 10 ⁇ m, but is not limited to the listed values. Other values within the numerical range are not limited to The same applies to the listed values.
  • the particle diameter D 90 of the LMFP secondary particles is 3-18 ⁇ m, for example, it can be 3 ⁇ m, 5 ⁇ m, 7 ⁇ m, 9 ⁇ m, 11 ⁇ m, 13 ⁇ m, 15 ⁇ m, 17 ⁇ m or 18 ⁇ m, but is not limited to the listed values and ranges. Other values not listed are also applicable.
  • the LMFP includes any one or at least two of LiMn 0.5 Fe 0.5 PO 4 , LiMn 0.6 Fe 0.4 PO 4 , LiMn 0.7 Fe 0.3 PO 4 , LiMn 0.8 Fe 0.2 PO 4 or LiMn 0.9 Fe 0.1 PO 4 Typical but non-limiting combinations include the combination of LiMn 0.5 Fe 0.5 PO 4 and LiMn 0.6 Fe 0.4 PO 4 , the combination of LiMn 0.7 Fe 0.3 PO 4 and LiMn 0.8 Fe 0.2 PO 4 , or the combination of LiMn 0.5 Fe 0.5 PO 4 and LiMn 0.9 Fe 0.1 PO 4 combination.
  • the present application provides a method for preparing a composite cathode material as described in the first aspect.
  • the preparation method includes: dry mixing LMFP and LFP according to the formula amount to obtain the composite cathode active material.
  • This application can obtain a composite cathode material in which small particles of LMFP wrap LFP through simple dry mixing. Blending LMFP and LFP with different primary particle sizes can increase the compaction density of the cathode material, thereby improving the electrochemical performance of the battery.
  • the dry mixing time is 0.5-1h, for example, it can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h, but is not limited to the listed values, and other values within the range are not listed. The same applies to numerical values.
  • the stirring speed of the dry mixing is 10-20 rpm, for example, it can be 10 rpm, 12 rpm, 14 rpm, 16 rpm, 18 rpm or 20 rpm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the dispersion speed of the dry mixing is 500-1500rpm, for example, it can be 500rpm, 700rpm, 900rpm, 1100rpm, 1300rpm or 1500rpm, but is not limited to the listed values, and other unlisted values within the value range are also applicable.
  • the present application provides a lithium ion battery, which includes the composite cathode material as described in the first aspect.
  • the negative active material of the lithium ion battery includes graphite material.
  • the separator of the lithium ion battery includes a PE film or a PP film.
  • the electrolyte of the lithium ion battery includes LiPF 6 .
  • This application uses LFP of different primary particle size types and blends it into LMFP with a smaller primary particle size to increase the compaction density and operating discharge platform voltage of the material, thereby improving the energy density, cycle performance and performance of lithium-ion batteries. Safety performance; and, LFP uses different particle size types to match LMFP, so that the appropriate voltage platform can be adjusted and designed according to needs, so that the voltage can be adjusted.
  • Figure 1 is a scanning electron microscope image of the composite cathode material described in Example 1.
  • the composite cathode material includes LMFP and LFP (LiFePO 4 ), wherein the primary particle size of the LMFP is between 80-150 nm; and the LFP includes four particle sizes.
  • Types of LFP materials, the primary particle sizes of the four types of LFP materials are respectively distributed between 100-200nm, 200-350nm, 350-500nm and 500-1000nm;
  • the primary particle size of the LFP is larger than the primary particle size of the LMFP; the mass ratio of the LMFP to LFP is 7:3;
  • the LMFP is LiMn 0.7 Fe 0.3 PO 4 , the particle size D 50 of its secondary particles is 5 ⁇ m, and the particle size D 90 of the secondary particles is 10 ⁇ m;
  • the preparation method of the composite cathode material includes: dry mixing LMFP and LFP according to the formula amount at a stirring speed of 15 rpm and a dispersion speed of 1000 rpm to obtain the composite cathode active material;
  • the composite cathode material includes LMFP and LFP (LiFePO 4 ), wherein the primary particle size of the LMFP is between 50-80 nm; and the LFP includes four particle sizes.
  • Types of LFP materials, the primary particle sizes of the four types of LFP materials are respectively distributed between 100-200nm, 200-350nm, 350-500nm and 500-1000nm;
  • the primary particle size of the LFP is larger than the primary particle size of the LMFP; the mass ratio of the LMFP to LFP is 7:3;
  • the LMFP is LiMn 0.8 Fe 0.2 PO 4 , the particle size D 50 of its secondary particles is 0.5 ⁇ m, and the particle size D 90 of the secondary particles is 3 ⁇ m;
  • the preparation method of the composite cathode material includes: dry mixing LMFP and LFP according to the formula amount at a stirring speed of 20 rpm and a dispersion speed of 1500 rpm to obtain the composite cathode active material.
  • the composite cathode material includes LMFP and LFP (LiFePO 4 ), wherein the primary particle size of the LMFP is between 20-50 nm; the LFP includes four particle sizes. Types of LFP materials, the primary particle sizes of the four types of LFP materials are respectively distributed between 100-200nm, 200-350nm, 350-500nm and 500-1000nm;
  • the primary particle size of the LFP is larger than the primary particle size of the LMFP; the mass ratio of the LMFP to LFP is 7:3;
  • the LMFP is LiMn 0.9 Fe 0.1 PO 4 , the particle size D 50 of its secondary particles is 5 ⁇ m, and the particle size D 90 of the secondary particles is 18 ⁇ m;
  • the preparation method of the composite cathode material includes: dry mixing LMFP and LFP according to the formula amount at a stirring speed of 10 rpm and a dispersion speed of 500 rpm to obtain the composite cathode active material.
  • Example 4 dry mixing LMFP and LFP according to the formula amount at a stirring speed of 10 rpm and a dispersion speed of 500 rpm to obtain the composite cathode active material.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Embodiment 1 is that the LFP includes three types of particle size LFP materials, and the primary particle sizes of the three types of LFP materials are respectively Distributed between 100-200nm, 200-350nm and 350-500nm, the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the type of the corresponding LFP is changed.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Embodiment 1 is that the LFP includes three types of particle size LFP materials, and the primary particle sizes of the three types of LFP materials are respectively Distributed between 200-350nm, between 350-500nm and between 500-1000nm, the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the type of the corresponding LFP is changed.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Embodiment 1 is that the LFP includes two types of particle size LFP materials, and the primary particle sizes of the two types of LFP materials are respectively Distributed between 200-350nm and 350-500nm, the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the type of the corresponding LFP is changed.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Embodiment 1 is that the LFP includes two types of particle size LFP materials, and the primary particle sizes of the two types of LFP materials are respectively Distributed between 500-1000nm and between 350-500nm, the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the type of the corresponding LFP is changed.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Example 1 is that the mass ratio of the LMFP to LFP is 8:2, and the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the corresponding mass ratio of LMFP and LFP is changed.
  • This embodiment provides a composite cathode material.
  • the only difference between the composite cathode material and Example 1 is that the mass ratio of the LMFP to LFP is 9:1, and the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the corresponding mass ratio of LMFP and LFP is changed.
  • This comparative example provides a composite cathode material.
  • the only difference between the composite cathode material and Example 1 is that the LFP includes a particle size type of LFP material, and the primary particle size distribution of the LFP material is in the range of 350 -500nm, the rest are the same as Example 1;
  • the preparation method of the composite cathode material is the same as in Example 1 except that the type of the corresponding LFP is changed.
  • This comparative example provides a cathode material.
  • the only difference between the cathode material and Embodiment 1 is that it does not include LFP, and the rest is the same as Embodiment 1.
  • the positive electrode material provided in the above examples and comparative examples is made into a positive electrode sheet, it is assembled with the graphite negative electrode sheet, PE separator and 1 mol/L LiPF 6 /EC+EMC electrolyte according to the general process of lithium ion battery preparation to form a soft package lithium Ion batteries, soft-pack lithium-ion batteries undergo 0.05C/0.1C/0.2C small current step charging, aging and volume separation to obtain the finished lithium-ion battery.
  • Compacted density test method Weigh m mass of the cathode materials obtained in the above examples and comparative examples, put them into a powder tableting mold, squeeze them under a pressure of 10 MPa for 2 minutes to form a cylindrical cathode material, and then measure the cylindrical cathode materials respectively. The height of the material at three different positions in the mold is averaged to obtain the height h of the cylindrical cathode material after extrusion.
  • Compaction density m/( ⁇ R 2 ⁇ h), where R is the height of the powder compaction mold. radius;
  • Capacity test method The LAND battery testing system performs a constant current and constant voltage charging-constant current discharge test on the prepared battery. In a voltage window of 2.5V-4.2V and a current density of 0.5C, the charging end current is 0.05C, 3 days before the test The average discharge capacity of three cycles is taken as the average value of three times.
  • Example 1 and Comparative Example 1 It can be seen from Example 1 and Comparative Example 1 that the particle size range of LFP in Comparative Example 1 is the same as that of LMFP, and it is impossible to blend large particles of LFP with smaller particles of LMFP. Therefore, the obtained composite cathode material The compacted density of the battery decreases, and the electrochemical capacity of the battery also decreases accordingly; from Example 1 and Comparative Example 2, it can be seen that Comparative Example 2 does not mix LFP, and its performance is compared with Example 1 that mixes LFP, and the pressure of its material is The real density and electrochemical capacity decreased significantly.
  • this application provides a composite cathode material, which is composed of large particles of LFP mixed with smaller particles of LMFP. By blending the two, the compaction density of the composite cathode material can be increased, thereby Effectively improve the energy density, cycle performance and safety performance of lithium-ion batteries.

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Abstract

本申请提供了一种复合正极材料及其制备方法与应用，所述复合正极材料包括LMFP和LFP；所述LMFP的一次颗粒粒径范围选自20-200nm；所述LFP的一次颗粒粒径范围选自200-350nm，150-500nm，100-1000nm或350-1000nm中至少两个范围的组合；所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径。

Description

一种复合正极材料及其制备方法与应用
本申请要求在2022年3月25日提交中国专利局、申请号为202210306398.6的中国专利申请的优先权，以上申请的全部内容通过引用结合在本申请中。
技术领域
本申请属于锂离子电池领域，涉及一种正极材料，尤其涉及一种复合正极材料及其制备方法与应用。
 背景技术
作为汽车动力来源，锂离子电池相比于传统化石燃料最大的短板就是其较低的能量密度，导致了新能源汽车市场上的“里程焦虑”，因此对于新能源乘用车而言，能量密度是其对锂离子动力电池的关键指标。为了追求单体电芯更高的能量密度，新能源乘用车首要采用能量密度更高的三元（NCM）锂离子电池，但近年来新能源汽车安全性问题凸显，磷酸铁锂（LFP）电池也作为新能源汽车的选择。
LFP材料理论克容量为170mAh/g，工作电压平台为3.22V，目前商业化LFP材料克容量能达到160mAh/g，已经接近理论极限，因此提升LFP电池能量密度的方向主要为提高材料的压实密度。但是，当前使用LFP材料的最高压实密度均低于2.65g/cm 3，使单体电芯能量密度难以突破190Wh/kg。三元材料相比LFP具有更高能量密度，其主要一个原因是其具有更高的工作电压3.8V，因此，提高材料的工作电压能有效地提高LFP电池的能量密度。
磷酸锰铁锂（LMFP）材料理论克容量与LFP相同，但它相对于Li +/Li的电极电势为4.1V，在相同的容量下，LMFP比LFP能量密度高15%，电芯能量密度能够突破200Wh/kg。另外，磷酸锰铁锂不含贵金属元素，原料成本低，环境友好，相比三元材料优势明显，是作为高能量密度电池的一种技术方向。
现有技术公开了改善三元电池安全性能的方法，包括如下步骤，1）将常见的正极材料与三元正极材料以及磷酸铁锂或磷酸锰铁锂混合，得到正极材料；2）将正极材料按照常规的锂离子电池正极极片制造工艺制备成三元电池的正极；3）将石墨和钛酸锂材料混合后按照常规的锂离子电池负极极片制造工艺制备成三元电池的负极；4）按常规的锂离子电池组装工艺、化成工艺制备成三元电池。其中，LMPF只是作为改善NCM电池安全性能的一种添加剂，即，在NCM材料中掺混LMFP材料进行使用，本质上正极活性物质还是以NCM材料为主，忽视了LMFP作为一种正极活性材料的潜力。
基于以上研究，需要提供一种复合正极材料，所述复合正极材料包括LMFP，相比于常规的LFP正极材料，其具有更高的放电平台电压，极大的提升了电池的能量密度；相比于常规的NCM正极材料，其具有更好的安全稳定性能。
 发明内容
本申请的目的在于提供一种复合正极材料及其制备方法与应用，所述复合正极材料采用LMFP与多种粒径范围内的LFP材料搭配，做到工作电压可调控，从而提升电池的能量密度及安全性能。
为达到此申请目的，本申请采用以下技术方案：
第一方面，本申请提供了一种复合正极材料，所述复合正极材料包括LMFP和LFP；
所述LMFP的一次颗粒粒径范围选自20-200nm；
所述LFP的一次颗粒粒径范围选自100-200nm，200-350nm，350-500nm，500-1000nm 中至少两个范围的组合；
所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径。
本申请所述复合正极材料中，小颗粒的LMFP间隙中均匀填充大颗粒的LFP材料，其中LFP为不同种粒径类型的组合材料，能够实现LMFP的一次颗粒粒径在20-200nm范围内从小至大分布时，较小和较大的LMFP之间均能填充LFP，实现大颗粒LFP的均匀填充，从而提升材料整体的压实密度，提高电池能量密度，改善电池的循环性能；并且，LFP采用不同粒径类型与LMFP搭配，能够做到电压可调控。
所述LMFP的一次颗粒粒径范围选自20-200nm是指，LMFP的一次颗粒粒径的最小值在20nm以上，例如可以是20nm、22nm、24nm、26nm、28nm或30nm，LMFP的一次颗粒粒径的最大值在200nm以下，例如可以是200nm、190nm、180nm、170nm、160nm或150nm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述LFP的一次颗粒粒径范围选自100-200nm，200-350nm，350-500nm，500-1000nm 中至少两个范围的组合，典型但非限制的组合包括200-350nm和350-500nm两个粒径范围的组合，500-1000nm和350-500nm两个粒径范围的组合，500-1000nm和100-200nm两个粒径范围的组合，200-350nm，350-500nm和500-1000nm三个粒径范围的组合，或200-350nm、350-500nm、500-1000nm和100-200nm四个粒径范围的组合。
所述LFP的一次颗粒粒径范围选自200-350nm是指，此粒径范围的LFP材料的一次颗粒的最小粒径在200nm以上，例如可以是200nm、210nm、220nm、230nm、240nm或250nm，LFP的一次颗粒的最大粒径在350nm以下，例如可以是350nm、340nm、330nm、320nm、310nm或300nm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述LFP的一次颗粒粒径范围选自150-500nm是指，此粒径范围的LFP材料的一次颗粒的最小粒径在150nm以上，例如可以是150nm、160nm、170nm、180nm、190nm或200nm，LFP的一次颗粒的最大粒径在500nm以下，例如可以是500nm、490nm、480nm、470nm、460nm或450nm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述LFP的一次颗粒粒径范围选自100-1000nm是指，此粒径范围的LFP材料的一次颗粒的最小粒径在100nm以上，例如可以是100nm、110nm、120nm、130nm、140nm或150nm，LFP的一次颗粒的最大粒径在1000nm以下，例如可以是1000nm、990nm、980nm、970nm、960nm或950nm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述LFP的一次颗粒粒径范围选自350-1000nm是指，此粒径范围的LFP材料的一次颗粒的最小粒径在350nm以上，例如可以是350nm、360nm、370nm、380nm、390nm或400nm，LFP的一次颗粒的最大粒径在1000nm以下，例如可以是1000nm、990nm、980nm、970nm、960nm或950nm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选的，所述LMFP与LFP的质量比为(5-9):(1-5)，例如可以是5:5、6:4、7:3、8:2或9:1，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述LMFP二次颗粒的粒径D 50为0.5-10μm，例如可以是0.5μm、1μm、3μm、5μm、7μm、9μm或10μm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述LMFP二次颗粒的粒径D 90为3-18μm，例如可以是3μm、5μm、7μm、9μm、11μm、13μm、15μm、17μm或18μm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述LMFP包括LiMn 0.5Fe 0.5PO 4、LiMn 0.6Fe 0.4PO 4、LiMn 0.7Fe 0.3PO 4、LiMn 0.8Fe 0.2PO 4或LiMn 0.9Fe 0.1PO 4中的任意一种或至少两种的组合，典型但非限制的组合包括LiMn 0.5Fe 0.5PO 4和LiMn 0.6Fe 0.4PO 4的组合，LiMn 0.7Fe 0.3PO 4和LiMn 0.8Fe 0.2PO 4的组合，或LiMn 0.5Fe 0.5PO 4和LiMn 0.9Fe 0.1PO 4的组合。
第二方面，本申请提供了一种如第一方面所述复合正极材料的制备方法，所述制备方法包括：按配方量采用干法混合LMFP与LFP，得到所述复合正极活性材料。
本申请通过简单地干法混合即可得到小颗粒LMFP包裹LFP的复合正极材料，不同一次颗粒粒径的LMFP和LFP掺混，能够提升正极材料的压实密度，从而提升电池的电化学性能。
优选地，所述干法混合的时间为0.5-1h，例如可以是0.5h、0.6h、0.7h、0.8h、0.9h或1h，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述干法混合的搅拌速度为10-20rpm，例如可以是10rpm、12rpm、14rpm、16rpm、18rpm或20rpm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述干法混合的分散速度为500-1500rpm，例如可以是500rpm、700rpm、900rpm、1100rpm、1300rpm或1500rpm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
第三方面，本申请提供了一种锂离子电池，所述锂离子电池包括如第一方面所述的复合正极材料。
优选地，所述锂离子电池的负极活性物质包括石墨材料。
优选地，所述锂离子电池的隔膜包括PE膜或PP膜。
优选地，所述锂离子电池的电解液包括LiPF 6。
相对于现有技术，本申请具有以下有益效果：
本申请采用不同一次颗粒粒径类型的LFP，掺混在一次颗粒粒径比其小的LMFP中，来提升材料的压实密度和工作放电平台电压，从而提升锂离子电池的能量密度、循环性能和安全性能；并且，LFP采用不同粒径类型与LMFP搭配，从而根据需求调整设计合适的电压平台，做到电压可调控。
 附图说明
图1是实施例1所述复合正极材料的扫描电镜图。
 实施方式 实施例
本实施例提供了一种复合正极材料，所述复合正极材料包括LMFP和LFP(LiFePO 4)，其中，所述LMFP的一次颗粒粒径在80-150nm之间；所述LFP包括四种粒径类型的LFP材料，四种类型的LFP材料的一次颗粒粒径分别分布在100-200nm之间，200-350nm之间，350-500nm之间和500-1000nm之间；
所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径；所述LMFP与LFP的质量比为7:3；
所述LMFP为LiMn 0.7Fe 0.3PO 4，其二次颗粒的粒径D 50为5μm，二次颗粒的粒径D 90为10μm；
所述复合正极材料的制备方法包括：按配方量，以15rpm的搅拌速度，1000rpm的分散速度，干法混合LMFP与LFP，得到所述复合正极活性材料；
本实施例所述复合正极材料的扫描电镜图如图1所示。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料包括LMFP和LFP(LiFePO 4)，其中，所述LMFP的一次颗粒粒径在50-80nm之间；所述LFP包括四种粒径类型的LFP材料，四种类型的LFP材料的一次颗粒粒径分别分布在100-200nm之间，200-350nm之间，350-500nm之间和500-1000nm ；
所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径；所述LMFP与LFP的质量比为7:3；
所述LMFP为LiMn 0.8Fe 0.2PO 4，其二次颗粒的粒径D 50为0.5μm，二次颗粒的粒径D 90为3μm；
所述复合正极材料的制备方法包括：按配方量，以20rpm的搅拌速度，1500rpm的分散速度，干法混合LMFP与LFP，得到所述复合正极活性材料。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料包括LMFP和LFP(LiFePO 4)，其中，所述LMFP的一次颗粒粒径在20-50nm之间；所述LFP包括四种粒径类型的LFP材料，四种类型的LFP材料的一次颗粒粒径分别分布在100-200nm之间，200-350nm之间，350-500nm之间和500-1000nm 之间；
所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径；所述LMFP与LFP的质量比为7:3；
所述LMFP为LiMn 0.9Fe 0.1PO 4，其二次颗粒的粒径D 50为5μm，二次颗粒的粒径D 90为18μm；
所述复合正极材料的制备方法包括：按配方量，以10rpm的搅拌速度，500rpm的分散速度，干法混合LMFP与LFP，得到所述复合正极活性材料。 实施例4
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LFP包括三种粒径类型的LFP材料，三种类型的LFP材料的一次颗粒粒径分别分布在100-200nm之间，200-350nm之间和350-500nm之间，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LFP的类型改变外，其余均与实施例1相同。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LFP包括三种粒径类型的LFP材料，三种类型的LFP材料的一次颗粒粒径分别分布在200-350nm之间，350-500nm之间和500-1000nm之间，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LFP的类型改变外，其余均与实施例1相同。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LFP包括两种粒径类型的LFP材料，两种类型的LFP材料的一次颗粒粒径分别分布在200-350nm之间和350-500nm之间，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LFP的类型改变外，其余均与实施例1相同。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LFP包括两种粒径类型的LFP材料，两种类型的LFP材料的一次颗粒粒径分别分布在500-1000nm之间和350-500nm之间，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LFP的类型改变外，其余均与实施例1相同。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LMFP与LFP的质量比为8:2，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LMFP与LFP的质量比改变外，其余均与实施例1相同。
实施例
本实施例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LMFP与LFP的质量比为9:1，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LMFP与LFP的质量比改变外，其余均与实施例1相同。
本对比例提供了一种复合正极材料，所述复合正极材料与实施例1的区别仅在于，所述LFP包括一种粒径类型的LFP材料，所述LFP材料的一次颗粒粒径分布在350-500nm之间，其余均与实施例1相同；
所述复合正极材料的制备方法除相应的LFP的类型改变外，其余均与实施例1相同。
本对比例提供了一种正极材料，所述正极材料与实施例1的区别仅在于，不包括LFP，其余均与实施例1相同。
以上实施例和对比例提供的正极材料制成正极片后，与石墨负极片、PE隔膜和1mol/L的LiPF 6/EC+EMC电解液，按照锂离子电池制备的一般工艺组装成软包锂离子电池，软包锂离子电池经过0.05C/0.1C/0.2C小电流阶梯充电，化成老化以及分容后得到成品的锂离子电池。
压实密度测试方法：称取m质量的上述实施例和对比例所得的正极材料，放入粉末压片模具中，在10Mpa的压力下挤压2min成圆柱形正极材料后，分别测量圆柱形正极材料在模具中的三个不同位置的高度，取平均值得到挤压后圆柱形正极材料的高度h，压实密度=m/(π×R 2×h)，其中R为粉末压实模具的半径；
容量测试方法：LAND电池测试系统对制备所得电池进行恒流恒压充电-恒流放电测试，在2.5V-4.2V的电压窗口，0.5C的电流密度下，充电截至电流0.05C，测试前3次循环放电容量，取3次容量平均值。
表1
压实密度(g/cm 3) 克容量(mAh/g)
实施例1 2.30 142.8
实施例2 2.20 140.4
实施例3 1.85 141.4
实施例4 2.20 140.8
实施例5 2.25 140.3
实施例6 2.10 140.6
实施例7 2.00 141.2
实施例8 2.15 141.3
实施例9 2.20 141.7
对比例1 1.70 139.8
对比例2 1.65 137.1
测试结果如表1所示：
从表1可以看出以下几点：
（1）由实施例1-9可知，本申请采用不同种粒径类型的LFP掺混LMFP，能够提升复合正极材料的压实密度，从而提升了锂离子电池的能量密度，从图1也可看出，本申请能够实现大颗粒的LFP与较小颗粒的LMFP的均匀掺混；同时，由实施例1与实施例4-7可知，LFP的粒径类型会影响复合正极材料的压实密度和电池容量，由实施例1与实施例8-9可知，LMFP与LFP的质量比也会影响正极材料和电池的性能。
（2）由实施例1与对比例1可知，对比例1中LFP的粒径范围与LMFP的相同，无法实现大颗粒的LFP与较小颗粒的LMFP进行掺混，因此，得到的复合正极材料的压实密度下降，电池的电化学容量也相应下降；由实施例1与对比例2可知，对比例2未掺混LFP，其性能相对于掺混了LFP的实施例1，其材料的压实密度和电化学容量明显下降。
综上所述，本申请提供一种复合正极材料，所述复合正极材料由大颗粒的LFP掺混较小颗粒的LMFP组成，通过二者掺混，能够提升复合正极材料的压实密度，从而有效提升锂离子电池了的能量密度、循环性能和安全性能。

Claims (10)

  1.  一种复合正极材料，所述复合正极材料包括LMFP和LFP；
    所述LMFP的一次颗粒粒径范围选自20-200nm；
    所述LFP的一次颗粒粒径范围选自100-200nm，200-350nm，350-500nm，500-1000nm中至少两个范围的组合；
    所述LFP的一次颗粒粒径大于LMFP的一次颗粒粒径。
  2.  根据权利要求1所述的复合正极材料，其中，所述LMFP与LFP的质量比为(5-9):(1-5)。
  3.  根据权利要求1或2所述的复合正极材料，其中，所述LMFP的二次颗粒的粒径D 50为0.5-10μm。
  4.  根据权利要求1-3任一项所述的复合正极材料，其中，所述LMFP的二次颗粒的粒径D 90为3-18μm。
  5.  根据权利要求1-4任一项所述的复合正极材料，其中，所述LMFP包括LiMn 0.5Fe 0.5PO 4、LiMn 0.6Fe 0.4PO 4、LiMn 0.7Fe 0.3PO 4、LiMn 0.8Fe 0.2PO 4或LiMn 0.9Fe 0.1PO 4中的任意一种或至少两种的组合。
  6.  一种如权利要求1-5任一项所述复合正极材料的制备方法，所述制备方法包括：按配方量采用干法混合LMFP与LFP，得到所述复合正极活性材料。
  7.  根据权利要求6所述的制备方法，其中，所述干法混合的时间为0.5-1h。
  8.  根据权利要求6所述的制备方法，其中，所述干法混合的搅拌速度为10-20rpm；
    所述干法混合的分散速度为500-1500rpm。
  9.  一种锂离子电池，所述锂离子电池包括如权利要求1-5任一项所述的复合正极材料。
  10.  根据权利要求9所述的锂离子电池，其中，所述锂离子电池的负极活性物质包括石墨材料；
    所述锂离子电池的隔膜包括PE膜或PP膜；
    所述锂离子电池的电解液包括LiPF 6。
PCT/CN2023/083886 2022-03-25 2023-03-24 一种复合正极材料及其制备方法与应用 Ceased WO2023179788A1 (zh)

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