WO2022057919A1 - 正极材料、正极片及电池 - Google Patents

正极材料、正极片及电池 Download PDF

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Publication number
WO2022057919A1
WO2022057919A1 PCT/CN2021/119309 CN2021119309W WO2022057919A1 WO 2022057919 A1 WO2022057919 A1 WO 2022057919A1 CN 2021119309 W CN2021119309 W CN 2021119309W WO 2022057919 A1 WO2022057919 A1 WO 2022057919A1
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Prior art keywords
positive electrode
lithium iron
manganese phosphate
iron manganese
phosphate material
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PCT/CN2021/119309
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English (en)
French (fr)
Inventor
陈娜
庄明昊
郝嵘
潘仪
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BYD Co Ltd
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BYD Co Ltd
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Priority to JP2023517875A priority Critical patent/JP7530513B2/ja
Priority to KR1020237012288A priority patent/KR102860985B1/ko
Priority to EP21868741.6A priority patent/EP4216313A4/en
Publication of WO2022057919A1 publication Critical patent/WO2022057919A1/zh
Priority to US18/122,538 priority patent/US20230223534A1/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
    • 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
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    • 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
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • 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
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • 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
    • H—ELECTRICITY
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    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2006/10—Solid density
    • 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
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    • H01M4/00—Electrodes
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    • 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
    • H01M2004/028—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 relates to the technical field of batteries, in particular to a positive electrode material, a positive electrode sheet and a battery.
  • the cathode material of lithium-ion batteries is critical to the performance of the battery.
  • the cathode materials commonly used in power batteries include ternary materials, lithium iron phosphate materials, and lithium manganese iron phosphate materials.
  • lithium manganese iron phosphate (LMFP for short) has higher safety and cyclability than ternary materials, and the potential of LMFP is much higher. Due to lithium iron phosphate (the potential of lithium iron phosphate is 3.4V), it is expected to improve the energy density of the battery. Therefore, the lithium iron manganese phosphate material with higher safety and higher energy density has gradually become the mainstream cathode material for power batteries.
  • the common product forms of LMFP on the market are mainly single-crystal-like and agglomerate.
  • the single-crystal-like material is composed of one or a few (no more than 5) primary particles, with very few internal grain boundaries; agglomerates
  • the material is a secondary particle material formed by agglomeration of many primary particles, and there are many internal grain boundaries.
  • the primary particles of single-crystal LMFP-like materials are relatively large, so that the degree of manganese dissolution of such materials during the battery cycle is low, but their capacity is low under the same metal ratio; while the primary particles of agglomerates are small and the specific surface area is small.
  • the present application provides a positive electrode material, a positive electrode sheet and a battery, wherein the positive electrode material adopts five kinds of LMFP materials whose D50 particle size decreases in turn, and the morphology, particle number ratio and specificity of the five kinds of LMFP materials are further controlled.
  • the size of D 50 can make the positive electrode sheet using the positive electrode material have a higher compaction density, and the battery with the positive electrode sheet can take into account the performance of high capacity, low dissolved manganese content, and high cycle stability.
  • the present application provides a positive electrode material
  • the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth iron manganese iron phosphate material.
  • the particle number ratio of the fifth lithium iron manganese phosphate material is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6) the first iron manganese phosphate Lithium material, the second lithium manganese iron phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material; wherein the first lithium iron manganese phosphate material is an agglomerate,
  • the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, and the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and
  • the D 50 1 to D 50 5 sequentially represent the value of the particle size D50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material, in units of ⁇ m; the value of a The range is 0.35-0.5, the value range of the b is 0.2-0.27, the value range of the c is 0.17-0.18, and the value range of the d is 0.15-0.16.
  • the present application provides a positive electrode slurry, the positive electrode slurry includes the positive electrode material described in the first aspect of the present application, a conductive agent and a solvent.
  • the present application provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, the positive electrode material layer includes the positive electrode material described in the first aspect of the present application, Or coated with the positive electrode slurry described in the second aspect of the present application.
  • the present application provides a battery including the positive electrode sheet described in the third aspect of the present application.
  • the beneficial effects of the present application include: when the five kinds of lithium manganese iron phosphate materials contained in the positive electrode material provided by the present application meet the above-mentioned specific D50 particle size relationship, the above-mentioned specific morphology requirements and specific particle number ratio requirements, the positive electrode material can be used for
  • the positive electrode slurry prepared from the material has good viscosity and stability
  • the positive electrode sheet made from the positive electrode material has a higher compaction density
  • the battery with the positive electrode sheet has higher capacity and higher cycle stability at the same time.
  • low dissolved manganese and other excellent electrical properties when the five kinds of lithium manganese iron phosphate materials contained in the positive electrode material provided by the present application meet the above-mentioned specific D50 particle size relationship, the above-mentioned specific morphology requirements and specific particle number ratio requirements.
  • an embodiment of the present application provides a positive electrode material, and the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth manganese iron phosphate material.
  • Lithium iron material and fifth lithium iron manganese phosphate material the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, and the fourth lithium iron manganese phosphate material
  • the particle number ratio of the material and the fifth lithium iron manganese phosphate material is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6) first manganese phosphate Lithium iron material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material; wherein, the first lithium iron manganese phosphate material is an agglomerate, and the third lithium iron manganese phosphate material is an agglomerate.
  • the lithium iron manganese tetraphosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, and the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals, respectively, and satisfy the following grains: Diameter relationship:
  • D 50 1 to D 50 5 represent the values of particle size D 50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material in sequence, and the unit is ⁇ m; the value range of a is 0.35 -0.5, the value range of b is 0.2-0.27, the value range of c is 0.17-0.18, and the value range of d is 0.15-0.16.
  • the above-mentioned D 50 1 to D 50 5 can be regarded as the particle size of the respective secondary particles in order (if the LMFP-based single crystal material consists of one primary particle, it can also be regarded as a "secondary particle") .
  • LMFP materials with different morphologies and different particle size D 50 values affect the length of the diffusion path of lithium ions, the amount of dissolved Mn, and the cycle stability.
  • the first lithium manganese iron phosphate material in the form of agglomerates has many grain boundaries, and the energy barrier to be overcome by the diffusion of lithium ions in it is large, but the particle size of the primary particles that make it up is small, and the diffusion path of lithium ions in it is short.
  • the fourth and fifth lithium manganese iron phosphate materials in quasi-single-crystal form have large primary particle size, long diffusion paths for lithium ions, but few grain boundaries and small diffusion energy barriers. Therefore, in the above morphology Under the combined effect of the requirements and D 50 particle size requirements, the charge and discharge capabilities of the above five kinds of lithium manganese iron phosphate materials can be basically the same.
  • the compaction density of the positive electrode sheet will still be low even under the combination of the above-mentioned various particles of different sizes; If the D 50 1 of the lithium material is too small, its primary particle size is lower, the specific surface area of the material will increase, and the side reaction between it and the electrolyte will increase, and the structural stability of the material during the cycle will become worse. The amount of dissolved Mn increases.
  • the compaction density of the positive electrode sheet will also be reduced to a certain extent; , The particle size of the fifth lithium iron manganese phosphate material will also be large, which will lengthen the diffusion path of lithium ions in these two materials and reduce the rate performance of the battery.
  • the value range of the a is 0.41 ⁇ a ⁇ 0.45, and the value range of the b is 0.21 ⁇ b ⁇ 0.23.
  • the a is 0.41, the b is 0.23, the c is 0.18, and the d is 0.16.
  • the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals respectively" can be understood as the second lithium iron manganese phosphate material is aggregates or quasi-single crystals or both. It contains agglomerates and quasi-single crystals.
  • the third lithium iron manganese phosphate material is agglomerates or quasi-single crystals or contains both agglomerates and quasi-single crystals.
  • the median diameter of the primary particles of the agglomerates is in the range of 100 nm-500 nm. That is, the median diameter of the primary particles of the first lithium iron manganese phosphate material is in the range of 100nm-500nm, and the median diameter of the primary particles of the second lithium iron manganese phosphate material in the form of agglomerates is in the range of 100nm-500nm range, the median particle diameter of the primary particles of the third lithium iron manganese phosphate material in the form of agglomerates is in the range of 100 nm-500 nm.
  • the agglomerates in the above-mentioned median particle size range can avoid the increase in the number of primary particles constituting the secondary particles of the LMFP material, resulting in an increase in the specific surface area of the secondary particles, thereby avoiding an increase in the specific surface area of the secondary particles.
  • the area where side reactions occur increases; at the same time, the crushing rate of secondary particles can be reduced in the process of pressing the positive electrode sheet, thereby avoiding the problem of causing new interfaces to appear and deteriorating battery performance; on the other hand, the above median particle size range
  • the agglomerates can reduce the diffusion path of lithium ions in the secondary particle material, thereby avoiding the problems that the capacity of the LMFP material is low, the battery impedance increases, and the power performance decreases.
  • the median particle size of the agglomerates is in the above range, which can avoid the increase of side reactions with the electrolyte due to the too small primary particles of the agglomerates, thereby avoiding the deterioration of the structural stability of the agglomerates and the increase in the amount of dissolved Mn.
  • the diffusion path of lithium ions in the agglomerates can be more suitable, so that the battery rate performance is better.
  • the primary particle size of the single crystal-like is in the range of 0.5 ⁇ m-2.5 ⁇ m. In this way, it can avoid that the single-crystal-like primary particles are too large and the diffusion path of lithium ions is lengthened, and the rate performance of the battery is deteriorated.
  • the primary particle size of the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may both be in the range of 1.5 ⁇ m-2.5 ⁇ m, and the third phosphoric acid in the form of a single crystal
  • the median particle size of the primary particles of the lithium manganese iron material is in the range of 1.0 ⁇ m-1.5 ⁇ m
  • the median particle size of the primary particles of the second lithium iron manganese phosphate material in the quasi-single crystal form is in the range of 0.5 ⁇ m-1.0 ⁇ m.
  • the particle number ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6).
  • the positive electrode sheet made from the above-mentioned positive electrode material can have a higher compaction density (2.55 g/cm 3 or more).
  • the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material The particle number ratio is 1:1:2:8:8. In this way, the positive electrode sheet can have a very high compaction density (eg, about 2.9 g/cm 3 ). Further, the mass ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be 100. :14:2.5:0.5:0.3.
  • the surfaces of the above-mentioned first to fifth lithium iron manganese phosphate materials may all have a carbon coating layer, so that the electrical conductivity of each of the lithium iron manganese phosphate materials can be improved.
  • the molar ratio of manganese to iron (Mn/Fe ratio) in the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material is in the range of 1.0-7.4.
  • the Mn/Fe ratios in the five lithium iron manganese phosphate materials can be equal or unequal, which is not specifically limited.
  • the LMFP materials in the form of agglomerates can be prepared in the following manner:
  • the raw materials for synthesizing LMFP ie, manganese source, iron source, phosphorus source, lithium source and carbon source
  • LMFP manganese source, iron source, phosphorus source, lithium source and carbon source
  • the sintering process sequentially includes a first heating section, a first constant temperature section, a second heating section, a second constant temperature section and a cooling section; wherein, The first heating section is from room temperature to the first constant temperature (such as 400°C), and the heating time can be 2.5h-3.5h; the constant temperature time of the first constant temperature section is 3.5h-5.5h; the second heating section is The first constant temperature (such as 400 ° C) rises to the second constant temperature (such as 700 ° C), and the heating time can be 2.5h-4.0h; the constant temperature time of the second constant temperature section can be 2.5h-4.5h; The second constant temperature (such as 750°C) is lowered to about 50°C, and the cooling time is 5.5h-7.5h.
  • the first constant temperature such as 400 ° C
  • the constant temperature time of the first constant temperature section is 3.5h-5.5h
  • the second heating section is The first constant temperature (such as 400 ° C) rises to the second constant temperature (such as 700 ° C), and
  • the sintered material is subjected to airflow crushing, wherein the pressure of the airflow crushing can be 3MPa-5MPa, and the time can be 2h-3h; then screen and classify to obtain the material with the desired particle size D 50 .
  • the mixing time in the above step (1), may be 0.5h-1.5h, and according to another embodiment of the present application, the mixing time in the above step (1) may be 0.75h-1.2 h.
  • ferromanganese phosphate can be selected as the manganese source, iron source and phosphorus source at the same time.
  • the lithium source may include, but is not limited to, at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, and lithium acetate.
  • the carbon source includes, but is not limited to, at least one of glucose, sucrose, starch, fructose, citric acid, ascorbic acid, and polyethylene glycol.
  • a grinding medium with a diameter of 0.6mm-0.8mm may be used to grind the material until the particle size of the material is below 50 ⁇ m, and then a grinding medium with a diameter of 0.1mm-0.3mm may be used for grinding. The medium is milled until the particle size of the material is 40nm-60nm.
  • the inlet temperature during spray drying can be 150°C-200°C, and according to another embodiment of the present application, the inlet temperature during spray drying is 160°C-180°C .
  • the above-mentioned preparation methods of the quasi-single-crystal LMFP material and the LMFP material of the agglomerate form are different in that the first constant temperature and the second constant temperature during sintering are different, and the pressure of airflow crushing is different.
  • the first heating section is raised from room temperature to a first constant temperature (such as 450°C), and the heating time can be 2.5h-3.5h; the first constant temperature The constant temperature time of the heating section is 3.5h-5.5h; the second heating section is from the first constant temperature (such as 450°C) to the second constant temperature (eg 750°C), and the heating time can be 2.5h-4.0h; The constant temperature time of the constant temperature section can be 2.5h-4.5h; the cooling section is from the second constant temperature (such as 750°C) to about 50°C, and the cooling time is 6.5h-8.5h.
  • airflow crushing can be carried out under the pressure of 5MPa-8MPa for 2h-3h;
  • an embodiment of the present application further provides a positive electrode slurry, the positive electrode slurry includes the above-mentioned positive electrode material and a conductive agent, a binder and a solvent.
  • the mass ratio of the positive electrode material, the conductive agent and the binder is 100:(0.5-5):(0.5-5).
  • the solid content of the positive electrode slurry is 10wt%-80wt%.
  • the conductive agent includes at least one of carbon nanotubes, conductive carbon black, and graphene, and according to another embodiment of the present application, the conductive agent includes three of carbon nanotubes, conductive carbon black, and graphene.
  • the three-dimensional conductive agent can make the positive electrode material layer formed by the positive electrode slurry have better conductivity. Further, the mass ratio of carbon nanotubes, conductive carbon black and graphene may be 6:5:2.
  • the binder is a conventional choice in the battery field, for example, it can be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), polypropylene
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVA polyvinyl alcohol
  • SBR styrene butadiene rubber
  • PAN polyimide
  • PAA polyacrylic acid
  • CMC sodium carboxymethylcellulose
  • alginate sodium alginate
  • PVDF can refer to a copolymer obtained by copolymerizing vinylidene fluoride and an olefin compound containing a polar group
  • the polar group includes at least one of a carboxyl group, an epoxy group, a hydroxyl group and a sulfonic acid group.
  • the presence of agglomerates can enhance the peel strength between the cathode coating formed by the cathode slurry and the current collector.
  • the solvent is a conventional choice in the battery field, for example, N-methylpyrrolidone (NMP) is used.
  • NMP N-methylpyrrolidone
  • the positive electrode slurry may further contain a dispersant, so as to better improve the dispersibility and stability of the positive electrode slurry.
  • the dispersant may be polyvinylpyrrolidone (PVP) or the like.
  • the first LMFP material, the second LMFP material and the third LMFP material with larger particle size can be directly added in the form of their powder, which can prevent sedimentation during slurry mixing, and the particle size is relatively small.
  • the small fourth LMFP material and the fifth LMFP material can be added either in the form of powder or in the form of slurries, wherein, in addition to organic solvents, the respective slurries can also contain dispersants, such as PVP etc.
  • an embodiment of the present application further provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, and the positive electrode material layer includes the above-mentioned positive electrode material Or coated with the above-mentioned positive electrode slurry.
  • the positive electrode sheet containing the above positive electrode material has a high compaction density.
  • the positive electrode material layer also includes a conductive agent and a binder.
  • the positive electrode material layer can be formed by coating the above-mentioned positive electrode slurry on the current collector.
  • an embodiment of the present application further provides a battery including the above positive electrode sheet.
  • the battery also has excellent electrical properties such as higher capacity, lower probability of dissolving manganese, and higher cycle stability.
  • the above-mentioned first to fifth LMFP materials are respectively denoted as particle 1, particle 2, particle 3, particle 4, particle 5, and 5 kinds of particles are selected according to the particle size and particle number ratio in Table 1, for subsequent mixing to obtain Positive electrode materials corresponding to different embodiments.
  • the chemical formula of LMFP in particle 1 to particle 5 is LiMn 0.65 Fe 0.35 PO 4 .
  • the test method for the particle size of each LMFP material is: the test equipment is a laser particle size analyzer, and the reference model is Malvern 2000/3000.
  • the test method is as follows: each LMFP material is dispersed in deionized water, ultrasonicated for 10 min, and the particle refractive index is 1.74; the particle size D 50 of each LMFP material is obtained by testing.
  • the method for measuring the number of particles of LMFP materials with different particle sizes is as follows: LMFP materials with different particle sizes are approximately spherical, and the mass of a single sphere is calculated according to the particle size D 50 and bulk density (about 3.6 g/cm 3 ) of each particle. By controlling the feeding quality of LMFP materials with different particle sizes, the number of particles of LMFP materials with different particle sizes is controlled.
  • the test method for the median particle size of primary particles of each LMFP material is as follows: take a scanning electron microscope (SEM) photo of each LMFP material at a magnification of 10,000 times, measure the size of about 300 primary particles artificially, and make a number distribution. , to obtain the median diameter of the primary particles.
  • SEM scanning electron microscope
  • Preparation of positive electrode slurry add a certain proportion of organic solvent NMP and binder PVDF into the mixer, and after stirring for 1 hour, add conductive agent (specifically, carbon tubes with a mass ratio of 0.6:0.5:0.3, conductive carbon Mixing of black and graphene), stir for 30min, then add particle 1, particle 2 and particle 3 in the form of their respective powders, after stirring for 1.5h, add the PVP-containing NMP slurry of particle 4 and particle 5, and stir 1.5h, after sieving, the positive electrode slurry was obtained.
  • the mass ratio of the positive electrode material composed of particles 1-particles 5 to the conductive agent, the binder PVDF, and the organic solvent NMP is 100:2:2:30.
  • Preparation of positive electrode sheet The positive electrode slurry corresponding to each example was coated on both sides of the aluminum foil respectively, and after drying, a positive electrode material layer was formed on the aluminum foil to obtain an unpressed positive electrode sheet. into a size of 40*100mm, and then use a large hydraulic tablet machine to perform tablet compression to obtain a positive electrode tablet after tableting.
  • the compaction density of the positive electrode sheet can be calculated according to the areal density of the positive electrode sheet and the thickness after pressing, and the results are summarized in Table 2.
  • Preparation of the battery First, prepare the positive electrode slurry corresponding to each example into a single-sided positive electrode sheet with an areal density of 2.0 g/dm 2 and a compacted density of 2.65 g/cm 3 , and each single-sided positive electrode sheet was fabricated. 2025 coin cell battery.
  • the positive electrode slurry corresponding to each embodiment was first prepared into a double-sided positive electrode sheet with an areal density of 4.0 g/dm 2 and a compacted density of 2.65 g/cm 3 ; and then provided with an areal density of 2.1 g/dm 2 and a compacted density It is a double-sided negative electrode sheet of 1.60 g/cm 3 ; the diaphragm is made of PP film, and the 053450 full battery is assembled.
  • the test method of specific capacity is: charge the button battery corresponding to each embodiment at 0.1C under constant current and constant voltage until the voltage is 4.3V, and the cut-off current is 0.05C; then discharge under constant current and constant voltage to 0.1C The voltage was 2.5V, and the charge-discharge cycle was carried out 3 times. The discharge capacity after the third cycle was taken and divided by the amount of dressing of the positive electrode material layer on the positive electrode sheet to calculate the specific capacity of the battery.
  • the test method of the rate performance is: at 25°C, the full battery corresponding to each example is first charged to 4.2V with a constant current of 0.2C, and then discharged to 2.5V with a constant current at different rates of 0.2C and 5C respectively, and the 5C is calculated.
  • the ratio of the discharge capacity at 0.2C to the discharge capacity at 0.2C, and this ratio is used to measure the rate performance of the battery.
  • the test method for the amount of dissolved Mn in the negative electrode is as follows: at 45°C, the full battery corresponding to each example is charged to 4.3V with a constant current of 1C, and then discharged to 2.5V with a constant current of 1C, after 500 charge-discharge cycles. , disassemble the battery, and test the Mn content in the negative electrode material of the negative pole piece; wherein the Mn content is measured by inductively coupled plasma-emission spectrometer (ICP).
  • ICP inductively coupled plasma-emission spectrometer
  • the compaction density of the positive electrode sheet can be reduced to 2.65 g. /cm 3 or more, the highest can reach 2.9g/cm 3 , the specific capacity of the battery is basically not significantly reduced, so that the battery can have a higher energy density.
  • the positive electrode materials of the above embodiments can also make the battery have excellent rate performance, for example, the ratio of the discharge capacity at 5C to 0.2C is 84%-92%, and the battery can be cycled 500 times at 45°C The amount of dissolved Mn in the negative electrode was low, not exceeding 420 ppm.

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Abstract

提供了一种正极材料、正极片及电池，其中，正极材料包括团聚体形式的第一磷酸锰铁锂材料，团聚体和/或类单晶形式的第二磷酸锰铁锂材料和第三磷酸锰铁锂材料，类单晶形式的第四磷酸锰铁锂材料和第五磷酸锰铁锂材料；且第一至第五磷酸锰铁锂材料的颗粒数量比为（0.8-1.2）:（0.8-1.2）:（1.6-2.4）:（6.4-9.6）:（6.4-9.6），粒径D50满足：D 50 5<D 50 4<D 50 3<D 50 2<D 50 1，D 50 2＝aD 50 1，D 50 3＝bD 50 1，D 50 4＝cD 50 1，D 50 5＝dD 50 1，5μm≤D 50 1≤15μm；其中，0.35≤a≤0.5，0.2≤b≤0.27，0.17≤c≤0.18，0.15≤d≤0.16。

Description

正极材料、正极片及电池
优先权信息
本申请请求于2020年09月18日向中国国家知识产权局提交的、专利申请号为202010989423.6、申请名称为“正极材料、正极浆料、正极片及电池”的中国专利申请的优先权，并且其全部内容通过引用结合在本申请中。
技术领域
本申请涉及电池技术领域，具体涉及一种正极材料、正极片及电池。
背景技术
锂离子电池的正极材料对电池的性能至关重要。动力电池普通采用的正极材料有三元材料、磷酸铁锂材料、磷酸锰铁锂材料，其中，磷酸锰铁锂(简称LMFP)的安全性和循环性高于三元材料，且LMFP的电位远高于磷酸铁锂(磷酸铁锂的电位为3.4V)，可有望提升电池的能量密度，因此，安全性更高、能量密度更高的磷酸锰铁锂材料逐渐成为动力电池的主流正极材料。
目前市场上常见的LMFP的产品形式主要有类单晶和团聚体两种，其中，类单晶材料是由一个或者少数个(不超过5个)一次颗粒构成，内部晶界极少；团聚体材料由很多个一次颗粒团聚形成的二次颗粒材料，内部晶界很多。类单晶LMFP材料的一次颗粒较大，使得该类材料在电池循环过程中的溶锰程度较低，但在同样金属比例下其容量发挥偏低；而团聚体的一次颗粒较小，比表面积大，该类材料的容量发挥较好，但团聚体材料在压片过程中容易压碎，造成该类材料的新鲜表面暴露在电解液中，进而导致在电池循环中发生较严重的溶锰现象，劣化循环性能。此外，目前，由类单晶和/或团聚体形式的LMFP材料制得的正极片的压实密度也较低。因此，有必要提供一种全新的LMFP产品，以使正极片具有较高压实密度，使电池可以兼顾高容量、高循环稳定性、低溶锰量等性能。
公开内容
本申请提供了一种正极材料、正极片及电池，其中，正极材料采用含5种D 50粒径依次减小的LMFP材料，并通过进一步控制5种LMFP材料的形貌、颗粒数量比以及具体D 50大小，可使采用该正极材料的正极片具有较高的压实密度，具有该正极片的电池可以兼顾高容量、低溶锰量、高循环稳定性等性能。
具体地，第一方面，本申请提供了一种正极材料，所述正极材料包括第一磷酸锰铁锂 材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料，所述第一磷酸锰铁锂材料、所述第二磷酸锰铁锂材料、所述第三磷酸锰铁锂材料、所述第四磷酸锰铁锂材料和所述第五磷酸锰铁锂材料的颗粒数量比为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6)的第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料；其中，所述第一磷酸锰铁锂材料为团聚体，所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料均为类单晶，所述第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶，且满足以下粒径关系：
D 50 5<D 50 4<D 50 3<D 50 2<D 50 1，且D 50 2＝aD 50 1，D 50 3＝bD 50 1，D 50 4＝cD 50 1，D 50 5＝dD 50 1，5μm≤D 50 1≤15μm；
其中，所述D 50 1至D 50 5依次表示所述第一磷酸锰铁锂材料至所述第五磷酸锰铁锂材料的粒径D50的值，单位均为μm；所述a的取值范围为0.35-0.5，所述b的取值范围为0.2-0.27，所述c的取值范围是0.17-0.18，所述d的取值范围是0.15-0.16。
第二方面，本申请提供了一种正极浆料，所述正极浆料包括本申请第一方面所述的正极材料，以及导电剂和溶剂。
第三方面，本申请提供了一种正极片，所述正极片包括集流体和设置在所述集流体上的正极材料层，所述正极材料层包括本申请第一方面所述的正极材料，或者采用本申请第二方面所述的正极浆料涂覆而成。
第四方面，本申请提供了一种电池，所述电池包括本申请第三方面所述的正极片。
本申请的有益效果包括：本申请提供的正极材料中含有的5种磷酸锰铁锂材料在满足上述特定D50粒径关系、上述特定形貌要求及特定颗粒数量比要求时，可使由该正极材料制得的正极浆料的粘度、稳定性较好，由该正极材料制得的正极片的压实密度较大，具有该正极片的电池同时具有较高的容量、较高的循环稳定性、较低的溶锰量等优异电性能。
本申请的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。
具体实施方式
以下所述是本申请的示例性实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。
在本申请的一个方面，本申请实施例提供了一种正极材料，该正极材料包括第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料，所述第一磷酸锰铁锂材料、所述第二磷酸锰铁锂材料、所述第三磷酸锰铁 锂材料、所述第四磷酸锰铁锂材料和所述第五磷酸锰铁锂材料的颗粒数量比为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6)的第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料；其中，第一磷酸锰铁锂材料为团聚体，第四磷酸锰铁锂材料和第五磷酸锰铁锂材料均为类单晶，第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶，且满足以下粒径关系：
D 50 5<D 50 4<D 50 3<D 50 2<D 50 1，且D 50 2＝aD 50 1，D 50 3＝bD 50 1，D 50 4＝cD 50 1，D 50 5＝dD 50 1，5μm≤D 50 1≤15μm；
其中，D 50 1至D 50 5依次表示所述第一磷酸锰铁锂材料至所述第五磷酸锰铁锂材料的粒径D 50的值，单位均为μm；a的取值范围为0.35-0.5，b的取值范围为0.2-0.27，c的取值范围是0.17-0.18，d的取值范围是0.15-0.16。
本申请中，可将上述D 50 1至D 50 5依次看成各自的二次颗粒的粒径(若LMFP类单晶材料由一个一次颗粒构成，也可将其看成“二次颗粒”)。不同形貌、不同粒径D 50值的LMFP材料影响锂离子在其中的扩散路径的长短及溶Mn量、循环稳定性等。团聚体形式的第一磷酸锰铁锂材料，其晶界较多，锂离子在其中的扩散所要攻克的能垒大，但组成其的一次颗粒粒径较小，锂离子在其中的扩散路径短，而类单晶形式的第四及第五磷酸锰铁锂材料的一次颗粒粒径大，锂离子在其中的扩散路径长，但晶界较少，扩散能垒小，因此，在上述形貌要求及D 50粒径要求的综合作用下，可使上述5种磷酸锰铁锂材料的充放电能力基本一致。
本申请中，若第一磷酸锰铁锂材料的D 50 1过小，即使在上述多种不同尺寸的颗粒搭配下，正极片的压实密度依然会较低；同时若该第一磷酸锰铁锂材料的D 50 1过小，其一次颗粒粒径更低，该材料的比表面积会增加，进而增加其与电解液之间的副反应，该材料在循环过程中的结构稳定性变差，溶Mn量增加。若第一磷酸锰铁锂材料的D 50 1过大，会造成正极片的压实密度也有一定程度的降低；此外，根据上述各颗粒之间的粒度关系，此时类单晶形式的第四、第五磷酸锰铁锂材料的颗粒粒径也会很大，这会使锂离子在这2种材料中的扩散路径变长，电池倍率性能降低。
若上述a、b、c、d不在上述范围内取值，则这5种磷酸锰铁锂材料之间就不能很好地进行粒度区分，从而不能依靠不同粒度级别的LMFP材料之间的多级填充来提高由它们制成的正极片的压实密度。
根据本申请的一个实施例，所述a的取值范围为0.41≤a≤0.45，所述b的取值范围为0.21≤b≤0.23。根据本申请的再一个实施例，所述a为0.41，所述b为0.23，所述c为0.18，所述d为0.16。
需要说明的是，“第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶”可以理解为第二磷酸锰铁锂材料为团聚体或类单晶体或同时含有团聚体和类单晶，同理第 三磷酸锰铁锂材料为团聚体或类单晶体或同时含有团聚体和类单晶。
根据本申请的一个实施例，所述正极材料中，所述团聚体的一次颗粒的中值粒径在100nm-500nm的范围。即，所述第一磷酸锰铁锂材料的一次颗粒的中值粒径在100nm-500nm的范围，团聚体形式的第二磷酸锰铁锂材料的一次颗粒的中值粒径在100nm-500nm的范围，团聚体形式的第三磷酸锰铁锂材料的一次颗粒的中值粒径在100nm-500nm的范围。
在相同的二次颗粒的粒径设计下，上述中值粒径范围的团聚体一方面可以避免构成该LMFP材料二次颗粒的一次颗粒的个数增加造成二次颗粒的比表面积增加，进而避免发生副反应的面积增加；同时在正极片的压片过程中，可以降低二次颗粒的破碎率，进而避免导致新的界面出现，劣化电池性能的问题；再一方面，上述中值粒径范围的团聚体可以降低锂离子在二次颗粒材料中的扩散路径，从而避免导致LMFP材料的容量发挥偏低，电池阻抗增加，功率性能降低的问题。另外上述团聚体的中值粒径在上述范围，可以避免因团聚体的一次颗粒过小而增加其与电解液的副反应，进而避免团聚体的结构稳定性变差、溶Mn量增加。此外，还可使锂离子在团聚体中的扩散路径较合适，使电池倍率性能较好。
根据本申请的一个实施例，所述类单晶的一次颗粒粒径在0.5μm-2.5μm的范围。这样可避免类单晶一次颗粒过大而使锂离子的扩散路径变长，使电池的倍率性能变差。根据本申请的一个具体实施例，所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的一次颗粒粒径可以均在1.5μm-2.5μm的范围，类单晶形式的第三磷酸锰铁锂材料的一次颗粒的中值粒径在1.0μm-1.5μm的范围，类单晶形式的第二磷酸锰铁锂材料的一次颗粒的中值粒径在0.5μm-1.0μm的范围。这样可使上述5种磷酸锰铁锂材料的充放电一致性更高。
本申请中，所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比可以为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6)。上述5种磷酸锰铁锂材料的颗粒数量比在上述范围可使由上述正极材料制得的正极片具有较高的压实密度(2.55g/cm 3以上)。根据本申请的一个实施例，所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比为1：1：2：8：8。这样，可使正极片具有极高的压实密度(例如约在2.9g/cm 3)。进一步地，所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的质量比可以为100：14：2.5：0.5：0.3。
根据本申请的一个实施例，上述第一至第五磷酸锰铁锂材料的表面还可以均具有碳包覆层，以使该各磷酸锰铁锂材料的导电性得到提升。
根据本申请的一个实施例，所述第一磷酸锰铁锂材料至第五磷酸锰铁锂材料中的锰铁摩尔比值(Mn/Fe比值)在1.0-7.4的范围内。这5种磷酸锰铁锂材料中的Mn/Fe比值可以相等 或不等，对此不进行具体限定。
上述团聚体形式的LMFP材料可以通过如下方式制备得到：
(1)将合成LMFP的原材料(即，锰源、铁源、磷源、锂源和碳源)按一定质量比混合，将混合后的物料与水进行湿法研磨以研磨至物料粒径在40nm-60nm；
(2)将上述研磨后的湿料进行喷雾干燥，得到干燥粉体；
(3)将上述干燥粉体在氧气浓度小于150ppm的氛围下进行烧结；其中，烧结过程依次包括第一升温段、第一恒温段、第二升温段、第二恒温段以及降温段；其中，第一升温段是由室温升至第一恒温温度(如400℃)，升温时间可以是2.5h-3.5h；第一恒温段的恒温时间为3.5h-5.5h；第二升温段是由第一恒温温度(如400℃)升至第二恒温温度(如700℃)，升温时间可以是2.5h-4.0h；第二恒温段的恒温时间可以是2.5h-4.5h；降温段是由第二恒温温度(如750℃)降至50℃左右，降温时间为5.5h-7.5h。
(4)将烧结后的物料进行气流破碎，其中，气流破碎的压力可以为3MPa-5MPa，时间可以为2h-3h；然后再进行筛选分级，得到所需粒径D 50的材料。
根据本申请的一个实施例，上述步骤(1)中，混合的时间可以为0.5h-1.5h，根据本申请的再一个实施例，上述步骤(1)中混合的时间可以为0.75h-1.2h。
根据本申请的一个实施例，步骤(1)中，可以选用磷酸锰铁同时充当锰源、铁源和磷源。锂源可以包括但不限于氢氧化锂、碳酸锂、硝酸锂、草酸锂、磷酸二氢锂、柠檬酸锂和醋酸锂中的至少一种。碳源包括但不限于葡萄糖、蔗糖、淀粉、果糖、柠檬酸、抗坏血酸和聚乙二醇中的至少一种。
根据本申请的一个实施例，上述步骤(1)中，研磨时可以先采用直径为0.6mm-0.8mm的研磨介质研磨至物料粒径在50μm以下，再采用直径为0.1mm-0.3mm的研磨介质研磨至物料粒径在40nm-60nm。
根据本申请的一个实施例，上述步骤(2)中，喷雾干燥时的进口温度可以为150℃-200℃，根据本申请的再一个实施例，喷雾干燥时的进口温度为160℃-180℃。
上述类单晶形式的LMFP材料与团聚体形式的LMFP材料的制备方法不同之处在于：烧结时的第一恒温温度、第二恒温温度不同；气流破碎的压力不同。
其中，在制备类单晶形式的LMFP材料时，烧结过程中，第一升温段是由室温升至第一恒温温度(如450℃)，升温时间可以是2.5h-3.5h；第一恒温段的恒温时间为3.5h-5.5h；第二升温段是由第一恒温温度(如450℃)升至第二恒温温度(如750℃)，升温时间可以是2.5h-4.0h；第二恒温段的恒温时间可以是2.5h-4.5h；降温段是由第二恒温温度(如750℃)降至50℃左右，降温时间为6.5h-8.5h。同时在制备类单晶形式的LMFP材料时，在上述烧结后，可以在5MPa-8MPa的压力下进行气流破碎2h-3h；然后再进行筛选分级，得到所需粒径 的材料。
在本申请的第二个方面，本申请实施例还提供了一种正极浆料，所述正极浆料包括上述正极材料以及导电剂、粘结剂和溶剂。
根据本申请的一个实施例，上述正极材料、导电剂以及粘结剂的质量比为100∶(0.5-5)∶(0.5-5)。根据本申请的再一个实施例，所述正极浆料中的固含量为10wt％-80wt％。
其中，所述导电剂包括碳纳米管、导电炭黑以及石墨烯中的至少一种，根据本申请的再一个实施例，所述导电剂包括碳纳米管、导电炭黑以及石墨烯中的三种，三种维度的导电剂可使由该正极浆料形成的正极材料层具有较好的导电性。进一步地，碳纳米管、导电炭黑以及石墨烯的质量比可以为6：5：2。
其中，所述粘结剂为电池领域的常规选择，例如可以选自聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚乙烯醇(PVA)、丁苯橡胶(SBR)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚丙烯酸(PAA)、聚丙烯酸酯、聚烯烃、羧甲基纤维素钠(CMC)和海藻酸钠中的一种或多种。其中，PVDF可以指通过偏氟乙烯与含极性基团的烯烃类化合物共聚得到的共聚物，极性基团包括羧基、环氧基、羟基和磺酸基中的至少一种，极性基团的存在可以增强正极浆料形成的正极涂层与集流体之间的剥离强度。
其中，所述溶剂为电池领域的常规选择，例如采用N-甲基吡咯烷酮(NMP)。
根据本申请的一个实施例，所述正极浆料中还可以含有分散剂，以更好地提高正极浆料的分散性和稳定性。其中，分散剂可以为聚乙烯吡咯烷酮(PVP)等。
其中，在配制上述正极浆料时，粒度较大的第一LMFP材料、第二LMFP材料和第三LMFP材料可以直接以其粉料的形式加入，这样可以防止在混浆时发生沉降，粒度较小的第四LMFP材料和第五LMFP材料既可以以粉料的形式加入，也可以以其浆料的形式加入，其中，各自的浆料中除含有有机溶剂外，也可以含有分散剂，如PVP等。
在本申请的第三个方面，本申请实施例还提供了一种正极片，所述正极片包括集流体和设置在所述集流体上的正极材料层，所述正极材料层包括上述正极材料或采用上述的正极浆料涂覆而成。由此，含有上述正极材料的正极片具有较高的压实密度。
所述正极材料层除包括上述正极材料外，还包括导电剂和粘结剂。正极材料层可以通过将上述正极浆料在集流体上涂覆而成。
在本申请的第四个方面，本申请实施例还提供了一种电池，该电池包括上述正极片。该电池同时具有较高的容量、较低概率的溶锰、较高的循环稳定性等优异电性能。
下面结合多个实施例对本申请实施例进行进一步的说明。
正极材料的制备：
将上述第一LMFP材料至第五LMFP材料分别记作颗粒1、颗粒2、颗粒3、颗粒4、颗粒5，根据表1的粒度、颗粒数量比分别选取5种颗粒，以待后续混合，得到不同实施例对应的正极材料。其中，颗粒1至颗粒5中LMFP的化学式为LiMn 0.65Fe 0.35PO 4。
其中，各LMFP材料的粒度的测试方法为：测试设备为激光粒度仪，参考型号为马尔文2000/3000。测试方法是：将各LMFP材料在去离子水中进行分散，超声10min，颗粒折射率1.74；进行测试，得到各LMFP材料的粒径D 50。
不同粒径LMFP材料的颗粒数量测试方法为：将不同粒径的LMFP材料近似为球形，根据各颗粒的粒径D 50以及体密度(约3.6g/cm 3)，来计算单个球的质量。通过控制不同粒径LMFP材料的投料质量，来控制不同粒径LMFP材料的颗粒数量。
各LMFP材料的一次颗粒中值粒径的测试方法为：拍摄各LMFP材料分别在放大倍数为10000倍的扫描电子显微镜(SEM)照片，人为测量300个左右的一次颗粒的尺寸，并作数量分布，得出一次颗粒的中值粒径。
正极浆料的制备：将一定比例的有机溶剂NMP与粘结剂PVDF加入到搅拌机中，搅拌1h后，再向其中加入导电剂(具体是质量比为0.6∶0.5∶0.3的碳管、导电炭黑、石墨烯的混合)，搅拌30min，再将颗粒1、颗粒2、颗粒3以各自粉料的形式加入，搅拌1.5h后，再加入颗粒4、颗粒5的含PVP的NMP浆料，搅拌1.5h，过筛后，得到正极浆料。其中，正极浆料中，颗粒1-颗粒5构成的正极材料与导电剂、粘结剂PVDF、有机溶剂NMP的质量比为100∶2∶2∶30。
正极片的制备：将各实施例对应的正极浆料分别涂覆在铝箔的两侧表面上，干燥后，在铝箔上形成正极材料层，得到未压正极极片，将未压正极极片制成40*100mm的大小，然后利用大液压片机进行压片，得到压片后的正极片。可以根据正极片的面密度和压片后的厚度，计算正极片压实密度，结果汇总在表2。
电池的制备：先将各实施例对应的正极浆料制备成面密度为2.0g/dm 2、压实密度为压实为2.65g/cm 3的单面正极片，将各单面正极片制作2025的扣式电池。
先将各实施例对应的正极浆料制备成面密度为4.0g/dm 2、压实密度为2.65g/cm 3的双面正极片；再提供面密度为2.1g/dm 2、压实密度为1.60g/cm 3的双面负极片；隔膜采用PP膜，组装成053450全电池。
测试各扣式电池的比容量，测试各全电池的倍率性能及在循环过程中的负极溶Mn量，结果汇总在表2。
其中，比容量的测试方法为：将各实施例对应的扣式电池在0.1C下恒流恒压充电至电压为4.3V，截止电流是0.05C；再在0.1C下恒流恒压放电至电压为2.5V，以此进行充放电循环3次，取第三个循环后的放电容量，并除以正极片上正极材料层的敷料量，计算电池的比容量。
倍率性能的测试方法为：在25℃下，将各实施例对应的全电池先以0.2C恒流充电至4.2V，再分别在0.2C、5C不同倍率下恒流放电至2.5V，计算5C下的放电容量与0.2C下的放电容量的比值，将此比值来衡量电池的倍率性能。
负极溶Mn量的测试方法为：在45℃下，将各实施例对应的全电池以1C恒流充电至4.3V，再以1C恒流放电至2.5V，以此进行充放电循环500次后，拆解电池，测试负极极片的负极料中的Mn含量；其中Mn的含量采用电感耦合等离子体-发射光谱仪(ICP)来测量。
此外，为突出本申请技术方案的有益效果，提供了对比例1-10的正极材料，其所用各LMFP材料的参数汇总在表1，所制得的极片、电池的性能汇总在表2。
表1 各实施例及对比例的正极材料的参数
Figure PCTCN2021119309-appb-000001
Figure PCTCN2021119309-appb-000002
Figure PCTCN2021119309-appb-000003
Figure PCTCN2021119309-appb-000004
Figure PCTCN2021119309-appb-000005
表2 各实施例及对比例的正极片、电池的性能参数
Figure PCTCN2021119309-appb-000006
Figure PCTCN2021119309-appb-000007
从表1及表2可以获知，实施例1-实施例18的正极材料在各颗粒的形貌、粒度、颗粒数量比等满足本申请前述要求时，可以使正极片的压实密度在2.65g/cm 3以上，最高可达到2.9g/cm 3，电池的比容量基本没有明显降低，这样可使电池具有较高的能量密度。此外，上 述各实施例的正极材料还可使电池具有较优异的倍率性能，例如，5C与0.2C下的放电容量的比率在84％-92％，且可使电池在45℃下循环500次后的负极溶Mn量较低，不超过420ppm。
此外，从对比例1-2与实施例1-3的对比可以看出，若第一LMFP材料过小，即使在多种颗粒尺寸搭配下，正极片的压实依然会降低，同时电池负极的溶Mn含量大大增加；若第一LMFP材料过大，也会使造成正极片的压实有一定程度的降低，并显著降低电池的倍率性能。
从对比例3-6与实施例2的对比可以看出，若第二LMFP材料至第五LMFP材料与第一LMFP材料之间的粒径D50的比值a、b、c、d不在前述定义的范围内时，不能使由它们制成的正极片具有较高的压实密度。从对比例7-10与实施例2的对比可以看出，若这5种LMFP材料的颗粒数量比不在前述定义的范围时，也会显著降低正极片的压实密度。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (8)

  1. 一种正极材料，其中，所述正极材料包括第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料，所述第一磷酸锰铁锂材料、所述第二磷酸锰铁锂材料、所述第三磷酸锰铁锂材料、所述第四磷酸锰铁锂材料和所述第五磷酸锰铁锂材料的颗粒数量比为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6)；其中，所述第一磷酸锰铁锂材料为团聚体，所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料均为类单晶，所述第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶，且满足以下粒径关系：
    D 50 5<D 50 4<D 50 3<D 50 2<D 50 1，且D 50 2＝aD 50 1，D 50 3＝bD 50 1，D 50 4＝cD 50 1，D 50 5＝dD 50 1，5μm≤D 50 1≤15μm；
    其中，所述D 50 1至D 50 5依次表示所述第一磷酸锰铁锂材料至所述第五磷酸锰铁锂材料的粒径D 50的值，单位均为μm；所述a的取值范围为0.35-0.5，所述b的取值范围为0.2-0.27，所述c的取值范围为0.17-0.18，所述d的取值范围为0.15-0.16。
  2. 如权利要求1所述的正极材料，其中，所述a的取值范围为0.41-0.45；所述b的取值范围为0.21-0.23。
  3. 如权利要求1或2所述的正极材料，其中，所述a为0.41，所述b为0.23，所述c为0.18，所述d为0.16。
  4. 如权利要求1-3中任一项所述的正极材料，其中，所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比为1：1：2：8：8。
  5. 如权利要求1-4中任一项所述的正极材料，其中，所述正极材料中，所述团聚体的一次颗粒的中值粒径在100nm-500nm的范围。
  6. 如权利要求1-5中任一项所述的正极材料，其中，所述正极材料中，所述类单晶的一次颗粒粒径在0.5μm-2.5μm的范围。
  7. 一种正极片，其中，所述正极片包括集流体和设置在所述集流体上的正极材料层，所述正极材料层包括如权利要求1-6中任一项所述的正极材料。
  8. 一种电池，其中，所述电池包括如权利要求7所述的正极片。
PCT/CN2021/119309 2020-09-18 2021-09-18 正极材料、正极片及电池 Ceased WO2022057919A1 (zh)

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