WO2022083089A1 - 一种正极材料、其制备方法及用途 - Google Patents

一种正极材料、其制备方法及用途 Download PDF

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Publication number
WO2022083089A1
WO2022083089A1 PCT/CN2021/089627 CN2021089627W WO2022083089A1 WO 2022083089 A1 WO2022083089 A1 WO 2022083089A1 CN 2021089627 W CN2021089627 W CN 2021089627W WO 2022083089 A1 WO2022083089 A1 WO 2022083089A1
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Prior art keywords
positive electrode
electrode material
optionally
silica sol
aluminum tripolyphosphate
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English (en)
French (fr)
Inventor
张章明
陆杭烁
曹嘉慧
张胜辉
陈德军
潘凌波
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Priority to US18/249,503 priority Critical patent/US20230395775A1/en
Priority to EP21881514.0A priority patent/EP4234497A4/en
Publication of WO2022083089A1 publication Critical patent/WO2022083089A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/40—Polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B25/418—After-treatment
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    • C01B33/00—Silicon; Compounds thereof
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    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
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    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
    • C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
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    • 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
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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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    • H01M4/366—Composites as layered products
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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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
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    • 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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    • H01M4/36—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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the application belongs to the field of lithium ion batteries, and relates to a positive electrode material, a preparation method and uses thereof.
  • Lithium-ion batteries have high energy density, high output power, green and environmentally friendly, and do not contain toxic substances such as lead, cadmium and mercury, and have broad application prospects in the field of electrical equipment.
  • Lithium-ion battery cathode material, anode material and electrolyte are the three main components of lithium-ion battery, and their performance basically determines the performance of lithium-ion battery. With the rapid development of lithium-ion battery applications, people have higher and higher requirements for lithium-ion batteries. At present, the common lithium-ion batteries cannot be used in a high temperature environment of 80 °C. How to widen the application temperature range of lithium-ion batteries has become the current lithium-ion battery. A major development hotspot for battery technology improvement.
  • the current research results show that the structure of lithium-ion battery cathode materials will continue to be destroyed during high-temperature storage, resulting in storage failure.
  • the active surface of the positive electrode material has a side reaction with the electrolyte, which will accelerate the destruction of the positive electrode material; the residual moisture in the electrolyte will accelerate the decomposition of LiPF 6 , resulting in high temperature storage failure.
  • LiPF 6 lithium salt will continue to decompose to produce HF and PF 5 .
  • the production of these two substances is unfavorable for high-temperature storage.
  • HF will corrode the positive electrode material, resulting in the destruction of the surface structure of the positive electrode material.
  • CN101308925A discloses a composite-coated positive electrode material for lithium ion batteries and a preparation method thereof, comprising: Li 0.8 ⁇ 1.2Ni 0.7 Co 0.2 Mn 0.1 O 2 , Li 0.8 ⁇ 1.2Ni 0.8 Co 0.1 Mn 0.1 O 2 or Li 0.8 ⁇ 1.2 Ni 0.9 Co 0.05 Mn 0.05 O 2 is a matrix, the crystal structure is a hexagonal system, the surface of the matrix is covered with a gradient functional material layer that accounts for 1-20% of the mass of the matrix, and the preparation method includes: powder making, raw material mixing, sintering , Surface coating, heat treatment, coating organic matter.
  • the metal oxide used is an inert material, and the ionic conductivity is not high, which reduces the capacity and rate performance of the positive electrode material, and its thermal conductivity Insufficient, the heat generated by the electrode material cannot be dissipated in time, so that the heat is continuously concentrated, and finally the temperature is raised, causing a safety hazard. And this makes it difficult to store the battery at high temperatures.
  • CN107742711A discloses a surface coating method of ternary positive electrode material.
  • the reaction of hydroxypropyl guar gum and borax can generate a gel system with three-dimensional network effect.
  • Borax is used as a cross-linking agent, and the boron cross-linking agent is cross-linked with guar gum.
  • multi-stage ionization occurs first to generate borate ion B(OH) 4 - , and then it forms a stable hydrogen bond with the cis-ortho-hydroxyl group in the guar gum molecule, and generates viscoelastic jelly through intermolecular cross-linking reaction , and then sintered to coat the boride on it, but this method has disadvantages.
  • Hydroxypropyl guar gum is an organic substance. High temperature sintering and carbonization will cause the cathode material to be reduced, resulting in the destruction of the corresponding structure.
  • CN108199047A discloses a method for coating oxide on the surface of lithium ion ternary positive electrode material.
  • the powder of lithium ion ternary positive electrode material is dispersed in a certain amount of deionized water; after the powder is uniformly dispersed, a certain amount of The organic acid or salt and the insoluble metal salt are reacted for a certain period of time; the treated ternary cathode material is then dried and heat treated at a certain temperature for a period of time to obtain an oxide-coated lithium ion ternary cathode material.
  • This document adopts the method of wet coating the precipitate, and the method of using polyacrylic acid or salt and insoluble salt. The method has limitations, and the particle size of the insoluble salt seriously affects its coating effect.
  • the purpose of this application is to provide a positive electrode material, its preparation method and use.
  • the damage of the surface structure of the positive electrode material can be effectively slowed down, thereby improving the high temperature storage performance.
  • the present application provides a preparation method of a positive electrode material, the preparation method specifically includes the following steps:
  • step (2) mixing the colloidal silica sol with the positive electrode material premix described in step (1) to form a positive electrode material mixture;
  • step (3) drying the positive electrode material mixture in step (2) to obtain a positive electrode material matrix
  • step (3) Sintering the positive electrode material matrix obtained in step (3) to obtain the positive electrode material.
  • the preparation method provided in this application can evenly coat the colloidal silica sol on the surface of the ternary positive electrode material, and the aluminum tripolyphosphate is uniformly dispersed between and on the surface of the ternary positive electrode material, which can effectively improve the lithium ion battery.
  • the storage time in the environment of 80 ⁇ 85 °C, its storage time can reach more than two months.
  • the mass fraction of the aluminum tripolyphosphate is 0.1 to 1%, such as 0.1%, 0.2%, 0.3% %, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%, etc.
  • the mixing method in step (1) is dry mixing.
  • the dry mixing is ball milling dry mixing.
  • the ball-to-material ratio in the ball mill dry mixing is 1.5:1 to 2:1, such as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1 or 2.1:1 .
  • the size of the large spherical particles in the ball mill and dry mixing is 4 mm, and the size of the small spherical particles is 2 mm.
  • the mixing time in the ball mill dry mixing is 5 to 25 minutes, such as 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes , 21min, 22min, 23min, 24min or 25min, etc.
  • the ball-milling mixing can make the ternary positive electrode material and the aluminum tripolyphosphate evenly mixed, and the agglomerated particles between the nano-aluminum tripolyphosphates can be opened under the action of the shearing force of the ball milling, and the agglomerated particles can be fully mixed with the positive electrode material. mix.
  • the preparation method of colloidal silica sol described in step (2) includes:
  • the molar ratio of added acid and/or CO2 is greater than 1.
  • the concentration of the sodium silicate solution is 5-25%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% %, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25% etc.
  • the acid includes any one or a combination of at least two of hydrochloric acid, phosphoric acid or sulfuric acid.
  • the net amount of silica in the colloidal silica sol is 0.1-1%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%, etc.
  • the colloidal silica sol acts as a binder, and the aluminum tripolyphosphate is pre-charged and bonded to the surface of the positive electrode material, wherein the aluminum tripolyphosphate is also dispersed between the ternary positive electrode materials.
  • the colloidal silica sol is an aqueous silica sol Si(OH) 4 .
  • the water-based silica sol Si(OH) 4 can form surface bonding by contacting the active oxygen on the surface of the positive electrode material, which can effectively reduce the alkali content on the surface of the ternary positive electrode material and improve the battery performance.
  • the drying in step (3) includes vacuum drying, blast drying and/or air drying, optionally vacuum drying.
  • the temperature used in the vacuum drying is 100-150°C, for example, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, and the like.
  • the vacuum drying vacuum degree is -0.05 to 0.1Mpa, such as -0.05Mpa, -0.04Mpa, -0.03Mpa, -0.02Mpa, -0.01Mpa, 0Mpa, 0.01Mpa, 0.02Mpa, 0.03Mpa, 0.04 Mpa, 0.05Mpa, 0.06Mpa, 0.07Mpa, 0.08Mpa, 0.09Mpa or 0.1Mpa, etc.
  • the vacuum drying time is 1 to 10 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.
  • the reason for choosing vacuum drying is that it can remove moisture faster, isolate CO 2 , and reduce the generation of lithium carbonate on the surface.
  • the sintering temperature in step (4) is 450-650°C, such as 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C , 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C or 650°C, etc.
  • the sintering time in step (4) is 1 to 10 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.
  • step (4) further includes: post-processing the product obtained by sintering.
  • step (2) after the colloidal silica sol is coated on the ternary positive electrode material, after a series of treatments such as drying and sintering, it is finally coated on the surface of the ternary positive electrode material in the form of silica.
  • the post-processing manner includes any one or a combination of at least two of crushing, screening or iron removal.
  • the preparation method of the positive electrode material described in this application includes:
  • the aluminum tripolyphosphate and the ternary positive electrode material are ball-milled and dry-mixed for 5-25 minutes at a ball-to-material ratio of 1.5:1 to 2:1, and the mixing time is 5-25 minutes to form a positive electrode material premix;
  • the preparation method of the silica sol includes: dissolving an aqueous sodium silicate solution, adding acid or CO 2 , forming a colloidal silica sol; the concentration of the sodium silicate solution is 5-25%; the acid includes any one or a combination of at least two of hydrochloric acid, phosphoric acid or sulfuric acid;
  • step (3) vacuum drying the positive electrode material mixture in step (2) at a temperature of 100-150° C. and a vacuum degree of -0.05-0.1 Mpa for 1-10 hours to obtain a positive electrode material matrix;
  • step (3) Sintering the cathode material matrix obtained in step (3) at a temperature of 450-650° C. for 1-10 hours, and then performing crushing, sieving or iron removal to finally obtain the cathode material.
  • the present application provides a positive electrode material prepared by the method for preparing a positive electrode material described in the first aspect.
  • the positive electrode material includes a ternary positive electrode material, aluminum tripolyphosphate and a binder.
  • the aluminum tripolyphosphate in the positive electrode material is hydrolyzed to generate triphosphate ions, which can effectively chelate with metal ions in the ternary positive electrode material, prevent metal ions from depositing on the negative electrode, protect the SEI film, and further reduce the High-temperature storage performance of lithium-ion batteries, especially in an environment of 80-85 °C.
  • the aluminum tripolyphosphate is dispersed between the ternary positive electrode materials and on the surface of the ternary positive electrode materials.
  • the aluminum tripolyphosphate is a nanoparticle.
  • the particle size of the aluminum tripolyphosphate is 2-20 nm, such as 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm , 18nm, 19nm or 20nm etc.
  • the nano-scale aluminum tripolyphosphate has a large specific surface area, so it plays the role of an inorganic binder.
  • the particle size of aluminum tripolyphosphate is too large, the specific surface area of the coating material is too small, resulting in insufficient coating of the positive electrode material, resulting in uneven coating.
  • the binder is a colloidal silica sol.
  • a silica coating layer is obtained.
  • the thickness of the silica coating layer is 1-10 nm, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, or 10 nm.
  • the present application further provides a lithium ion battery, the lithium ion battery including the positive electrode material according to the second aspect.
  • the aluminum tripolyphosphate in the positive electrode material provided by this application is hydrolyzed to generate triphosphate ions, which can effectively chelate with surface metal ions, thereby inhibiting the dissolution of metal elements, preventing the deposition of metal ions in the negative electrode, and enhancing the SEI membrane, which further improves the high-temperature storage performance of lithium-ion batteries.
  • the aqueous silica sol Si(OH) 4 in the positive electrode material provided by the present application forms surface bonding with the active oxygen on the surface of the positive electrode material, which can effectively reduce the alkali content on the surface of the ternary positive electrode material and improve the battery performance.
  • the aluminum tripolyphosphate in this application is nano-level, has a large specific surface area, can play the role of an inorganic binder, and plays a role in a cross-linked network, so that the coating material can be well covered on the active material surface, more comprehensive coverage of active sites.
  • the lithium-ion battery provided by the present application can effectively suppress the decomposition of the electrolyte and the deterioration of the positive electrode material in an environment of 80-85° C., and can be stored for more than two months.
  • FIG. 1 is a graph of voltage values stored at 80° C. for the lithium-ion batteries provided in Example 1 and Comparative Examples 1-3.
  • a positive electrode material the preparation method of which comprises the following steps:
  • the aluminum tripolyphosphate powder with a particle size of 2nm and the nickel-cobalt-manganese ternary positive electrode material (NCM811) are ball-milled and dry-mixed, wherein the total mass of the aluminum tripolyphosphate powder and the nickel-cobalt-manganese ternary positive electrode material is used. Calculated as 100%, the mass fraction of aluminum tripolyphosphate powder is 0.1%, the ball-to-material ratio in ball milling and dry mixing is 1.5:1, the large ball particles used in ball milling are 4mm, the small ball particles are 2mm, and the ball milling time is 5min.
  • the positive electrode material premix is ready for use;
  • step (3) vacuum drying the positive electrode material mixture in step (2), the drying temperature is 150°C, the vacuum drying degree is adjusted to -0.05Mpa, and dried for 1 hour to obtain a positive electrode material matrix;
  • step (3) Sintering the cathode material matrix obtained in step (3), setting the sintering temperature to 650° C., sintering for 1 hour, crushing, sieving, and iron removal, and finally obtaining a cathode material.
  • the positive electrode material prepared in this example includes a ternary positive electrode material, aluminum tripolyphosphate and a silica coating layer.
  • the aluminum tripolyphosphate is dispersed between the ternary positive electrode materials, the surface of the ternary positive electrode material and the interior of the ternary positive electrode material; the silica coating layer is coated on the ternary positive electrode material surface.
  • the mass percentage content of aluminum tripolyphosphate is 0.1%, and the thickness of the silica coating layer is 10 nm.
  • a positive electrode material the preparation method of which comprises the following steps:
  • the aluminum tripolyphosphate powder with a particle size of 20nm is mixed with the nickel-cobalt-manganese ternary positive electrode material (NCM811), wherein the total mass of the aluminum tripolyphosphate powder and the nickel-cobalt-manganese ternary positive electrode material is In terms of 100%, the mass fraction of aluminum tripolyphosphate powder is 1%, the ball-to-material ratio in the ball milling and dry mixing is 1.5:1, the large ball particles used in the ball milling are 4mm, the small ball particles are 2mm, and the ball milling time is 5min to form a positive electrode. Material premix ready for use;
  • step (2) First prepare colloidal silica sol, dissolve sodium silicate aqueous solution with a concentration of 25%, add excess CO 2 to prepare colloidal silica sol with a net amount of silicon of 1%, and dissolve the colloidal silica to oxidize
  • the silica sol is mixed with the positive electrode material in step (1) to form a positive electrode material mixture;
  • the drying temperature is 100° C. and the vacuum drying degree is adjusted to 1 Mpa, and drying is performed for 10 hours to obtain the positive electrode material matrix;
  • step (3) vacuum drying the positive electrode material mixture in step (2), the drying temperature is 135°C, the vacuum drying degree is adjusted to -0.09Mpa, and dried for 5 hours to obtain the positive electrode material matrix;
  • step (3) Sintering the cathode material matrix obtained in step (3), setting the sintering temperature to 450° C., sintering for 10 hours, crushing, sieving, and iron removal to finally obtain a cathode material.
  • the positive electrode material prepared in this example includes a ternary positive electrode material, aluminum tripolyphosphate and a silica coating layer.
  • the aluminum tripolyphosphate is dispersed between the ternary positive electrode materials, the surface of the ternary positive electrode material and the interior of the ternary positive electrode material; the silica coating layer is coated on the ternary positive electrode material surface.
  • the mass percentage content of aluminum tripolyphosphate is 1%, and the thickness of the silica coating layer is 1 nm.
  • a positive electrode material the preparation method of which comprises the following steps:
  • step (3) vacuum drying the positive electrode material mixture in step (2), the drying temperature is 135°C, the vacuum drying degree is adjusted to -0.05Mpa, and dried for 5 hours to obtain the positive electrode material matrix;
  • step (3) Sintering the cathode material matrix obtained in step (3), setting the sintering temperature to 550° C., sintering for 8 hours, crushing, sieving, and iron removal, and finally obtaining a cathode material.
  • the positive electrode material prepared in this example includes a ternary positive electrode material, aluminum tripolyphosphate and a silica coating layer.
  • the aluminum tripolyphosphate is dispersed between the ternary positive electrode materials, the surface of the ternary positive electrode material and the interior of the ternary positive electrode material; the silica coating layer is coated on the ternary positive electrode material surface.
  • the mass percentage content of aluminum tripolyphosphate is 0.4%, and the thickness of the silica coating layer is 5 nm.
  • a positive electrode material the preparation method of which comprises the following steps:
  • the aluminum tripolyphosphate powder with a particle size of 2nm is mixed with the nickel-cobalt-manganese ternary positive electrode material (NCM811), wherein the total mass of the aluminum tripolyphosphate powder and the nickel-cobalt-manganese ternary positive electrode material is In terms of 100%, the mass fraction of aluminum tripolyphosphate powder is 0.1%, the ball-to-material ratio in ball milling and dry mixing is 1.5:1, the large ball particles used in ball milling are 4mm, the small ball particles are 2mm, and the ball milling time is 5min to form a positive electrode. Material premix ready for use;
  • step (3) vacuum drying the positive electrode material mixture in step (2), the drying temperature is 135°C, the vacuum drying degree is adjusted to -0.05Mpa, and dried for 5 hours to obtain the positive electrode material matrix;
  • step (3) Sintering the cathode material matrix obtained in step (3), setting the sintering temperature to 550° C., sintering for 8 hours, crushing, sieving, and iron removal, and finally obtaining a cathode material.
  • the positive electrode material prepared in this example includes a ternary positive electrode material, aluminum tripolyphosphate and a silica coating layer.
  • the aluminum tripolyphosphate is dispersed between the ternary positive electrode materials, the surface of the ternary positive electrode material and the interior of the ternary positive electrode material; the silica coating layer is coated on the ternary positive electrode material surface.
  • the mass percentage content of aluminum tripolyphosphate is 0.5%, and the thickness of the silica coating layer is 4 nm.
  • Example 1 Compared with Example 1, other preparation steps are the same as Example 1 except that step (1) is adjusted as follows.
  • the aluminum tripolyphosphate powder with a particle size of 20nm is mixed with the nickel-cobalt-manganese ternary positive electrode material (NCM811), wherein the total mass of the aluminum tripolyphosphate powder and the nickel-cobalt-manganese ternary positive electrode material is In terms of 100%, the mass fraction of aluminum tripolyphosphate powder is 1%, the ball-to-material ratio in ball milling and dry mixing is 1.5:1, the large ball particles used in ball milling are 4mm, the small ball particles are 2mm, and the ball milling time is 25min to form a positive electrode. Material premix ready for use;
  • Example 1 Compared with Example 1, other preparation steps are the same as Example 1 except that step (1) is adjusted as follows.
  • Example 1 Compared with Example 1, other preparation steps are the same as those in Example 1, except that the preparation of the colloidal silica sol in step (2) is adjusted as follows.
  • Example 1 Compared with Example 1, other preparation steps are the same as those in Example 1, except that the preparation of the colloidal silica sol in step (2) is adjusted as follows.
  • the nickel-cobalt-manganese ternary positive electrode material is not subjected to any coating treatment, no ball milling is mixed with aluminum tripolyphosphate powder, and no silica sol is added for mixing treatment.
  • Example 1 Compared with Example 1, other preparation steps are the same as Example 1 except that step (1) is adjusted as follows.
  • the positive electrode material includes a ternary positive electrode material and a colloidal silica sol, and the colloidal silica sol is coated on the surface of the ternary positive electrode material. Except for this, this comparative example is consistent with Example 1.
  • this comparative example is the same as Example 1 except that step (2) is omitted.
  • the aluminum tripolyphosphate powder with a particle size of 10nm is mixed with the nickel-cobalt-manganese ternary positive electrode material (NCM811), and the ball-to-material ratio in the dry-mixing ball milling is 1.5:1, and the large ball particles used in the ball milling are 4 mm, The pellet size is 2 mm, and the ball milling time is 5 min to form a positive electrode material premix for use.
  • NCM811 nickel-cobalt-manganese ternary positive electrode material
  • the positive electrode material includes a mixture of ternary positive electrode material and aluminum tripolyphosphate phosphate powder, but no colloidal silica sol is coated on the surface of the ternary positive electrode material.
  • this comparative example is the same as that of Example 1. be consistent.
  • Table 1 shows that the batteries of different embodiments and comparative examples are stored in a high temperature box at 80°C, and the voltage value (V) is calculated every 200h.
  • the voltage value of the prepared battery decayed rapidly after 40 days; in Comparative Example 3, the battery was prepared by mixing nano-scale aluminum tripolyphosphate, but without colloidal silica sol as the positive electrode material of the binder. Its voltage value began to decay rapidly after 45 days. It can be seen that the ternary positive electrode material in this application is coated with aluminum tripolyphosphate, and the colloidal silica sol is used as the binder, which can achieve the technical effect of improving the high temperature resistance of the battery, especially the long-term storage at 80-85 °C.

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Abstract

提供了一种正极材料、其制备方法及用途。正极材料包括三元正极材料、三聚磷酸铝和粘结剂。其制备方法包括：(1)将三聚磷酸铝和三元正极材料混合反应，形成正极材料预混合物；(2)将胶体式二氧化硅溶胶与正极材料预混合物混合，形成正极材料混合物；(3)将正极材料混合物干燥，得到正极材料基体；(4)将所述正极材料基体烧结，得到正极材料。其可用作锂离子电池的正极材料。

Description

一种正极材料、其制备方法及用途 技术领域
本申请属于锂离子电池领域，涉及一种正极材料、其制备方法及用途。
背景技术
锂离子电池能量密度高、输出功率大，绿色环保对环境友好，不含有铅、镉汞等有毒物质，在电器设备领域有着广泛的应用前景。锂离子电池正极材料、负极材料和电解液作为锂离子电池的三个主要组成部分，其性能基本决定了锂离子电池的性能。随着锂离子电池应用的快速发展，人们对锂离子电池的要求越来越高，目前普遍的锂离子电池，不能在高温80℃环境下应用,如何拓宽锂离子的应用温度范围成为当下锂离子电池技术提升的一大开发热点。
目前的研究结果表明，锂离子电池正极材料在高温存储当中,结构会不断破坏,导致存储失效。同时正极材料的活性表面与电解液产生副反应，会加速正极材料破坏；电解液当中残留的水分会加速LiPF 6的分解，导致高温存储失效。
同时，锂离子电池在高温存储当中，LiPF 6锂盐会不断的分解，产生HF与PF 5，这两种物质的产生对于高温存储不利，其中HF会腐蚀正极材料，导致正极材料表面结构破坏。
CN101308925A公开了一种锂离子电池复合包覆正极材料及其制备方法，包括以Li 0.8～1.2Ni 0.7Co 0.2Mn 0.1O 2、Li 0.8～1.2Ni 0.8Co 0.1Mn 0.1O 2或Li 0.8～1.2Ni 0.9Co 0.05Mn 0.05O 2为基体，晶体结构为六方晶系，基体表面包覆有占基体质量比1～20％的梯度功能材料层，其制备方法包括：粉体制作、原料混合、烧结、表面包覆、热处理、包覆有机物。隔绝高镍三元材料和电解液的接触，提高电池的循环稳定性，但所使用的金属氧化物是惰性材料，离子电导率不高， 使正极材料的容量和倍率性能下降，而且其导热能力不足，不能及时将电极材料产生的热散发出去，使热量不断集中，最后使温度升高，造成安全隐患。而且这样使得电池在高温下不易存储。
CN107742711A公开了一种三元正极材料的表面包覆方法,利用羟丙基胍胶与硼砂反应可生成三维网状效果的凝胶体系，硼砂作为交联剂，硼交联剂与胍胶交联时，首先发生多级电离，产生硼酸盐离子B(OH) 4 -，再与胍胶分子中的顺式邻位羟基形成稳定的氢键，通过分子间的交联反应生成粘弹性冻胶,然后经过烧结,将硼化物包覆在其上面,但该方法存在缺点，羟丙基胍胶是一种有机物，高温烧结碳化，会导致正极材料被还原，导致对应结构破坏。
CN108199047A公开了一种在锂离子三元正极材料表面包覆氧化物的方法，首先将锂离子三元正极材料粉末分散于一定量的去离子水中；待粉末分散均匀后，向其中加入一定量的有机酸或盐和不溶性金属盐，反应一定的时间；再将处理后的三元正极材料烘干，在一定的温度下热处理一段时间，得到氧化物包覆的锂离子三元正极材料。该文献采用湿法包覆沉淀物的方法，采用聚丙烯酸或盐与不溶性盐的方法，采用该方法具有局限性，不溶性盐的粒度严重影响其包覆效果。
目前普通的锂离子电池普遍不能耐高温存储，在80℃以上的环境当中，由于电解液的分解或者正极材料的衰退等原因，基本上就不能使用。
如何解决锂离子电池能耐高温存储，尤其是在80～85℃的环境中能够存储两个月以上，是目前急需解决的技术问题。
发明内容
本申请的目的在于提供一种正极材料，其制备方法及用途。本申请通过将 三元正极材料与三聚磷酸铝进行混合，能够有效减缓正极材料表面结构的破坏，从而改善高温存储性能。
为达到此发明目的，本申请采用以下技术方案：
第一方面，本申请提供一种正极材料的制备方法，所述制备方法具体包括以下步骤：
(1)将三聚磷酸铝和三元正极材料进行混合，形成正极材料预混合物；
(2)将胶体式二氧化硅溶胶与步骤(1)所述正极材料预混合物混合，形成正极材料混合物；
(3)将步骤(2)中的所述正极材料混合物进行干燥，得到正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体进行烧结，得到所述正极材料。
本申请所提供的制备方法，可以将胶体式二氧化硅溶胶均匀包覆于三元正极材料表面，三聚磷酸铝均匀地分散于三元正极材料之间以及表面，可以有效的提高锂离子电池在80～85℃的环境中的存储时间，其存储时间可达两个月以上。
可选地，步骤(1)中以三聚磷酸铝与三元正极材料的总质量为100％计，所述三聚磷酸铝的质量分数为0.1～1％，例如0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％或1.0％等。
本申请中，三聚磷酸铝的添加量超过1％会导致正极材料克容量降低；低于0.1％会导致表面包覆不均匀。
可选地，步骤(1)中所述混合的方法为干法混合。
可选地，所述干法混合为球磨干混。
可选地，所述球磨干混中球料比为1.5:1～2:1，例如1.5:1、1.6:1、1.7:1、1.8:1、1.9:1、2.0:1或2.1:1。
可选地，所述球磨干混中大球颗粒为4mm，小球颗粒为2mm。
可选地，所述球磨干混中混料时间为5～25min，例如5min、6min、7min、8min、9min、10min、11min、12min、13min、14min、15min、16min、17min、18min、19min、20min、21min、22min、23min、24min或25min等。
本申请中，球磨混合可以使三元正极材料与三聚磷酸铝混合均匀，纳米三聚磷酸铝之间的团聚颗粒在球磨剪切力的作用下，团聚颗粒可以打开，与正极材料进行充分的混合。
可选地，步骤(2)中所述胶体式二氧化硅溶胶的制备方法包括：
溶解硅酸钠水溶液，加酸和/或CO 2，形成硅溶胶。
可选地，加入的酸和/或CO 2的摩尔比大于1。
可选地，所述硅酸钠溶液的浓度为5～25％，例如5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％或25％等。
可选地，所述酸包括盐酸、磷酸或硫酸中的任意一种或至少两种的组合。
可选地，所述胶体式二氧化硅溶胶中硅净量为0.1～1％，例如0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％或1.0％等。
本申请中，胶体式二氧化硅溶胶起到粘合剂的作用，将三聚磷酸铝预充粘合于正极材料表面，其中，所述三聚磷酸铝还分散于三元正极材料之间。
可选地，所述胶体式二氧化硅溶胶为水性硅溶胶Si(OH) 4。
本申请中，水性硅溶胶Si(OH) 4通过与正极材料表面的活性氧接触，可以形 成表面键合作用，能有效降低三元正极材料表面碱含量，提高电池性能。
可选地，步骤(3)中所述干燥包括真空干燥、鼓风干燥和/或风干干燥，可选为真空干燥。
可选地，所述真空干燥所用温度为100～150℃，例如100℃、110℃、120℃、130℃、140℃或150℃等。
可选地，所述真空干燥真空度为-0.05至0.1Mpa，例如-0.05Mpa、-0.04Mpa、-0.03Mpa、-0.02Mpa、-0.01Mpa、0Mpa、0.01Mpa、0.02Mpa、0.03Mpa、0.04Mpa、0.05Mpa、0.06Mpa、0.07Mpa、0.08Mpa、0.09Mpa或0.1Mpa等。
可选地，所述真空干燥时间为1～10h，例如1h、2h、3h、4h、5h、6h、7h、8h、9h或10h等。
本申请中，选用真空干燥的原因为，可以更快的去除水分，隔绝CO 2，减少表面碳酸锂的生成。
可选地，步骤(4)中所述烧结的温度为450～650℃，例如450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃或650℃等。
可选地，步骤(4)中所述烧结时间为1～10h，例如1h、2h、3h、4h、5h、6h、7h、8h、9h或10h等。
可选地，步骤(4)还包括：对所述烧结得到的产品进行后处理。
本申请中，经由步骤(2)，将胶体式二氧化硅溶胶包覆于三元正极材料后，经过一系列干燥烧结等处理，最终以二氧化硅的形式包覆于三元正极材料表面。
可选地，所述后处理的方式包括破碎、筛分或除铁中的任意一种或至少两种的组合。
作为可选的技术方案，本申请所述正极材料的制备方法包括：
(1)将三聚磷酸铝和三元正极材料以1.5:1～2:1的球料比进行球磨干混5～25min，混料时间为5-25min，形成正极材料预混合物；
(2)将胶体式二氧化硅溶胶与步骤(1)所述正极材料预混合物混合，形成正极材料混合物，其中所述硅溶胶的制备方法包括：溶解硅酸钠水溶液，加入酸或CO 2，形成胶体式二氧化硅溶胶；所述硅酸钠溶液的浓度为5～25％；所述酸包括盐酸、磷酸或硫酸中的任意一种或至少两种的组合；
(3)将步骤(2)中的所述正极材料混合物在100～150℃的温度下、-0.05至0.1Mpa的真空度下进行真空干燥1～10h，得到正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体在450～650℃的温度下烧结1～10h，再进行破碎、筛分或除铁，最终获得所述正极材料。
第二方面，本申请提供一种由第一方面所述的正极材料的制备方法制得的正极材料。
可选地，所述正极材料包括三元正极材料、三聚磷酸铝和粘结剂。
本申请中，所述正极材料中三聚磷酸铝水解产生三磷酸根离子，可以有效与三元正极材料中的金属离子进行螯合，防止金属离子在负极沉积，保护了SEI膜，进而降低了锂离子电池的高温存储性能，尤其是在80～85℃的环境中。
可选地，所述三聚磷酸铝分散于三元正极材料之间以及三元正极材料表面。
可选地，所述三聚磷酸铝为纳米颗粒。
可选地，所述三聚磷酸铝的颗粒尺寸为2-20nm，例如2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm或20nm等。
本申请中，纳米级的三聚磷酸铝，具有较大的比表面积，因此起到了无机粘结剂的作用，其交联网状作用使得包覆物质能够很好的覆盖在活性物质表面，可以全面的覆盖活性位点；但是如果三聚磷酸铝颗粒尺寸过大会因为包覆物质的比表面积太小，导致正极材料被包覆不足，导致包覆不均匀。
可选地，所述粘结剂为胶体式的二氧化硅溶胶。
可选地，所述胶体式的二氧化硅溶胶干燥后，得到的为二氧化硅包覆层。
可选地，所述二氧化硅包覆层的厚度为1～10nm，例如1nm、2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm或10nm等。
第三方面，本申请还提供一种锂离子电池，所述锂离子电池包括如第二方面所述的正极材料。
相对于现有技术，本申请具有以下有益效果：
(1)本申请所提供的正极材料中的三聚磷酸铝水解产生三磷酸根离子，可以有效地与表面金属离子螯合，从而抑制金属元素溶出，防止金属离子在负极的沉积，增强了SEI膜，进一步提高了锂离子电池的高温存储性能。
(2)本申请提供的正极材料中的水性硅溶胶Si(OH) 4，通过与正极材料表面的活性氧，形成表面键合作用，能有效降低三元正极材料表面碱含量，提高电池性能。
(3)本申请中的三聚磷酸铝为纳米级别的，具有较大的比表面积，可以起到无机粘结剂的作用，起交联网状作用能够使得包覆物质很好的覆盖在活性物质表面，更加全面的覆盖活性位点。
(4)本申请所提供的锂离子电池可在80～85℃的环境当中，有效抑制电解液的分解以及正极材料的衰退，并且可以存储两个月以上。
附图说明
图1是实施例1和对比例1-3所提供的锂离子电池在80℃下存储的电压值曲线图。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1：
一种正极材料，其制备方法包括以下步骤：
(1)将颗粒尺寸为2nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行球磨干混，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为0.1％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用；
(2)先制备胶体状二氧化硅溶胶，溶解浓度为5％的硅酸钠水溶液，加入过量的CO 2，制成硅净量为0.1％的胶体式二氧化硅溶胶，将胶体式二氧化硅溶胶与步骤(1)正极材料混合，形成正极材料混合物；
(3)将步骤(2)中的所述正极材料混合物进行真空干燥，干燥温度为150℃，真空干燥度调整为-0.05Mpa，干燥1h，得到正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体进行烧结，烧结温度设置为650℃，烧结1h，进行破碎，筛分，除铁，最终获得正极材料。
本实施例制得的正极材料包括三元正极材料、三聚磷酸铝和二氧化硅包覆层。所述三聚磷酸铝分散于所述三元正极材料之间、所述三元正极材料表面与 所述三元正极材料的内部；所述二氧化硅包覆层包覆于所述三元正极材料表面。其中，三聚磷酸铝的质量百分含量为0.1％，二氧化硅包覆层厚度为10nm。将本实施例中得到的正极材料，与导电剂SP、5130PVDF胶，按照96.9％:2％:1.1％比例进行制浆，打浆制成极片，组装成18650锂离子电池，充电至于4.1V，置于80℃高温箱中存储1500小时，每隔200小时测定电压情况。
实施例2
一种正极材料，其制备方法包括以下步骤：
(1)将颗粒尺寸为20nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为1％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用；
(2)先制备胶体式二氧化硅溶胶，溶解浓度为25％的硅酸钠水溶液，加入过量的CO 2，制成硅净量为1％的胶体式二氧化硅溶胶，将胶体式二氧化硅溶胶与步骤(1)正极材料混合，形成正极材料混合物；干燥温度为100℃真空干燥度调整为1Mpa，干燥10h，得到所述正极材料基体；
(3)将步骤(2)中的所述正极材料混合物进行真空干燥，干燥温度为135℃，真空干燥度调整为-0.09Mpa，干燥5h，得到所述正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体，进行烧结，烧结温度设置为450℃，烧结10h，进行破碎，筛分，除铁，最终获得正极材料。
本实施例制得的正极材料包括三元正极材料、三聚磷酸铝和二氧化硅包覆层。所述三聚磷酸铝分散于所述三元正极材料之间、所述三元正极材料表面与 所述三元正极材料的内部；所述二氧化硅包覆层包覆于所述三元正极材料表面。其中，三聚磷酸铝的质量百分含量为1％，二氧化硅包覆层厚度为1nm。
本实施例中电池制备以及测试同实施例1保持一致。
实施例3
一种正极材料，其制备方法包括以下步骤：
(1)将颗粒尺寸为10nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为0.5％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用；
(2)先制备胶体式二氧化硅溶胶，溶解浓度为10％的硅酸钠水溶液，加入过量的盐酸，制成硅净量为0.5％的胶体式二氧化硅溶胶，将胶体式二氧化硅溶胶与步骤(1)正极材料预混合物混合，形成正极材料混合物；
(3)将步骤(2)中的所述正极材料混合物进行真空干燥，干燥温度为135℃，真空干燥度调整为-0.05Mpa，干燥5h，得到所述正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体，进行烧结，烧结温度设置为550℃，烧结8h，进行破碎，筛分，除铁，最终获得正极材料。
本实施例制得的正极材料包括三元正极材料、三聚磷酸铝和二氧化硅包覆层。所述三聚磷酸铝分散于所述三元正极材料之间、所述三元正极材料表面与所述三元正极材料的内部；所述二氧化硅包覆层包覆于所述三元正极材料表面。其中，三聚磷酸铝的质量百分含量为0.4％，二氧化硅包覆层厚度为5nm。
本实施例中电池制备以及测试同实施例1保持一致。
实施例4
一种正极材料，其制备方法包括以下步骤：
(1)将颗粒尺寸为2nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为0.1％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用；
(2)先制备胶体式二氧化硅溶胶，溶解浓度为10％的硅酸钠水溶液，加入过量的磷酸，制成硅净量为0.5％的胶体式二氧化硅溶胶，将胶体式二氧化硅溶胶与步骤(1)正极材料预混合物混合，形成正极材料混合物；
(3)将步骤(2)中的所述正极材料混合物进行真空干燥，干燥温度为135℃，真空干燥度调整为-0.05Mpa，干燥5h，得到所述正极材料基体；
(4)将步骤(3)中得到的所述正极材料基体，进行烧结，烧结温度设置为550℃，烧结8h，进行破碎，筛分，除铁，最终获得正极材料。
本实施例制得的正极材料包括三元正极材料、三聚磷酸铝和二氧化硅包覆层。所述三聚磷酸铝分散于所述三元正极材料之间、所述三元正极材料表面与所述三元正极材料的内部；所述二氧化硅包覆层包覆于所述三元正极材料表面。其中，三聚磷酸铝的质量百分含量为0.5％，二氧化硅包覆层厚度为4nm。
本实施例中电池制备以及测试同实施例1保持一致。
实施例5
与实施例1相比，除将步骤(1)调整如下外，其它制备步骤与实施例1相同。
(1)将颗粒尺寸为20nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为1％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为25min，形成正极材料预混合物待用；
实施例6
与实施例1相比，除将步骤(1)调整如下外，其它制备步骤与实施例1相同。
(1)将颗粒尺寸为10nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，其中以三聚磷酸铝粉料与镍钴锰三元正极材料的总质量为100％计，三聚磷酸铝粉料的质量分数为0.5％，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为15min，形成正极材料预混合物待用；
实施例7
与实施例1相比，除将步骤(2)中胶体式二氧化硅溶胶的制备调整如下外，其它制备步骤与实施例1相同。
(2)先制备胶体式二氧化硅溶胶，溶解浓度为25％的硅酸钠水溶液，加入过量的CO 2，制成硅净量为1％的胶体式二氧化硅溶胶。
实施例8
与实施例1相比，除将步骤(2)中胶体式二氧化硅溶胶的制备调整如下外，其它制备步骤与实施例1相同。
(2)先制备胶体式二氧化硅溶胶，溶解浓度为10％的硅酸钠水溶液，加入 过量的盐酸，制成硅净量为0.5％的胶体式二氧化硅溶胶。
对比例1
本对比例中不对镍钴锰三元正极材料进行任何包覆处理，无球磨混合三聚磷酸铝粉料处理，也没有加入硅溶胶进行混合处理。
对比例2
与实施例1相比，除将步骤(1)调整如下外，其它制备步骤与实施例1相同。
(1)将镍钴锰三元正极材料进行球磨，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用。
本对比例中正极材料包括三元正极材料与胶体式二氧化硅溶胶，所述胶体式二氧化硅溶胶包覆于三元正极材料表面，除此以外，本对比例与实施例1保持一致。
对比例3
与实施例1相比，本对比例除将步骤(2)省略外，其它制备步骤与实施例1相同。
(1)将颗粒尺寸为10nm的三聚磷酸铝粉料与镍钴锰三元正极材料(NCM811)进行混合反应，球磨干混中球料比为1.5:1，球磨所用大球颗粒为4mm，小球颗粒为2mm，球磨时间为5min，形成正极材料预混合物待用。
本对比例中正极材料包括三元正极材料与三聚磷酸磷酸铝粉末混合，但无所述胶体式二氧化硅溶胶包覆于三元正极材料表面，除此以外，本对比例与实 施例1保持一致。
从图1可以看出，实施例1所提供的锂离子电池在80℃下的存储时间明显增加，且衰减更加缓慢。而对比例1-3中的锂离子电池不进行任何包覆或者只是包覆三聚磷酸铝或二氧化硅，在80℃下的存储时间远远低于实施例1所提供的锂离子电池。
表1为不同实施例与对比例的电池在80℃高温箱中存储，每隔200h电压值(V)据值。
表1
Figure PCTCN2021089627-appb-000001
Figure PCTCN2021089627-appb-000002
从实施例1-8的电压测试结果可知，在80℃高温箱中，其电压衰减较对比例1-3更加缓慢，可以在80℃高温环境下存储两个月以上；而对比例1中，未进行包覆的镍钴锰正极材料制成的电池其电压值在30天后就开始迅速衰减，严重影响了电池性能；对比例2中，未混合纳米级别三聚磷酸铝的镍钴锰正极材料制成的电池，其电压值在40天后迅速衰减；对比例3中，混合纳米级别的三聚磷酸铝，但无胶体式二氧化硅溶胶作为粘结剂的正极材料，制备而成的电池，其电压值在45天后开始迅速衰减。由此可知，本申请中三元正极材料包覆三聚磷酸铝，以胶体式二氧化硅溶胶作为粘结剂，可以达到提高电池耐高温尤其是80-85℃较长时间存储的技术效果。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此。

Claims (12)

  1. 一种正极材料的制备方法，其中，所述制备方法包括以下步骤：
    (1)将三聚磷酸铝和三元正极材料进行混合，形成正极材料预混合物；
    (2)将胶体式二氧化硅溶胶与步骤(1)所述正极材料预混合物混合，形成正极材料混合物；
    (3)将步骤(2)中的所述正极材料混合物进行干燥，得到正极材料基体；
    (4)将步骤(3)中得到的所述正极材料基体进行烧结，得到所述正极材料。
  2. 根据权利要求1所述的正极材料的制备方法，其中，步骤(1)中以三聚磷酸铝与三元正极材料的总质量为100％计，所述三聚磷酸铝的质量分数为0.1～1％。
  3. 根据权利要求1或2所述的正极材料的制备方法，其中步骤(1)所述混合的方法为干法混合。
  4. 根据权利要求3所述的正极材料的制备方法，其中，所述干法混合为球磨干混；
    可选地，所述球磨干混中球料比为1.5:1～2:1；
    可选地，所述球磨干混中混料时间为5～25min。
  5. 根据权利要求1-4任一项所述的正极材料的制备方法，其中，步骤(2)中所述胶体式二氧化硅溶胶的制备方法包括：
    溶解硅酸钠水溶液，加入CO 2和/或酸，形成胶体式二氧化硅溶胶；
    可选地，所述硅酸钠水溶液的浓度为5～25％；
    可选地，所述酸包括盐酸、磷酸或硫酸中的任意一种或至少两种的组合；
    可选地，所述胶体式二氧化硅溶胶中硅净量为0.1～1％。
  6. 根据权利要求1-5任一项所述的正极材料的制备方法，其中，步骤(3)中所述干燥包括真空干燥、鼓风干燥和/或风干干燥，可选为真空干燥；
    可选地，所述真空干燥所用温度为100～150℃；
    可选地，所述真空干燥的真空度为-0.05至0.1Mpa；
    可选地，所述真空干燥的时间为1～10h。
  7. 根据权利要求1-6任一项所述的正极材料的制备方法，其中，步骤(4)中所述烧结的温度为450～650℃；
    可选地，步骤(4)中所述烧结的时间为1～10h；
    可选地，步骤(4)还包括：对所述烧结得到的产品进行后处理；
    可选地，所述后处理的方式包括破碎、筛分或除铁中的任意一种或至少两种的组合。
  8. 根据权利要求1-7任一项所述的正极材料的制备方法，其中，所述制备方法包括：
    (1)将三聚磷酸铝和三元正极材料以1.5:1～2:1的球料比进行球磨干混5～25min，混料时间为5-25min，形成正极材料预混合物待用；
    (2)将胶体式二氧化硅溶胶与步骤(1)所述正极材料预混合物混合，形成正极材料混合物，其中所述胶体式二氧化硅溶胶的制备方法包括：溶解硅酸钠水溶液，加入酸或CO 2，形成胶体式二氧化硅溶胶；其中，所述硅酸钠溶液的浓度为5～25％；所述酸包括盐酸、磷酸或硫酸中的任意一种或至少两种的组合；
    (3)将步骤(2)中的所述正极材料混合物在100～150℃的温度下、-0.05至0.1Mpa的真空度下进行真空干燥1～10h，得到正极材料基体；
    (4)将步骤(3)中得到的所述正极材料基体在450～650℃的温度下烧结1～10h，再进行破碎、筛分或除铁，最终获得所述正极材料。
  9. 一种正极材料，其中，所述正极材料由权利要求1-8所述的正极材料的制备方法制得。
  10. 根据权利要求9所述的正极材料，其中，所述正极材料包括三元正极材料、三聚磷酸铝和粘结剂；
    可选地，所述三聚磷酸铝分散于三元正极材料之间以及三元正极材料表面。
  11. 根据权利要求9或10所述的正极材料，其中，所述三聚磷酸铝为纳米颗粒；
    可选地，所述三聚磷酸铝的颗粒平均尺寸为2～20nm；
    可选地，所述粘结剂为胶体式的二氧化硅溶胶；
    可选地，所述胶体式的二氧化硅溶胶干燥后，得到的为包覆于三元正极材料表面的二氧化硅包覆层；
    可选地，所述二氧化硅包覆层的厚度为1～10nm。
  12. 一种锂离子电池，其中，所述锂离子电池包括如权利要求9-11任一项所述的正极材料。
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