WO2024124696A1 - 磷酸锰铁包覆的三元正极材料、制备方法及应用 - Google Patents

磷酸锰铁包覆的三元正极材料、制备方法及应用 Download PDF

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WO2024124696A1
WO2024124696A1 PCT/CN2023/078166 CN2023078166W WO2024124696A1 WO 2024124696 A1 WO2024124696 A1 WO 2024124696A1 CN 2023078166 W CN2023078166 W CN 2023078166W WO 2024124696 A1 WO2024124696 A1 WO 2024124696A1
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phosphate
positive electrode
electrode material
ternary positive
coating
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English (en)
French (fr)
Inventor
李爱霞
余海军
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • 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
    • H01M4/48—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 invention relates to the technical field of lithium battery materials, and in particular to a ternary positive electrode material coated with manganese iron phosphate, a preparation method and an application thereof.
  • the positive electrode material determines the performance of lithium-ion batteries and is also the component with the highest cost in lithium-ion batteries.
  • the main positive electrode materials are lithium cobalt oxide, lithium manganese oxide, nickel cobalt manganese oxide and lithium iron phosphate.
  • lithium nickel cobalt manganese oxide is an excellent positive electrode material, it has the problem of poor compatibility with electrolytes.
  • Surface coating technology is the most commonly used and effective improvement method, which can improve the stability of the surface structure of the positive electrode material and improve the cycle performance of the battery under high voltage.
  • Lithium iron manganese phosphate has a similar crystal structure to lithium iron phosphate, and is safe, has a long life, and is low in cost. Its discharge voltage is synergistic with the ternary material. By coating lithium iron manganese phosphate on the surface of the ternary material, the advantages of both can be maximized and the defects of the ternary material itself can be improved. Most of the existing coating methods are mechanical grinding, and the lithium iron manganese phosphate particles are coated on the surface of the ternary material through mechanical action.
  • CN107546379A discloses a method for preparing lithium iron manganese phosphate coated ternary materials by mechanical fusion, and nanometer-scale lithium iron manganese phosphate particles are coated on the surface of micrometer-scale ternary material particles under the action of mechanical fusion.
  • mechanical means have the problem of weak bonding between the coating layer and the core, and it is difficult to achieve tight and uniform coating.
  • the purpose of the present invention is to provide a ternary positive electrode material coated with ferromanganese phosphate, a preparation method and an application thereof.
  • the present invention is achieved in that:
  • the present invention provides a method for preparing a ternary positive electrode material coated with ferromanganese phosphate, comprising:
  • Pre-coating coating the carbon conductive mesh and the phosphorus source containing phosphate on the ternary positive electrode material to obtain a pre-coated ternary positive electrode material;
  • the synthesis of the ferromanganese phosphate coating layer uses the phosphate in the phosphorus source of the pre-coated ternary positive electrode material as the reaction site to synthesize the ferromanganese phosphate to obtain the ternary positive electrode material coated with ferromanganese phosphate.
  • the pre-coating includes phosphorus source coating and carbon conductive mesh coating
  • the carbon conductive mesh coating is to coat the carbon conductive mesh on the surface of the phosphorus source by vacuum vapor deposition coating;
  • the gases used in the vapor deposition are methane and acetylene;
  • the molar ratio of methane to acetylene is 1:1 to 5:1.
  • the temperature of the carbon conductive mesh coating step is 300 to 500° C.
  • the time is 2 to 10 hours
  • the pressure is -18 to -22 kPa.
  • the phosphorus source coating is obtained by mixing the ternary cathode material, the phosphorus source and the dispersant and then ball milling;
  • the mass ratio of the ternary positive electrode material, the phosphorus source and the dispersant is (5-15):1:(6-20);
  • the phosphorus source is at least one of ammonium polyphosphate, ammonium orthophosphate, diammonium hydrogen phosphate or diammonium dihydrogen phosphate;
  • the dispersant is one or both of ethanol and water;
  • the ball milling speed is 200-500 r/min
  • the ball-to-material ratio is (10-50):1
  • the ball milling time is 3-10 h;
  • the ball milling is performed in a planetary ball mill
  • the ball milling step is followed by drying at 60-100° C. for 0.5-3 h.
  • the pre-coating is to coat the ternary positive electrode material with a mixture of a phosphorus source and a carbon source;
  • the ternary cathode material is placed in a spray coating device, spray coated, and then sintered;
  • the coating solution used in the spray coating step is a mixed solution of organic matter and phosphoric acid and/or phosphate;
  • the mass ratio of the organic matter to phosphoric acid and/or phosphate is 1:1 to 3;
  • the mixed solution accounts for 1% to 15% of the mass of the ternary cathode material
  • the phosphate is at least one of diammonium phosphate, ammonium phosphate, and diammonium hydrogen phosphate;
  • the organic matter is at least one of sucrose, glucose and starch;
  • the spray coating spray time is 0.5 to 3 hours;
  • the sintering is carried out at 300-600° C. in an air atmosphere for 2-10 hours.
  • the synthesis of ferromanganese phosphate is to disperse the pre-coated ternary positive electrode material in a solution containing divalent manganese ions and iron ions to react to obtain a ternary positive electrode material coated with ferromanganese phosphate;
  • the concentration of manganese ions is 0.1 to 1 mol/L, and the concentration of iron ions is 0.1 to 1 mol/L;
  • the reaction time is 0.5 to 3 hours;
  • the ternary positive electrode material is lithium nickel cobalt manganese oxide.
  • the present invention provides a ternary positive electrode material coated with manganese iron phosphate, which is obtained according to the method described in any one of the aforementioned embodiments.
  • the present invention provides a method for preparing a ternary positive electrode material coated with lithium iron manganese phosphate, comprising mixing the ternary positive electrode material coated with lithium iron manganese phosphate as described in any one of the aforementioned embodiments with a lithium source and a dispersant, grinding, drying and sintering to obtain a ternary positive electrode material coated with lithium iron manganese phosphate.
  • the drying is spray drying, the spray drying air inlet temperature is 200-250°C, and the air outlet temperature is 100-120°C;
  • the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate;
  • the mixing and grinding time is 1 h to 5 h;
  • the sintering is carried out under a protective atmosphere at 300 to 800° C. for 2 to 10 hours;
  • the protective atmosphere is a reducing atmosphere or argon.
  • the present invention provides an application of the ferromanganese phosphate described in any one of the aforementioned embodiments in a battery positive electrode material.
  • Pre-coating the ternary positive electrode material can obtain a coating layer with a conductive network and rich in phosphate, which can be used as a phosphorus source for the subsequent synthesis of lithium manganese iron phosphate.
  • the conductive network plays the role of fixing the phosphorus source.
  • Phosphate as the reaction site for the synthesis of lithium iron manganese phosphate, can achieve more uniform lithium iron manganese phosphate coating.
  • the internal conductive network and the lithium iron manganese phosphate coating layer work together to isolate the contact between the ternary positive electrode material and the electrolyte, and improve the conductivity of the positive electrode material and the battery capacity.
  • Manganese and iron ions react with phosphates in the conductive network to generate ferromanganese phosphate, so that part of the ferromanganese phosphate is embedded in the conductive network, thereby improving the coating strength of the coating layer.
  • An overly dense coating layer will affect the transmission of lithium ions. After the phosphate in the phosphorus source is dissolved, the original coating layer on the surface of the ternary positive electrode material will become loose, forming a lithium ion channel and accelerating the transmission of lithium ions.
  • FIG1 is a SEM image of the sample prepared in Example 1;
  • FIG. 2 is a TEM image of the sample prepared in Example 1.
  • This embodiment provides a method for preparing a ternary positive electrode material coated with manganese iron phosphate, comprising:
  • Pre-coating coating the carbon conductive mesh and the phosphorus source containing phosphate on the ternary positive electrode material to obtain a pre-coated ternary positive electrode material;
  • the synthesis of the ferromanganese phosphate coating layer uses the phosphate in the phosphorus source of the pre-coated ternary positive electrode material as the reaction site to synthesize the ferromanganese phosphate to obtain the ternary positive electrode material coated with ferromanganese phosphate.
  • the ternary positive electrode material is pre-coated to obtain a coating layer with a conductive network and rich in phosphate.
  • Manganese, iron ions and phosphates in the conductive network react to form ferromanganese phosphate, so that part of the ferromanganese phosphate is embedded in the conductive network, and the coating strength of the coating layer is improved.
  • Phosphates are used as reaction sites for subsequent ferromanganese phosphate synthesis.
  • the phosphates can make the coating layer originally on the surface of the ternary positive electrode material loose after dissolution, forming a lithium ion channel, accelerating the transmission of lithium ions, and avoiding the overly dense coating layer that affects the transmission of lithium ions; the conductive network plays the role of fixing the phosphorus source, and at the same time, it works together with the lithium iron manganese phosphate coating layer to isolate the contact between the ternary positive electrode material and the electrolyte, and improve the conductivity and battery capacity of the positive electrode material.
  • the carbon conductive network is to adjust the coating means and parameters so that the carbon conductive layer is covered with holes as evenly as possible, which is equivalent to a "mesh", so that the phosphates in the phosphorus source can react with manganese ions and iron ions, and can also be used as a channel for phosphate dissolution or iron ions and manganese ions to enter.
  • the phosphorus source and the carbon conductive mesh can be coated separately to form two relatively independent coating layers, or they can be coated in a mixed layer in which the carbon conductive layer forms a grid-like structure and the phosphorus source is filled in the gaps of the grid.
  • the pre-coating includes phosphorus source coating and carbon conductive mesh coating
  • the carbon conductive mesh coating is to coat the carbon conductive mesh on the surface of the phosphorus source by vacuum vapor deposition coating;
  • the gases used for the vapor deposition are methane and acetylene
  • the molar ratio of methane to acetylene is 1:1 to 5:1.
  • the phosphorus source and the carbon conductive mesh are coated separately, the phosphorus source is coated in the inner layer, and the carbon conductive mesh is covered on the outer side, forming two relatively independent coating layers, and the phosphorus source can be exposed outside from the mesh holes of the carbon conductive mesh, which is convenient for the subsequent synthesis of ferromanganese phosphate.
  • the carbon conductive mesh in this embodiment is coated by vapor deposition, so that the carbon conductive mesh can be coated relatively evenly.
  • the temperature of the carbon conductive mesh coating step is 300 to 500° C.
  • the time is 2 to 10 hours
  • the pressure is -18 to -22 kPa.
  • the coating in this embodiment is a carbon conductive mesh rather than a carbon conductive layer, the uniformity of the carbon layer coverage needs to be considered.
  • the phosphorus source coating is obtained by mixing the ternary cathode material, the phosphorus source and the dispersant and then ball milling;
  • the mass ratio of the ternary cathode material, the phosphorus source and the dispersant is (5-15):1:(6-20);
  • the phosphorus source is at least one of ammonium polyphosphate, ammonium orthophosphate, diammonium hydrogen phosphate or diammonium dihydrogen phosphate;
  • the dispersant is one or both of ethanol and water
  • the ball milling speed is 200-500 r/min
  • the ball-to-material ratio is (10-50):1
  • the ball milling time is 3-10 h;
  • the ball milling is performed in a planetary ball mill
  • the ball milling step is followed by drying at 60-100° C. for 0.5-3 h.
  • the phosphorus source can be an ammonium phosphate salt, for example, ammonium polyphosphate.
  • Ammonium polyphosphate as a phosphorus source will not only dissolve phosphate, making the original coating layer on the surface of lithium nickel cobalt manganese oxide loose and forming lithium ion channels, but the decomposition of ammonium polyphosphate will also increase the number of lithium ion channels and accelerate the transmission of lithium ions.
  • the pre-coating is to coat the ternary positive electrode material with a mixture of a phosphorus source and a carbon source;
  • the ternary cathode material is placed in a spray coating device, spray coated, and then sintered;
  • the coating solution used in the spray coating step is a mixed solution of organic matter and phosphoric acid and/or phosphate
  • the mass ratio of the organic matter to phosphoric acid and/or phosphate is 1:1 to 3;
  • the mixed solution accounts for 1% to 15% of the mass of the ternary cathode material
  • the phosphate is at least one of diammonium phosphate, ammonium phosphate, and diammonium hydrogen phosphate;
  • the organic matter is at least one of sucrose, glucose, and starch;
  • the spray coating has a spraying time of 0.5 to 3 hours;
  • the sintering is carried out at 300-600° C. in an air atmosphere for 2-10 hours.
  • a mixture of a phosphorus source and a carbon source is used to coat the ternary positive electrode material to obtain a mixed layer of a carbon conductive network and a phosphorus source.
  • the carbon conductive network in this embodiment has a relatively three-dimensional structure, which enables the phosphorus source to be relatively firmly fixed in the network of the carbon conductive network.
  • the synthesis of ferromanganese phosphate is to disperse the pre-coated ternary positive electrode material in a solution containing divalent manganese ions and iron ions to react to obtain a ternary positive electrode material coated with ferromanganese phosphate;
  • the concentration of manganese ions is 0.1 to 1 mol/L, and the concentration of iron ions is 0.1 to 1 mol/L;
  • the reaction time is 0.5 to 3 hours
  • the ternary positive electrode material is lithium nickel cobalt manganese oxide.
  • evenly distributed phosphates are used as reaction sites for the synthesis of lithium iron manganese phosphate, which can achieve more uniform lithium iron manganese phosphate coating.
  • the internal conductive network and the lithium iron manganese phosphate coating layer work together to isolate the contact between lithium nickel cobalt manganese oxide and the electrolyte, and improve the conductivity of the positive electrode material and the battery capacity.
  • the present invention provides a ternary positive electrode material coated with manganese iron phosphate, which is obtained according to the method described in any one of the aforementioned embodiments.
  • the present invention provides a method for preparing a ternary positive electrode material coated with lithium iron manganese phosphate, comprising mixing the ternary positive electrode material coated with lithium iron manganese phosphate as described in any one of the aforementioned embodiments with a lithium source and a dispersant, grinding, drying and sintering to obtain a ternary positive electrode material coated with lithium iron manganese phosphate.
  • the drying is spray drying, the spray drying air inlet temperature is 200-250°C, and the air outlet temperature is 100-120°C;
  • the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate;
  • the mixing and grinding time is 1 h to 5 h;
  • the sintering is carried out under a protective atmosphere at 300-800° C. for 2-10 hours;
  • the protective atmosphere is a reducing atmosphere or argon.
  • the present invention provides an application of the ferromanganese phosphate described in any one of the aforementioned embodiments in a battery positive electrode material.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Step 1 Take 50g of lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ), add 5g of ammonium polyphosphate and 55g of dispersant, and ball mill in a planetary ball mill.
  • the dispersant is ethanol
  • the ball milling speed is 300r/min
  • the ball-to-material ratio is 15:1
  • the ball milling time is 3h.
  • Step 2 Then, a conductive carbon mesh is coated on the surface of the positive electrode material by vacuum vapor deposition coating.
  • the gas used is a mixture of methane and acetylene in a molar ratio of 2:1.
  • the coating temperature is 400°C
  • the time is 2h
  • the pressure is -20kPa.
  • the spray drying inlet temperature is 200°C and the outlet temperature is 100°C.
  • the dry powder is sintered at 700°C for 8 hours under argon gas, and the sintered product is crushed to obtain a ternary positive electrode material coated with manganese iron lithium phosphate.
  • the SEM and TEM characterization results are shown in Figures 1 and 2.
  • the obtained positive electrode material was mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 9:0.2:0.3, and N-methylpyrrolidone was used as a dispersant. After mixing evenly, it was coated on aluminum foil, dried at 80°C for 5h, and then vacuum dried at 100°C for 12h. PP was used as a separator, 1M lithium hexafluorophosphate (EC/DMC/DEC, volume ratio of 1:1:1) was used as an electrolyte, and a metal lithium sheet was used as a negative electrode.
  • the positive electrode made of the above materials was assembled into a button battery and a constant current charge and discharge test was performed at a voltage of 2.0 to 4.3V.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • step 2 specifically includes: spraying pre-coating the ternary positive electrode material with a coating solution.
  • 100g of the ternary positive electrode material is placed in a spray coating device for spray coating, and the spray time is 0.5h.
  • the coating solution is a mixed solution of 3g of diammonium phosphate and 2g of sucrose.
  • the coated ternary positive electrode material is sintered at 400°C in an air atmosphere for 3h to obtain a pre-coated ternary positive electrode material.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • This embodiment provides a battery, which differs from the preparation method of the battery provided in Example 2 in that in Example 3, the amounts of ternary positive electrode material, phosphorus source and organic matter are adjusted to obtain a pre-coated ternary positive electrode material with the same carbon and phosphoric acid content as in Example 1.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • This embodiment provides a battery, which is different from the preparation method of the battery provided in Example 1 in that in Example 4, the coating time of step 2 is 5 hours and the pressure is -20 kPa.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • This embodiment provides a battery, which is different from the preparation method of the battery provided in Example 1 in that, in Example 5, the coating time of step 2 is 10 h and the pressure is -20 kPa.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • This embodiment provides a battery, which is different from the preparation method of the battery provided in Embodiment 1 in that, in Embodiment 6, the amount of lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) added in step 1 is 25 g.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • This embodiment provides a battery, which is different from the preparation method of the battery provided in Embodiment 1 in that, in Embodiment 6, the amount of lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) added in step 1 is 75 g.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • This embodiment provides a battery, which differs from the preparation method of the battery provided in Embodiment 2 in that, in Embodiment 8, the coating solution in step 1 is a mixed solution of 2 g of diammonium dihydrogen phosphate and 2 g of sucrose.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • This embodiment provides a battery, which is different from the preparation method of the battery provided in Example 2 in that in Example 9, the coating solution in step 1 is a mixed solution of 6 g of diammonium dihydrogen phosphate and 2 g of sucrose.
  • Comparative Example 1 provides a battery, which differs from the preparation method of the battery provided in Example 1 in that, in Comparative Example 1, no ammonium polyphosphate is added in step 1, and a phosphorus source in a stoichiometric ratio of lithium manganese iron phosphate is added in step 3, and a lithium manganese iron phosphate-coated ternary positive electrode material is obtained after sintering.
  • Comparative Example 2 Compared with Example 1, the difference of Comparative Example 2 is that it does not include step 1 and step 2 in Example 1, that is, the pre-coating treatment of the ternary positive electrode material is not performed.
  • step 3 a phosphorus source is added according to the stoichiometric ratio of lithium manganese iron phosphate, and after sintering, a ternary positive electrode material coated with lithium manganese iron phosphate is obtained.
  • Step 3 Compared with Example 1, the difference of Comparative Example 3 is that Step 1 and Step 2 in Example 1 are not included, that is, the pre-coating treatment of the ternary positive electrode material is not performed.
  • Step 3 a phosphorus source in a stoichiometric ratio of lithium manganese iron phosphate and 3% sucrose by mass fraction of manganese iron phosphate are added, and a ternary positive electrode material coated with lithium manganese iron phosphate is obtained after sintering.
  • the battery performance obtained in Examples 1-9 and Comparative Examples 1-3 was tested, and the results are shown in Table 1.
  • the battery prepared by the positive electrode material coated with lithium manganese iron phosphate provided in the embodiment of the present invention has better cycle performance and more excellent cycle stability, indicating that the lithium manganese iron phosphate coating layer is tightly combined with the ternary material.
  • the carbon layer coated by vapor deposition is more stable, and has certain advantages in conductivity and gram capacity.
  • the vapor deposition time is particularly important. If the coating time is too long and the carbon coating layer is too thick, the conductivity will be enhanced but the gram capacity will be reduced.

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Abstract

本发明公开了磷酸锰铁包覆的三元正极材料、制备方法及应用，其中磷酸锰铁包覆的三元正极材料的制备方法包括：预包覆，将碳导电网和含有磷酸根的磷源包覆在三元正极材料上，得到预包覆三元正极材料；磷酸锰铁包覆层的合成，以预包覆三元正极材料磷源中的磷酸根为反应位点合成磷酸锰铁，得到磷酸锰铁包覆的三元正极材料。本申请预先包覆三元正极材料，能够获得具有导电网且富有磷酸根的包覆层，导电网起到固定磷源的作用，磷酸根作为磷酸锰铁锂合成的反应位点，能够实现更均匀的磷酸锰铁锂包覆，使得部分磷酸锰铁嵌入导电网里，提高包覆层的包覆强度，既隔绝了三元正极材料与电解液的接触，又能提高正极材料的导电性和电池容量。

Description

磷酸锰铁包覆的三元正极材料、制备方法及应用 技术领域
本发明涉及锂电材料技术领域，具体而言，涉及磷酸锰铁包覆的三元正极材料、制备方法及应用。
背景技术
随着新能源汽车的快速发展，锂离子电池产业也被推向风口。正极材料决定了锂离子电池的性能，同时也是锂离子电池中成本占比最高的组分。目前正极材料主要有钴酸锂、锰酸锂、镍钴锰酸锂和磷酸铁锂等，镍钴锰酸锂虽然是十分优秀的正极材料，但存在于电解液兼容性差的问题。表面包覆技术是最为常用和有效的改善手段，可以提高正极材料表面结构的稳定性、改善电池高电压下的循环性能。
磷酸锰铁锂与磷酸铁锂晶体结构相似，具有安全、寿命长、成本低的特点，其放电电压与三元材料具有协同性，通过将磷酸锰铁锂包覆在三元材料表面，能够最大程度发挥二者的优点，改善三元材料自身缺陷。现有的包覆手段多为机械研磨，通过机械的作用使得磷酸锰铁锂颗粒包覆在三元材料表面，如CN107546379A公开了一种机械融合制备磷酸锰铁锂包覆三元材料的方法，将纳米级磷酸锰铁锂颗粒，在机械融合的作用下，包覆在微米级的三元材料颗粒表面。但是机械的手段存在包覆层与内核结合力弱的问题，难以实现紧密而均匀的包覆。
鉴于此，特提出本发明。
发明内容
本发明的目的在于提供磷酸锰铁包覆的三元正极材料、制备方法及应用。
本发明是这样实现的：
第一方面，本发明提供一种磷酸锰铁包覆的三元正极材料的制备方法，包括：
预包覆，将碳导电网和含有磷酸根的磷源包覆在三元正极材料上，得到预包覆三元正极材料；
磷酸锰铁包覆层的合成，以预包覆三元正极材料磷源中的磷酸根为反应位点合成磷酸锰铁，得到磷酸锰铁包覆的三元正极材料。
在本申请的其他实施例中，所述预包覆包括磷源包覆和碳导电网包覆；
所述碳导电网包覆是采用真空气相沉积包覆的方式在磷源表面包覆碳导电网；
优选地，所述气相沉积采用的气体为甲烷和乙炔；
更优选地，所述甲烷和乙炔的摩尔比为1:1～5:1。
在本申请的其他实施例中，所述碳导电网包覆步骤的温度为300～500℃，时间2～10h，压力为-18～-22kPa。
在本申请的其他实施例中，所述磷源包覆是将三元正极材料、磷源和分散剂混合后进行球磨得到；
优选地，所述三元正极材料、磷源和分散剂的质量比为(5～15)：1:(6～20)；
优选地，所述磷源为聚磷酸铵、正磷酸铵、磷酸氢二铵或磷酸二氢铵中的至少一种；
优选地，所述分散剂为乙醇和水中的一种或两种；
优选地，所述球磨步骤中，球磨转速为200～500r/min，球料比为(10～50)：1，球磨时间为3～10h；
更优选地，所述球磨在行星球磨仪中进行；
优选地，所述球磨步骤后在60～100℃下干燥0.5～3h。
在本申请的其他实施例中，所述预包覆是采用磷源和碳源的混合料对三元正极材料进行包覆；
优选地，将三元正极材料置于喷雾包覆设备中，进行喷雾包覆，然后进行烧结；
优选地，所述喷雾包覆步骤中采用的包覆溶液为有机物与磷酸和/或磷酸盐的混合溶液；
优选地，所述有机物与磷酸和/或磷酸盐的质量比为1:1～3；
优选地，所述混合溶液占三元正极材料质量的1％～15％；
优选地，所述磷酸盐为磷酸二氢铵、磷酸铵、磷酸氢二铵中的至少一种；
优选地，所述有机物为蔗糖、葡萄糖、淀粉中的至少一种；
优选地，所述喷雾包覆的喷雾时间0.5～3h；
优选地，所述烧结是在300～600℃，空气气氛下烧结2～10h。
在本申请的其他实施例中，所述合成磷酸锰铁是将预包覆三元正极材料分散在含二价锰离子和铁离子的溶液中进行反应，得到磷酸锰铁包覆的三元正极材料；
优选地，所述含二价锰离子和铁离子的溶液中，锰离子的浓度为0.1～1mol/L，铁离子的浓度为0.1～1mol/L；
优选地，所述反应时间为0.5～3h；
优选地，所述三元正极材料为镍钴锰酸锂。
第二方面，本发明提供一种磷酸锰铁包覆的三元正极材料，根据前述实施方式任意一项所述方法得到。
第三方面，本发明提供一种磷酸锰铁锂包覆的三元正极材料的制备方法，将前述实施方式任意一项所述的磷酸锰铁包覆的三元正极材料与锂源和分散剂混合研磨，干燥和烧结，得到磷酸锰铁锂包覆的三元正极材料。
在本申请的其他实施例中，所述干燥为喷雾干燥，所述喷雾干燥进风温度为200～250℃，出风温度为100～120℃；
优选地，锂源为碳酸锂、氢氧化锂、草酸锂、醋酸锂中的一种或多种；
优选地，所述混合研磨时间为1h～5h；
优选地，所述烧结是保护性气氛下，在300～800℃烧结2～10h；
更优选地，所述保护性气氛为还原性气氛或氩气。
第四方面，本发明提供一种前述实施方式任意一项所述的磷酸锰铁在电池正极材料中的应用。
本发明具有以下有益效果：
1、预先包覆三元正极材料，能够获得具有导电网且富有磷酸根的包覆层，可作为后续磷酸锰铁锂合成的磷源，导电网起到固定磷源的作用。
2、磷酸根作为磷酸锰铁锂合成的反应位点，能够实现更均匀的磷酸锰铁锂包覆，内部导电网与磷酸锰铁锂包覆层共同作用，既隔绝了三元正极材料与电解液的接触，又能提高正极材料的导电性和电池容量。
3、锰、铁离子和导电网络中的磷酸根反应生成磷酸锰铁，使得部分磷酸锰铁嵌入导电网里，提高包覆层的包覆强度。
4、过于致密的包覆层会影响锂离子传输，磷源中的磷酸根溶出后可使原本在三元正极材料表面的包覆层变得疏松，形成锂离子通道，加速锂离子的传输。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为实施例1所制备样品的SEM图；
图2为实施例1所制备样品的TEM图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本实施例提供一种磷酸锰铁包覆的三元正极材料的制备方法，包括：
预包覆，将碳导电网和含有磷酸根的磷源包覆在三元正极材料上，得到预包覆三元正极材料；
磷酸锰铁包覆层的合成，以预包覆三元正极材料磷源中的磷酸根为反应位点合成磷酸锰铁，得到磷酸锰铁包覆的三元正极材料。
本实施例中，预先包覆三元正极材料，能够获得具有导电网且富有磷酸根的包覆层，锰、铁离子和导电网中的磷酸根反应生成磷酸锰铁，使得部分磷酸锰铁嵌入导电网里，提高包覆层的包覆强度，磷酸根作为后续磷酸锰铁合成的反应位点在有利于实现均匀的磷酸锰铁锂包覆的同时，磷酸根溶出后可使原本在三元正极材料表面的包覆层变得疏松，形成锂离子通道，加速锂离子的传输，避免过于致密的包覆层会影响锂离子传输；导电网起到固定磷源的作用，同时与磷酸锰铁锂包覆层共同作用，既隔绝了三元正极材料与电解液的接触，又能提高正极材料的导电性和电池容量。本实施例中，碳导电网是通过调整包覆手段和参数，使得碳导电层上尽量均匀的覆盖有孔洞，相当于“网眼”，使得磷源中的磷酸根能够与锰离子和铁离子进行反应，同时也可以作为磷酸根溶出或铁离子和锰离子进入的通道。
预包覆步骤中，磷源和碳导电网可以分别包覆，形成相对独立的两个包覆层，也可以包覆在一个混合层内，碳导电层在其中形成类似网格的结构，磷源填充在网格的间隙内。
在本申请的其他实施例中，所述预包覆包括磷源包覆和碳导电网包覆；
所述碳导电网包覆是采用真空气相沉积包覆的方式在磷源表面包覆碳导电网；
一些优选实施例中，所述气相沉积采用的气体为甲烷和乙炔；
一些更优选实施例中，所述甲烷和乙炔的摩尔比为1:1～5:1。
磷源和碳导电网分别包覆，磷源包覆在内层，碳导电网罩设在外侧，形成相对独立的两个包覆层，磷源可以从碳导电网的网孔处裸露在外面，方便后续磷酸锰铁的合成。
本实施例中的碳导电网采用气相沉积包覆的方式，可以使得碳导电网相对均匀的包覆。
在本申请的其他实施例中，所述碳导电网包覆步骤的温度为300～500℃，时间2～10h，压力为-18～-22kPa。
由于本实施例中包覆的为碳导电网而非碳导电层，所以一方面需要考虑碳层覆盖的均匀 程度，另一方面需要控制碳层的厚度，以形成“碳导电网”而“非碳导电层”，所以需要调控沉积参数，以优化碳导电网的结构。
在本申请的其他实施例中，所述磷源包覆是将三元正极材料、磷源和分散剂混合后进行球磨得到；
一些优选实施例中，所述三元正极材料、磷源和分散剂的质量比为(5～15)：1:(6～20)；
一些优选实施例中，所述磷源为聚磷酸铵、正磷酸铵、磷酸氢二铵或磷酸二氢铵中的至少一种；
一些优选实施例中，所述分散剂为乙醇和水中的一种或两种；
一些优选实施例中，所述球磨步骤中，球磨转速为200～500r/min，球料比为(10～50)：1，球磨时间为3～10h；
一些更优选实施例中，所述球磨在行星球磨仪中进行；
一些优选实施例中，所述球磨步骤后在60～100℃下干燥0.5～3h。
本实施例中，磷源可以为磷酸铵盐，例如可以为聚磷酸铵，聚磷酸铵作为磷源，不但会有磷酸根溶出，使原本在镍钴锰酸锂表面的包覆层变得疏松，形成锂离子通道，而且聚磷酸铵分解也会增加锂离子通道的数量，加速锂离子的传输。
在本申请的其他实施例中，所述预包覆是采用磷源和碳源的混合料对三元正极材料进行包覆；
一些优选实施例中，将三元正极材料置于喷雾包覆设备中，进行喷雾包覆，然后进行烧结；
一些优选实施例中，所述喷雾包覆步骤中采用的包覆溶液为有机物与磷酸和/或磷酸盐的混合溶液；
一些优选实施例中，所述有机物与磷酸和/或磷酸盐的质量比为1:1～3；
一些优选实施例中，所述混合溶液占三元正极材料质量的1％～15％；
一些优选实施例中，所述磷酸盐为磷酸二氢铵、磷酸铵、磷酸氢二铵中的至少一种；
一些优选实施例中，所述有机物为蔗糖、葡萄糖、淀粉中的至少一种；
一些优选实施例中，所述喷雾包覆的喷雾时间0.5～3h；
优选地，所述烧结是在300～600℃，空气气氛下烧结2～10h。
本实施例中采用磷源和碳源的混合料对三元正极材料进行包覆，得到碳导电网和磷源的混合层，本实施例中的碳导电网结构相对立体，能够使得磷源能够相对牢固的固定在碳导电网的网络内。
在本申请的其他实施例中，所述合成磷酸锰铁是将预包覆三元正极材料分散在含二价锰离子和铁离子的溶液中进行反应，得到磷酸锰铁包覆的三元正极材料；
一些优选实施例中，所述含二价锰离子和铁离子的溶液中，锰离子的浓度为0.1～1mol/L，铁离子的浓度为0.1～1mol/L；
一些优选实施例中，所述反应时间为0.5～3h；
一些优选实施例中，所述三元正极材料为镍钴锰酸锂。
本实施例中以均匀分布的磷酸根作为磷酸锰铁锂合成的反应位点，能够实现更均匀的磷酸锰铁锂包覆，内部导电网与磷酸锰铁锂包覆层共同作用，既隔绝了镍钴锰酸锂与电解液的接触，又能提高正极材料的导电性和电池容量。
第二方面，本发明提供一种磷酸锰铁包覆的三元正极材料，根据前述实施方式任意一项所述方法得到。
第三方面，本发明提供一种磷酸锰铁锂包覆的三元正极材料的制备方法，将前述实施方式任意一项所述的磷酸锰铁包覆的三元正极材料与锂源和分散剂混合研磨，干燥和烧结，得到磷酸锰铁锂包覆的三元正极材料。
在本申请的其他实施例中，所述干燥为喷雾干燥，所述喷雾干燥进风温度为200～250℃，出风温度为100～120℃；
一些优选实施例中，锂源为碳酸锂、氢氧化锂、草酸锂、醋酸锂中的一种或多种；
一些优选实施例中，所述混合研磨时间为1h～5h；
一些优选实施例中，所述烧结是保护性气氛下，在300～800℃烧结2～10h；
一些更优选实施例中，所述保护性气氛为还原性气氛或氩气。
第四方面，本发明提供一种前述实施方式任意一项所述的磷酸锰铁在电池正极材料中的应用。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1：
步骤1：取50g的镍钴锰酸锂(LiNi0.8Co0.1Mn0.1O2)，向其中加入5g聚磷酸铵和55g分散剂，在行星球磨仪中球磨处理。其中，分散剂为乙醇，球磨转速为300r/min，球料比为15：1，球磨时间为3h。球磨后在60℃下干燥2h得到聚磷酸铵包覆的三元正极材料。
步骤2：随后采用真空气相沉积包覆的方式在上述正极材料表面包覆导电碳网，所用气体为摩尔比2:1的甲烷与乙炔的混合气体，其中包覆温度为400℃，时间2h，压力为-20kPa。
步骤3：在磁力搅拌条件下，将预包覆三元正极材料加入500ml含二价锰、铁的溶液中， 其中，锰、铁离子浓度为0.5mol/L。反应2h，得到磷酸锰铁包覆的正极材料。利用ICP对材料中磷、铁和锰的含量进行测量，过滤后与按Fe：Mn：Li＝0.8:0.2:1的化学计量比与氢氧化锂和乙醇混合研磨3h，固液体积比为1:1。将上述混合浆料进行喷雾干燥，得到干燥粉体。喷雾干燥进风温度为200℃，出风温度为100℃。将干燥粉体置于氩气下700℃烧结8h，烧结后的产物进行粉碎，得到磷酸锰铁锂包覆的三元正极材料，其SEM和TEM表征结果如图1和图2所示。
将所得的正极材料与乙炔黑，聚偏氟乙烯按质量比9:0.2:0.3混合，以N-甲基吡咯烷酮为分散剂，混合均匀后涂覆于铝箔上，80℃鼓风干燥5h后，于100℃真空干燥12h。以PP作为隔膜，1M六氟磷酸锂(EC/DMC/DEC，体积比为1：1：1)为电解液，以金属锂片为负极，与上述材料制得的正极组装成钮扣电池并在2.0～4.3V的电压下进行恒电流充放电测试。
实施例2：
本实施例提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在实施例2中，步骤2具体包括：用包覆溶液对三元正极材料进行喷雾预包覆。将100g三元正极材料置于喷雾包覆设备中进行喷雾包覆，喷雾时间0.5h。包覆溶液为3g磷酸二氢铵和2g蔗糖的混合溶液。将包覆后的三元正极材料在400℃，空气气氛下烧结3h，得到预包覆三元正极材料。
实施例3：
本实施例提供了一种电池，其与实施例2提供的电池的制备方法的区别在于，在实施例3中，调整三元正极材料、磷源和有机物的用量，得到与实施例1中碳和磷酸含量相同的预包覆三元正极材料。
实施例4：
本实施例提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在实施例4中，步骤2的包覆时间5h，压力为-20kPa。
实施例5：
本实施例提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在实施例5中，步骤2的包覆时间10h，压力为-20kPa。
实施例6：
本实施例提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在实施例6中，步骤1镍钴锰酸锂(LiNi0.8Co0.1Mn0.1O2)的加入量为25g。
实施例7：
本实施例提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在实施例6中，步骤1镍钴锰酸锂(LiNi0.8Co0.1Mn0.1O2)的加入量为75g。
实施例8：
本实施例提供了一种电池，其与实施例2提供的电池的制备方法的区别在于，在实施例8中，步骤1包覆溶液为2g磷酸二氢氨和2g蔗糖的混合溶液。
实施例9：
本实施例提供了一种电池，其与实施例2提供的电池的制备方法的区别在于，在实施例9中，步骤1包覆溶液为6g磷酸二氢氨和2g蔗糖的混合溶液。
对比例1：
对比例1提供了一种电池，其与实施例1提供的电池的制备方法的区别在于，在对比例1中，步骤1中没有加入聚磷酸铵，步骤3中加入按磷酸锰铁锂化学计量比配比的磷源，烧结后得到磷酸锰铁锂包覆的三元正极材料。
对比例2
与实施例1相比，对比例2的区别在于未包含实施例1中的步骤1和步骤2，即未进行三元正极材料的预包覆处理。步骤3中加入按磷酸锰铁锂化学计量比配比的磷源，烧结后得到磷酸锰铁锂包覆的三元正极材料。
对比例3
与实施例1相比，对比例3的区别在于未包含实施例1中的步骤1和步骤2，即未进行三元正极材料的预包覆处理。步骤3中加入按磷酸锰铁锂化学计量比配比的磷源，以及磷酸锰铁质量分数3％的蔗糖，烧结后得到磷酸锰铁锂包覆的三元正极材料。对实施例1-9和对比例1-3得到的电池性能进行测试，结果见表1。
表1各实施例和对比例得到产品的性能对比

根据上表所显示的数据可知，相较于直接包覆磷酸锰铁锂的正极材料制备得到的电池而言，本发明的实施例所提供的包覆磷酸锰铁锂的正极材料所制备得到的电池具有更好的循环性能，具有更优异的循环稳定性，说明磷酸锰铁锂包覆层与三元材料结合紧密。
进一步地，相比于喷雾包覆，气相沉积包覆的碳层相对于喷雾包覆的碳层更稳定，导电性和克容量方面均有一定的优势；气相沉积包覆过程中，气相沉积的时间尤为重要，包覆时间过长，碳包覆层过厚，导电性增强但会降低克容量。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，包括：
    预包覆，将碳导电网和含有磷酸根的磷源包覆在三元正极材料上，得到预包覆三元正极材料；
    磷酸锰铁包覆层的合成，以预包覆三元正极材料磷源中的磷酸根为反应位点合成磷酸锰铁，得到磷酸锰铁包覆的三元正极材料。
  2. 根据权利要求1所述的磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，所述预包覆包括磷源包覆和碳导电网包覆；
    所述碳导电网包覆是采用真空气相沉积包覆的方式在磷源表面包覆碳导电网；
    优选地，所述气相沉积采用的气体为甲烷和乙炔；
    更优选地，所述甲烷和乙炔的摩尔比为1:1～5:1。
  3. 根据权利要求2所述的磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，所述碳导电网包覆步骤的温度为300～500℃，时间2～10h，压力为-18～-22kPa。
  4. 根据权利要求2所述的磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，所述磷源包覆是将三元正极材料、磷源和分散剂混合后进行球磨得到；
    优选地，所述三元正极材料、磷源和分散剂的质量比为(5～15)：1:(6～20)；
    优选地，所述磷源为聚磷酸铵、正磷酸铵、磷酸氢二铵或磷酸二氢铵中的至少一种；
    优选地，所述分散剂为乙醇和水中的一种或两种；
    优选地，所述球磨步骤中，球磨转速为200～500r/min，球料比为(10～50)：1，球磨时间为3～10h；
    更优选地，所述球磨在行星球磨仪中进行；
    优选地，所述球磨步骤后在60～100℃下干燥0.5～3h。
  5. 根据权利要求1所述的磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，所述预包覆是采用磷源和碳源的混合料对三元正极材料进行包覆；
    优选地，将三元正极材料置于喷雾包覆设备中，进行喷雾包覆，然后进行烧结；
    优选地，所述喷雾包覆步骤中采用的包覆溶液为有机物与磷酸和/或磷酸盐的混合溶液；
    优选地，所述有机物与磷酸和/或磷酸盐的质量比为1:1～3；
    优选地，所述混合溶液占三元正极材料质量的1％～15％；
    优选地，所述磷酸盐为磷酸二氢铵、磷酸铵、磷酸氢二铵中的至少一种；
    优选地，所述有机物为蔗糖、葡萄糖、淀粉中的至少一种；
    优选地，所述喷雾包覆的喷雾时间0.5～3h；
    优选地，所述烧结是在300～600℃，空气气氛下烧结2～10h。
  6. 根据权利要求1所述的磷酸锰铁包覆的三元正极材料的制备方法，其特征在于，所述合成磷酸锰铁是将预包覆三元正极材料分散在含二价锰离子和铁离子的溶液中进行反应，得到磷酸锰铁包覆的三元正极材料；
    优选地，所述含二价锰离子和铁离子的溶液中，锰离子的浓度为0.1～1mol/L，铁离子的浓度为0.1～1mol/L；
    优选地，所述反应时间为0.5～3h；
    优选地，所述三元正极材料为镍钴锰酸锂。
  7. 一种磷酸锰铁包覆的三元正极材料，其特征在于，根据权利要求1-6任意一项所述方法得到。
  8. 一种磷酸锰铁锂包覆的三元正极材料的制备方法，其特征在于，将权利要求1-7任意一项所述的磷酸锰铁包覆的三元正极材料与锂源和分散剂混合研磨，干燥和烧结，得到磷酸锰铁锂包覆的三元正极材料。
  9. 根据权利要求8所述的磷酸锰铁锂包覆的三元正极材料的制备方法，其特征在于，所述干燥为喷雾干燥，所述喷雾干燥进风温度为200～250℃，出风温度为100～120℃；
    优选地，锂源为碳酸锂、氢氧化锂、草酸锂、醋酸锂中的一种或多种；
    优选地，所述混合研磨时间为1h～5h；
    优选地，所述烧结是保护性气氛下，在300～800℃烧结2～10h；
    更优选地，所述保护性气氛为还原性气氛或氩气。
  10. 一种权利要求1-7任意一项所述的磷酸锰铁在电池正极材料中的应用。
PCT/CN2023/078166 2022-12-14 2023-02-24 磷酸锰铁包覆的三元正极材料、制备方法及应用 Ceased WO2024124696A1 (zh)

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