CN111952560A - Composite cathode material, preparation method thereof and lithium ion battery - Google Patents

Composite cathode material, preparation method thereof and lithium ion battery Download PDF

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Publication number
CN111952560A
CN111952560A CN202010749149.5A CN202010749149A CN111952560A CN 111952560 A CN111952560 A CN 111952560A CN 202010749149 A CN202010749149 A CN 202010749149A CN 111952560 A CN111952560 A CN 111952560A
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rock salt
solid electrolyte
salt structure
oxyfluoride
anode material
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谭强强
周运成
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—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

Abstract

The invention provides a composite cathode material, a preparation method thereof and a lithium ion battery. The composite anode material comprises a core and a coating layer coated on the surface of the core, wherein the core comprises an unordered rock salt structure oxyfluoride anode material, and the coating layer comprises a solid electrolyte. The preparation method comprises the following steps: 1) mixing and ball-milling raw materials for preparing the unordered rock salt structure oxyfluoride anode material to obtain the unordered rock salt structure oxyfluoride anode material; 2) mixing raw materials for preparing the solid electrolyte with a complexing agent in a solvent, mixing the obtained product with the unordered rock salt structure oxyfluoride anode material, evaporating, and carrying out heat treatment on the obtained gel to obtain the composite anode material. The composite anode material effectively solves the problem of capacity loss of the anode material with the disordered rock salt structure in the electrolyte through the solid electrolyte coating layer, and has good stability, high conductivity, high voltage application range and higher discharge capacity.

Description

Composite cathode material, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of energy storage materials, and relates to a composite cathode material, a preparation method thereof and a lithium ion battery.
Background
Since the 90 s of the last century, through a great deal of research, lithium ion batteries have been applied to a wider range and have played a very important role in daily life. In recent years, the rapid development of electric automobiles puts forward new requirements on lithium ion batteries.
The currently commercialized lithium ion battery positive electrode material mainly comprises ordered layered rock salt transition metal oxidation and olivine-structured phosphate, wherein the ordered layered rock salt transition metal oxidation is the most widely applied. However, the cations in the crystal structure of the ordered layered rock salt structure material are completely and orderly arranged, which causes the lithium ions in the ordered layered rock salt structure material not to be completely removed, resulting in the disadvantages of low specific discharge capacity, low energy density and the like, and the requirements of the current electric automobile for high capacity and high energy density of the lithium ion battery cannot be met.
The positive electrode material having a disordered rock salt structure was previously thought to be disadvantageous in lithium ion migration due to the disordered arrangement of cations and low capacity, and therefore has not received sufficient attention. Recently, Lee et al of MIT in the United states discovered that when the lithium content in the disordered rock salt structure material is increased to a certain degree, the electrochemical performance of the disordered rock salt structure material is remarkably improved, thereby arousing the research interest of people on the disordered rock salt structure material. Subsequently, Chen et al found that oxyfluoride with disordered rock salt structure can also be used as a battery anode material and has higher specific capacity and energy density. However, as reported in the current research, the disordered rock salt structure has some problems, such as poor cycle performance, dissolution of transition metal ions in the material during the cycle process, irreversible capacity loss, and the like.
CN109305700A discloses a preparation method of a niobium/tantalum cation-containing disordered rock salt structure cathode material, belonging to the field of new energy materials. The method adopts a stable water-soluble citric acid Nb/Ta precursor to synthesize the Nb/Ta cation disordered rock salt structure-containing oxide cathode material by a wet chemical method.
CN110372039A discloses a method for preparing a positive electrode material with a cation disordered rock salt structure by a high-valence transition metal ion replacement combination strategy, which is to mix lithium salt with an oxide of a high-valence transition metal element M (at least one of Ti, V2, Nb, Mo and Zr), an oxide of M' (at least one of Fe, Ni and Mn) and villiaumite by a solid-phase ball milling method, and then carry out high-temperature treatment, thereby obtaining the positive electrode material.
CN105742616A discloses a lithium ion battery anode material with a disordered rock salt structure and a preparation method thereof. Putting LiNiTiNbO into NaOH solution, adding Bi (NO) and Ca (NO), continuously stirring at the temperature of 50-80 ℃, finally filtering, and heating the solid-phase substance at the temperature of 400-700 ℃ for 5-15h to obtain CaO/BiO/LiNiTiNbO.
However, the above method still has problems that the cycle performance is to be enhanced and the irreversible capacity loss is too large.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a composite cathode material, a preparation method thereof and a lithium ion battery. The composite anode material provided by the invention is a solid electrolyte coated unordered rock salt structure lithium ion battery anode material, has higher discharge capacity and stable cycle performance, and can be applied to high-voltage and high-capacity lithium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite cathode material, which comprises an inner core and a coating layer coated on the surface of the inner core, wherein the inner core comprises a disordered rock salt structure oxyfluoride cathode material, and the coating layer comprises a solid electrolyte.
The composite anode material provided by the invention effectively solves the problem of capacity loss caused by dissolution of transition metal elements in electrolyte by a solid electrolyte coating layer, and has good stability, high conductivity, high voltage application range and higher discharge capacity.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferable technical scheme of the invention, the chemical formula of the disordered rock salt structure oxyfluoride cathode material is LiMn1-xMxO2yLiF, where 0. ltoreq. x.ltoreq.1, for example 0, 0.2, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 etc., 0. ltoreq. y.ltoreq.2, for example y is 0, 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.5 or 2 etc., M is a metal element.
Preferably, 0.5. ltoreq. x.ltoreq.0.8, 0.6. ltoreq. y.ltoreq.1.4.
Preferably, M is any one or a combination of at least two of Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn or Sb.
Preferably, M is any one or a combination of at least two of Ti, V or Mo. Typical but non-limiting combinations are: a combination of Ti and V, a combination of Ti and Mo, a combination of V and Mo, a combination of Ti, V and Mo. The oxyfluoride anode material with the disordered rock salt structure containing the metal ions can provide higher specific capacity and energy density, and can keep higher capacity after being coated with solid electrolyte.
Preferably, the particle size of the inner core is below 100 nm.
Preferably, the solid electrolyte has a chemical formula of Li1.3Al0.3Ti1.7(PO4)3. The solid electrolyte has relatively high lithium ion conductivity and can reach 7 x 10 at room temperature-4S·cm-1. Coating a layer of Li on the surface of the disordered rock salt cathode material1.3Al0.3Ti1.7(PO4)3The solid electrolyte not only can reduce the direct contact between the electrolyte and the anode material, reduce the decomposition of the electrolyte and inhibit the oxygen loss on the surface of the anode material, thereby effectively improving the stability of the material, but also can improve the diffusion rate of lithium ions on the surface of the materialThereby further improving the electrochemical performance of the cathode material.
Preferably, the mass fraction of the solid electrolyte is 0.5 to 10 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, etc., preferably 1 to 5 wt%, based on 100% by mass of the composite positive electrode material. In the invention, if the mass fraction of the solid electrolyte is too high, the solid electrolyte coating layer is too thick, which is not beneficial to the reaction of the core cathode material and lithium ions; if the mass fraction of the solid electrolyte is too low, the solid electrolyte cannot completely cover the cathode material, and good protection cannot be provided for the core cathode material.
In a second aspect, the present invention provides a method for preparing a composite positive electrode material according to the first aspect, the method comprising the steps of:
(1) mixing and ball-milling raw materials for preparing the unordered rock salt structure oxyfluoride anode material to obtain the unordered rock salt structure oxyfluoride anode material;
(2) mixing raw materials for preparing the solid electrolyte with a complexing agent in a solvent, mixing the obtained product with the unordered rock salt structure oxyfluoride anode material obtained in the step (1), evaporating, and carrying out heat treatment on the obtained gel to obtain the composite anode material.
In the preparation method, a ball milling (especially high-energy ball milling) method is used in the step (1), and high energy generated during ball collision is used to enable raw material powder to generate solid-phase reaction to generate a nanoscale disordered rock salt cathode material, and meanwhile, the particle size of the product is ensured to be below 100nm, and special particle size control is not needed; and (2) using a sol-gel method to ensure that elements on the atomic scale are uniformly distributed, ensuring that ions in the sol are uniformly distributed on the surface of the core anode material, and controlling the thickness and the coating condition of a solid electrolyte coating layer by controlling the mass fractions of citric acid and the solid electrolyte.
In the present invention, it is difficult to obtain a disordered rock salt structure without using ball milling.
The preparation method provided by the invention is simple in process and easy to control.
As a preferable technical scheme of the invention, the raw materials for preparing the oxyfluoride cathode material with the disordered rock-salt structure in the step (1) comprise: a lithium source, a manganese source, an M source, and a fluorine source.
Preferably, the lithium source comprises any one of lithium carbonate, lithium hydroxide or lithium oxide or a combination of at least two thereof.
Preferably, the manganese source comprises any one or a combination of at least two of manganese monoxide, manganese dioxide or manganese sesquioxide.
Preferably, the M source comprises an oxide of the M element and/or a carbonate of the M element.
Preferably, M is any one or a combination of at least two of Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn, or Sb, preferably any one or a combination of two of Ti, V, or Mo. Typical but non-limiting combinations are: a combination of Ti and V, a combination of Ti and Mo, and a combination of V and Mo.
Preferably, the M source is any one or a combination of two of titanium dioxide, vanadium pentoxide and molybdenum trioxide.
Preferably, the fluorine source comprises any one of lithium fluoride, ammonium fluoride or tetrafluoroterephthalic acid or a combination of at least two thereof.
In the invention, the raw materials for preparing the disordered rock salt structure oxyfluoride cathode material can be proportioned according to the required element proportion in the chemical formula of the disordered rock salt structure oxyfluoride cathode material.
As a preferred technical scheme of the invention, the ball milling in the step (1) is carried out in a protective atmosphere.
Preferably, the protective atmosphere comprises any one or a combination of two of nitrogen, argon or helium.
Preferably, the ball milling in step (1) is high energy ball milling. The high-energy ball milling refers to ball milling with the ball milling rotating speed of more than 400 rpm.
Preferably, the rotation speed of the high-energy ball mill is 400-800rpm, such as 400rpm, 500rpm, 600rpm, 700rpm or 800rpm, etc.
Preferably, the ball milling time of the high energy ball milling is 10-48h, such as 10h, 20h, 30h, 40h or 48 h.
Preferably, the high energy ball mill has a ball to material ratio of 1:1 to 20:1, such as 1:1, 2:1, 5:1, 10:1, 15:1, or 20:1, etc.
As a preferred embodiment of the present invention, the raw materials for preparing the solid electrolyte in step (2) include a lithium source, an aluminum source, a titanium source and a phosphorus source.
Preferably, the lithium source comprises lithium nitrate and/or lithium acetate.
Preferably, the aluminium source comprises aluminium nitrate and/or aluminium acetate.
Preferably, the titanium source comprises tetrabutyl titanate and/or tetraethyl titanate.
Preferably, the source of phosphorus comprises tributyl phosphate and/or triethyl phosphate.
Preferably, the complexing agent in step (2) comprises any one or a combination of two of citric acid, ethylene diamine tetraacetic acid, ethylene glycol or triethanolamine.
Preferably, the solvent of step (2) comprises ethanol and/or water.
Preferably, in the step (2), the molar ratio of the total moles of metal ions in the raw materials for preparing the solid electrolyte to the moles of the complexing agent is 1:1 to 1:2, such as 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1: 2. In the invention, if the total mole number of the metal ions is too high relative to the mole number of the complexing agent, the solid electrolyte can form larger particles and can not be uniformly coated on the surface of the disordered rock salt cathode material; if the total mole number of the metal ions is too low relative to the mole number of the complexing agent, the carbon content in the precursor is too high, and the solid electrolyte is prevented from forming good contact with the surface of the disordered rock salt cathode material.
In a preferred embodiment of the present invention, the mixing method of mixing the raw material for preparing the solid electrolyte and the complexing agent in the solvent in the step (2) is stirring with heating.
Preferably, the heating temperature is 60-80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like.
Preferably, the mixing time of the raw materials for preparing the solid electrolyte and the complexing agent mixed in the solvent in the step (2) is 2-4h, such as 2h, 2.5h, 3h, 3.5h or 4 h.
In the step (2), the amount of the disordered rock salt structure oxyfluoride cathode material in the step (1) can be determined according to the required coating amount.
Preferably, the temperature of evaporation in step (2) is 60-80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, etc.
Preferably, the evaporation in step (2) is accompanied by stirring.
As a preferred embodiment of the present invention, the temperature of the heat treatment in step (2) is 450 ℃ or 800 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃. In the invention, if the heat treatment temperature in the step (2) is too high, the disordered rock salt cathode material is subjected to phase change decomposition; if the temperature of the heat treatment in step (2) is too low, the solid electrolyte may not form a good crystal form and may be in an amorphous glass state.
Preferably, the time of the heat treatment in the step (2) is 3-12h, such as 3h, 4h, 5h, 6h, 8h, 10h or 12 h.
Preferably, the atmosphere of the heat treatment of step (2) includes an air atmosphere.
Preferably, the gel is dried before the heat treatment in step (2).
Preferably, the drying temperature is 130-180 ℃, such as 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) mixing raw materials for preparing the oxyfluoride anode material with the disordered rock salt structure, and carrying out high-energy ball milling for 10-48h at the rotating speed of 400-800rpm and the ball-material ratio of 1:1-20:1 in a protective atmosphere to obtain the oxyfluoride anode material with the disordered rock salt structure;
(2) heating and stirring raw materials for preparing the solid electrolyte and a complexing agent in a solvent for 2-4h at 60-80 ℃, mixing the obtained product with the unordered rock salt structure oxyfluoride anode material in the step (1), keeping the heating temperature and stirring, evaporating, and performing 130-180 ℃ treatment on the obtained gel; then carrying out heat treatment at the temperature of 450-800 ℃ for 3-12h in the air atmosphere to obtain the composite cathode material;
wherein the molar ratio of the total mole number of metal ions in the raw materials for preparing the solid electrolyte to the mole number of the complexing agent is 1:1-1: 2.
In a third aspect, the present invention provides a lithium ion battery comprising the composite cathode material according to the first aspect.
The lithium ion battery provided by the invention has excellent rate capability and cycle performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite cathode material provided by the invention takes the cathode material with the disordered rock salt structure as a main body, and has the advantages of high voltage and high specific capacity compared with the cathode material of the lithium ion battery with the layered ordered rock salt structure; the solid electrolyte is coated on the surface of the lithium ion battery anode material with the disordered rock salt structure, so that the problem of dissolution of transition metal ions in the anode material with the disordered rock salt structure in an electrolyte is effectively solved, the stability of the material is improved, and the circulating stability of the material is improved; the coating with the solid electrolyte has higher lithium ion conductivity and reduces the influence of the coating layer on the performance of the battery material compared with the coating with oxides, phosphates and the like. The first discharge capacity of the composite anode material provided by the invention can reach 326mAh/g, and the capacity retention rate after 50 charge-discharge cycles can reach 92.8%.
(2) The preparation method provided by the invention is simple in process and easy to control.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the present inventionExamples in the following examples, a disordered rock salt structure oxyfluoride positive electrode material LiMn was used1-xMxO2yLiF as LMMOF, and Li as a solid electrolyte1.3Al0.3Ti1.7(PO4)3Is recorded as LATP:
example 1
In this example, a composite positive electrode material was prepared as follows:
(1) lithium oxide, manganese monoxide, titanium dioxide, vanadium pentoxide, molybdenum trioxide and lithium fluoride according to LiMn0.6Ti0.1V0.2Mo0.1O2Weighing LiF according to the proportion, ball-milling at 600rpm for 20 hours in an argon atmosphere to ensure that the particle size is below 100nm and a solid phase reaction is generated, wherein the ball-to-material ratio is 10:1, and obtaining the LMMOF disordered rock salt structure lithium ion battery anode material.
(2) At room temperature, weighing lithium nitrate, aluminum nitrate, tetrabutyl titanate and tributyl phosphate according to the proportion of LATP, and weighing according to nMetal:nCitric acid:nEthylenediaminetetraacetic acidWeighing citric acid and ethylenediamine tetraacetic acid complexing agent according to the proportion of 1:1:1.5, dissolving the citric acid and ethylenediamine tetraacetic acid complexing agent and metal salt in absolute ethyl alcohol, and heating and stirring the mixture for 3 hours at 70 ℃. And weighing LMMOF according to the LATP coating amount of 3 wt%, adding into the solution, evaporating the solvent to form gel, and transferring into a 140 ℃ oven for drying. And (3) carrying out heat treatment on the dried gel precursor at 550 ℃ for 6h to obtain the LATP @ LMMOF solid electrolyte coated unordered rock salt structure lithium ion battery anode material.
The composite cathode material prepared by the embodiment has a core of a disordered rock salt structure oxyfluoride cathode material LiMn0.6Ti0.1V0.2Mo0.1O2LiF, the coating layer coated on the surface of the inner core is solid electrolyte Li1.3Al0.3Ti1.7(PO4)3In the composite cathode material, the mass fraction of the solid electrolyte is 3 wt%.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 2
The difference from example 1 is the steps(1) Lithium oxide, manganese monoxide, titanium dioxide, vanadium pentoxide, molybdenum trioxide and lithium fluoride are mixed according to the general formula LiMn0.6Ti0.1V0.2Mo0.1O2The ratio of 0.6LiF was weighed, i.e. y is 0.6.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 3
The difference from example 1 is that step (1) comprises reacting lithium oxide, manganese monoxide, titanium dioxide, vanadium pentoxide, molybdenum trioxide and lithium fluoride in the general formula LiMn0.6Ti0.1V0.2Mo0.1O2The ratio of 1.4LiF was weighed, i.e. y is 1.4.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 4
The difference from the example 1 is that the ball milling atmosphere in the step (1) is nitrogen, the ball milling speed is 450rpm, the ball milling time is 40h, and the ball-to-material ratio is 20: 1.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 5
The difference from example 1 is that in step (2), the complexing agent is citric acid and ethylene glycol, and the ratio of metal ions to the complexing agent is nMetal:nCitric acid:nEthylene glycol＝1:1:2。
The test results of the composite cathode material provided in this example are shown in table 1.
Example 6
The difference from example 1 is that in step (2), the complexing agent is citric acid and triethanolamine, and the ratio of metal ions to complexing agent is nMetal:nCitric acid:nTriethanolamine＝1:1:1。
The test results of the composite cathode material provided in this example are shown in table 1.
Example 7
The difference from example 1 is that the stirring temperature in step (2) is 80 ℃ and the stirring time is 2 hours.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 8
The difference from example 1 is that the stirring temperature in step (2) is 60 ℃ and the stirring time is 4 hours.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 9
The difference from example 1 is that the LATP coating amount in step (2) is 1% by weight.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 10
The difference from example 1 is that the LATP coating amount in step (2) is 5% by weight.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 11
The difference from example 1 is that the drying temperature in step (2) was 130 ℃.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 12
The difference from example 1 is that the drying temperature in step (2) is 180 ℃.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 13
The difference from example 1 is that the heat treatment temperature in step (2) was 450 ℃ and the heat treatment time was 12 hours.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 14
The difference from example 1 is that the heat treatment temperature in step (2) was 800 ℃ and the heat treatment time was 3 hours.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 15
In this example, a composite positive electrode material was prepared as follows:
(1) lithium carbonate, manganese dioxide, vanadium pentoxide and lithium fluoride according to LiMn0.67V0.33O2Weighing 1.2LiF, and ball-milling for 40h at 450rpm in an argon atmosphere to ensure that the particle size is below 100nm and a solid phase reaction is generated, wherein the ball-to-material ratio is 20:1, so as to obtain the LMMOF disordered rock salt structure lithium ion battery anode material.
(2) At room temperature, weighing lithium acetate, aluminum acetate, tetraethyl titanate and triethyl phosphate according to the proportion of LATP, and weighing according to nMetal:nEthylene glycol:nEthylenediaminetetraacetic acidWeighing ethylene glycol and ethylene diamine tetraacetic acid complexing agent according to the proportion of 1:2:1, dissolving the ethylene glycol and the ethylene diamine tetraacetic acid complexing agent and metal salt in absolute ethyl alcohol, and heating and stirring the mixture for 2 hours at 80 ℃. And (3) weighing LMMOF according to the LATP coating amount of 3 wt%, adding the LMMOF into the solution, and transferring the LMMOF into a 160 ℃ oven for drying after the LMMOF is evaporated to form gel. And (3) carrying out heat treatment on the dried gel precursor at 550 ℃ for 5h to obtain the LATP @ LMMOF solid electrolyte coated unordered rock salt structure lithium ion battery anode material.
The composite cathode material prepared by the embodiment has a core of a disordered rock salt structure oxyfluoride cathode material LiMn0.67V0.33O21.2LiF, the coating layer coated on the surface of the inner core is solid electrolyte Li1.3Al0.3Ti1.7(PO4)3In the composite cathode material, the mass fraction of the solid electrolyte is 3 wt%.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 16
In this example, a solid electrolyte coated disordered rock salt structure lithium ion battery positive electrode material was prepared as follows:
(1) mixing lithium hydroxide, manganese oxide, titanium dioxide and lithium fluoride according to LiMn0.5Ti0.5O2Weighing 0.8LiF, and ball-milling at 800rpm for 20h in a nitrogen atmosphere to ensure that the particle size is below 100nm and a solid phase reaction is generated, wherein the ball-to-material ratio is 1:1, so as to obtain the LMMOF disordered rock salt structure lithium ion battery anode material.
(2) At room temperature, adding lithium acetate, aluminum acetate and titanic acidWeighing tetrabutyl ester and tributyl phosphate according to the proportion of LATP, and weighing nMetal:nCitric acid:nEthylenediaminetetraacetic acid:nEthylene glycolWeighing citric acid, ethylene diamine tetraacetic acid and an ethylene glycol complexing agent according to the proportion of 1:1:1:1, dissolving the citric acid, the ethylene diamine tetraacetic acid and the ethylene glycol complexing agent and metal salt in absolute ethyl alcohol, and heating and stirring the mixture at 80 ℃ for 2 hours. And (3) weighing LMMOF according to the LATP coating amount of 3 wt%, adding the LMMOF into the solution, and transferring the LMMOF into a 180 ℃ oven for drying after the solvent is evaporated to form gel. And (3) carrying out heat treatment on the dried gel precursor at 530 ℃ for 4h to obtain the LATP @ LMMOF solid electrolyte coated unordered rock salt structure lithium ion battery anode material.
The composite cathode material prepared by the embodiment has a core of a disordered rock salt structure oxyfluoride cathode material LiMn0.5Ti0.5O20.8LiF, the coating layer coated on the surface of the inner core is solid electrolyte Li1.3Al0.3Ti1.7(PO4)3In the composite cathode material, the mass fraction of the solid electrolyte is 3 wt%.
The test results of the composite cathode material provided in this example are shown in table 1.
Example 17
In this example, a composite positive electrode material was prepared as follows:
(1) lithium carbonate, manganese monoxide, molybdenum trioxide and lithium fluoride according to LiMn0.75Mo0.25O2Weighing 1.4LiF, and ball-milling at 400rpm for 48 hours in a nitrogen atmosphere to ensure that the particle size is below 100nm and a solid phase reaction is generated, wherein the ball-to-material ratio is 20:1, so as to obtain the LMMOF disordered rock salt structure lithium ion battery cathode material.
(2) At room temperature, weighing lithium nitrate, aluminum nitrate, tetraethyl titanate and triethyl phosphate according to the proportion of LATP, and weighing according to nMetal:nCitric acidWeighing citric acid and an ethylene diamine tetraacetic acid complexing agent according to the proportion of 1:1, dissolving the citric acid and the ethylene diamine tetraacetic acid complexing agent and metal salt in absolute ethyl alcohol, and heating and stirring the mixture for 3 hours at 60 ℃. And (3) weighing LMMOF according to the LATP coating amount of 2 wt%, adding the LMMOF into the solution, and transferring the LMMOF into a 150 ℃ oven for drying after the solvent is evaporated to form gel. Heat-treating the dried gel precursor at 500 ℃ for 6h to obtain LATP @ LThe MMOF solid electrolyte coats the lithium ion battery anode material with the disordered rock salt structure.
The composite cathode material prepared by the embodiment has a core of a disordered rock salt structure oxyfluoride cathode material LiMn0.75Mo0.25O21.4LiF, the coating layer coated on the surface of the inner core is solid electrolyte Li1.3Al0.3Ti1.7(PO4)3In the composite cathode material, the mass fraction of the solid electrolyte is 2 wt%.
The test results of the composite cathode material provided in this example are shown in table 1.
Comparative example 1
The difference from example 1 is that in step (1) lithium oxide, manganese monoxide, titanium dioxide, vanadium pentoxide, molybdenum trioxide are produced according to the general formula LiMn0.6Ti0.05V0.1Mo0.05O2The ratio of (a) is weighed, namely y is 0, and the F element is not contained.
The test results of the composite positive electrode material provided in this comparative example are shown in table 1.
Comparative example 2
The difference from example 1 is that the coating amount of LATP in step (2) is 0 wt%, i.e. no coating is performed.
The test results of the positive electrode material provided in this comparative example are shown in table 1.
Test method
The products provided in the examples and comparative examples were tested for performance using the following methods:
coating the positive electrode material prepared in a certain example or a comparative example, a Super P conductive agent and a PVDF binder according to a mass ratio of 7:2:1 on an aluminum foil to serve as a positive electrode plate, using metal lithium as a negative electrode and 1mol/L LiPF6The LIR-2025 button half cells were assembled from the EC + DMC + EMC (v/v ═ 1:1:1) electrolyte and Celgard2400 separator and tested.
The first discharge efficiency and capacity retention after 50 charge-discharge cycles were tested using a blue cell test system at 0.1C discharge/0.1C charge conditions. The test results are shown in the following table.
TABLE 1
Figure RE-GDA0002707594490000141
Figure RE-GDA0002707594490000151
As can be seen from table 1, examples 2 and 3 for example 1, the content of F in the material was changed, resulting in a decrease in the first discharge capacity; examples 9 and 10 for example 1, the coating amount of LATP was changed, resulting in a decrease in the first discharge capacity and a decrease in the capacity retention rate, indicating that too little or too much coating would adversely affect the battery material; example 13 for example 1, the temperature of the heat treatment was lowered to lower the capacity retention rate, which indicates that too low a temperature is not favorable for the generation of LATP; example 14 with respect to example 1, the heat treatment temperature was increased to greatly reduce the first discharge capacity and the capacity retention rate, which indicates that an excessively high heat treatment temperature would destroy the disordered rock salt oxyfluoride cathode material.
Comparative example 1 the first discharge capacity was greatly reduced for example 1, indicating that F can increase the battery capacity in the structure.
In comparison, in example 1, the capacity retention rate is greatly reduced in comparison with example 2, which shows that the LATP coating layer can effectively improve the cycle stability of the disordered rock salt oxyfluoride cathode material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The composite cathode material is characterized by comprising an inner core and a coating layer coated on the surface of the inner core, wherein the inner core comprises an oxyfluoride cathode material with a disordered rock salt structure, and the coating layer comprises a solid electrolyte.
2. The composite positive electrode material according to claim 1, wherein the chemical formula of the disordered rock salt structure oxyfluoride positive electrode material is LiMn1-xMxO2yLiF, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, and M is a metal element;
preferably, 0.5. ltoreq. x.ltoreq.0.8, 0.6. ltoreq. y.ltoreq.1.4;
preferably, M is any one or combination of at least two of Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn or Sb;
preferably, the M is any one or a combination of at least two of Ti, V or Mo;
preferably, the particle size of the inner core is below 100 nm;
preferably, the solid electrolyte has a chemical formula of Li1.3Al0.3Ti1.7(PO4)3；
Preferably, the mass fraction of the solid electrolyte is 0.5 to 10 wt%, preferably 1 to 5 wt%, based on 100% by mass of the composite positive electrode material.
3. A method for preparing a composite positive electrode material according to claim 1 or 2, characterized in that the method comprises the steps of:
(1) mixing and ball-milling raw materials for preparing the unordered rock salt structure oxyfluoride anode material to obtain the unordered rock salt structure oxyfluoride anode material;
(2) mixing raw materials for preparing the solid electrolyte with a complexing agent in a solvent, mixing the obtained product with the unordered rock salt structure oxyfluoride anode material obtained in the step (1), evaporating, and carrying out heat treatment on the obtained gel to obtain the composite anode material.
4. The preparation method according to claim 3, wherein the raw material for preparing the unordered rock salt structure oxyfluoride cathode material in step (1) comprises: a lithium source, a manganese source, an M source, and a fluorine source;
preferably, the lithium source comprises any one of lithium carbonate, lithium hydroxide or lithium oxide or a combination of at least two thereof;
preferably, the manganese source comprises any one or a combination of at least two of manganese monoxide, manganese dioxide or manganese sesquioxide;
preferably, the M source comprises an oxide of the M element and/or a carbonate of the M element;
preferably, M is any one or a combination of at least two of Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn or Sb, preferably any one or a combination of two of Ti, V or Mo;
preferably, the M source is any one or combination of two of titanium dioxide, vanadium pentoxide or molybdenum trioxide;
preferably, the fluorine source comprises any one of lithium fluoride, ammonium fluoride or tetrafluoroterephthalic acid or a combination of at least two thereof.
5. The method of claim 3 or 4, wherein the ball milling of step (1) is performed under a protective atmosphere;
preferably, the protective atmosphere comprises any one or a combination of two of nitrogen, argon or helium;
preferably, the ball milling in the step (1) is high-energy ball milling;
preferably, the rotating speed of the high-energy ball mill is 400-800 rpm;
preferably, the ball milling time of the high-energy ball milling is 10-48 h;
preferably, the ball-to-material ratio of the high-energy ball mill is 1:1-20: 1.
6. The production method according to any one of claims 3 to 5, wherein the raw materials for producing the solid electrolyte in step (2) include a lithium source, an aluminum source, a titanium source and a phosphorus source;
preferably, the lithium source comprises lithium nitrate and/or lithium acetate;
preferably, the aluminium source comprises aluminium nitrate and/or aluminium acetate;
preferably, the titanium source comprises tetrabutyl titanate and/or tetraethyl titanate;
preferably, the source of phosphorus comprises tributyl phosphate and/or triethyl phosphate;
preferably, the complexing agent in the step (2) comprises any one or a combination of two of citric acid, ethylene diamine tetraacetic acid, ethylene glycol or triethanolamine;
preferably, the solvent of step (2) comprises ethanol and/or water;
preferably, in the step (2), the molar ratio of the total moles of metal ions in the raw materials for preparing the solid electrolyte to the moles of the complexing agent is 1:1 to 1: 2.
7. The production method according to any one of claims 3 to 6, wherein the mixing method of mixing the raw materials for producing the solid electrolyte and the complexing agent in the solvent in the step (2) is stirring with heating;
preferably, the heating temperature is 60-80 ℃;
preferably, the mixing time of the raw materials for preparing the solid electrolyte and the complexing agent in the solvent in the step (2) is 2-4 h;
preferably, the temperature of the evaporation in the step (2) is 60-80 ℃;
preferably, the evaporation in step (2) is accompanied by stirring.
8. The method according to any one of claims 3 to 7, wherein the temperature of the heat treatment in step (2) is 450-800 ℃;
preferably, the time of the heat treatment in the step (2) is 3-12 h;
preferably, the atmosphere of the heat treatment of step (2) comprises an air atmosphere;
preferably, the gel is dried before the heat treatment in step (2);
preferably, the temperature of the drying is 130-.
9. The method for preparing according to any one of claims 3 to 8, characterized in that it comprises the steps of:
(1) mixing raw materials for preparing the oxyfluoride anode material with the disordered rock salt structure, and carrying out high-energy ball milling for 10-48h at the rotating speed of 400-800rpm and the ball-material ratio of 1:1-20:1 in a protective atmosphere to obtain the oxyfluoride anode material with the disordered rock salt structure;
(2) heating and stirring raw materials for preparing the solid electrolyte and a complexing agent in a solvent for 2-4h at 60-80 ℃, mixing the obtained product with the unordered rock salt structure oxyfluoride anode material in the step (1), keeping the heating temperature and stirring, evaporating, and performing 130-180 ℃ treatment on the obtained gel; then carrying out heat treatment at the temperature of 450-800 ℃ for 3-12h in the air atmosphere to obtain the composite cathode material;
wherein the molar ratio of the total mole number of metal ions in the raw materials for preparing the solid electrolyte to the mole number of the complexing agent is 1:1-1: 2.
10. A lithium ion battery comprising the composite positive electrode material according to claim 1 or 2.
CN202010749149.5A 2020-07-30 2020-07-30 Composite cathode material, preparation method thereof and lithium ion battery Pending CN111952560A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461058A (en) * 2021-07-15 2021-10-01 河南理工大学 Cathode material Li with disordered rock salt structure1.3Mo0.3V0.4O2Method of synthesis of
CN113889617A (en) * 2021-09-29 2022-01-04 国联汽车动力电池研究院有限责任公司 Composite-structure high-manganese-based material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160351973A1 (en) * 2015-06-01 2016-12-01 Energy Power Systems LLC Nano-engineered coatings for anode active materials, cathode active materials, and solid-state electrolytes and methods of making batteries containing nano-engineered coatings
CN108832096A (en) * 2018-06-13 2018-11-16 中科廊坊过程工程研究院 A kind of codope anode material for lithium-ion batteries and preparation method thereof and lithium ion battery
CN110112383A (en) * 2019-04-17 2019-08-09 湖北锂诺新能源科技有限公司 The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160351973A1 (en) * 2015-06-01 2016-12-01 Energy Power Systems LLC Nano-engineered coatings for anode active materials, cathode active materials, and solid-state electrolytes and methods of making batteries containing nano-engineered coatings
CN108832096A (en) * 2018-06-13 2018-11-16 中科廊坊过程工程研究院 A kind of codope anode material for lithium-ion batteries and preparation method thereof and lithium ion battery
CN110112383A (en) * 2019-04-17 2019-08-09 湖北锂诺新能源科技有限公司 The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461058A (en) * 2021-07-15 2021-10-01 河南理工大学 Cathode material Li with disordered rock salt structure1.3Mo0.3V0.4O2Method of synthesis of
CN113461058B (en) * 2021-07-15 2022-09-09 宜宾职业技术学院 Cathode material Li with disordered rock salt structure 1.3 Mo 0.3 V 0.4 O 2 Method of synthesis of
CN113889617A (en) * 2021-09-29 2022-01-04 国联汽车动力电池研究院有限责任公司 Composite-structure high-manganese-based material and preparation method and application thereof
CN113889617B (en) * 2021-09-29 2023-08-15 国联汽车动力电池研究院有限责任公司 Composite structure high manganese-based material and preparation method and application thereof

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