CN110797519A - Lithium ion battery positive electrode material, preparation method and lithium ion battery - Google Patents

Lithium ion battery positive electrode material, preparation method and lithium ion battery Download PDF

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CN110797519A
CN110797519A CN201911101561.XA CN201911101561A CN110797519A CN 110797519 A CN110797519 A CN 110797519A CN 201911101561 A CN201911101561 A CN 201911101561A CN 110797519 A CN110797519 A CN 110797519A
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lithium
ion battery
source
lithium ion
gel
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CN110797519B (en
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谭强强
夏青
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Langfang green industry technology service center
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
    • 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
    • H01M4/58—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
    • 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

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Abstract

The invention relates to a lithium ion battery anode material, a preparation method and a lithium ion battery, wherein the lithium ion battery anode material has the chemical formula: li2Mn1‑yMyO2X/C, wherein, 0<y<1, M is + 4-valent transition metal, X is halogen element, and Mn is + 2-valent; the preparation method comprises the following steps: dissolving a lithium source, a manganese source, an M source and a halogen element source in a solvent, then adding a reducing agent and a thickening agent, and uniformly mixing to obtain a mixed solution; heating the mixed solution to obtain gel, and drying the gel to obtain dry gel; heating the dry gel and preserving heat to ensure that the dry gel is completely burnt in a self-propagating way to generate fluffy powder; heat treatment under protective atmosphereAnd (3) fluffing the powder, and cooling to obtain the lithium ion battery anode material. The anode material provided by the invention has higher specific cyclic capacity and stability.

Description

Lithium ion battery positive electrode material, preparation method and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium batteries, relates to an electrode material, and particularly relates to a lithium ion battery anode material, a preparation method and a lithium ion battery.
Background
With the rapid development of new energy automobiles, the lithium ion battery industry has entered a rapid development stage. The key materials influencing the performance of the lithium ion battery mainly comprise a positive electrode material, a negative electrode material, electrolyte and the like. The positive electrode material is a main factor for limiting the performance of the battery at present, and the cost of the positive electrode material is close to 40% of that of the lithium ion battery.
The lithium ion battery realizes large-scale application and simultaneously meets a series of requirements of low cost, safety, no natural resource limitation, high energy density and the like. The anode materials of the lithium ion batteries studied at present mainly include lithium cobaltate, lithium nickelate, lithium nickel cobaltate and lithium iron phosphate. However, LiCoO2High cost, and Co3+Toxic, the material is structurally unstable when overcharged; LiNiO2The synthesis conditions are harsh, part of lithium sites are occupied by nickel sites, the degree of order is low, and the reversibility is poor; binary material LiNi1-xCoxO2(0<x<1) Although the advantages of several materials are combined, the capacity of the material is difficult to reach 200mAh/g, and the requirement of high specific energy of the electric automobile cannot be met.
The positive electrode material based on manganese base attracts wide attention due to the advantages of low cost, rich resources and the like, but LiMnO2Poor thermal stability at high temperatures; spinel-structured LiMn2O4During cycling, phase transitions can occur resulting in capacity loss; ternary material LiNi1-xCoxMnyO2(0<x<1,0<y<1) The capacity is difficult to reach 200mAh/g, and the requirement of high specific energy of the electric automobile can not be met.
CN 102394303A discloses a method for preparing lithium ion battery anode material lithium manganese silicate, which adopts SiO2The method adopts the processes of pretreatment, ultrasonic dissolution, glue preparation, gel, drying, presintering and roasting as raw materials, and adopts an ultrasonic-assisted method to inhibit the formation of large particles, so that the particle size distribution of the product is uniform, and the calcining temperature is reduced.
CN 102280621A discloses a method for preparing lithium manganese phosphate/carbon of lithium ion battery material by sol-gel, which comprises mixing lithium source compound, manganese source compound, phosphorus source compound and complexing agent compound according to mol ratio, dissolving in solvent or dispersing in solution to obtain mixed material, adjusting pH value of the solution to 0.5-3.7 by concentrated nitric acid or concentrated ammonia water, and obtaining sol solution. And (3) evaporating the sol solution to dryness in a water bath to obtain dry gel, and drying and roasting to obtain the carbon-coated lithium manganese phosphate.
CN 105322151A discloses a preparation method of a modified lithium ion battery cathode material lithium nickel manganese oxide, which comprises the steps of mixing manganese salt and nickel salt materials, preparing a nickel manganese precursor by a sol-gel method, mixing the nickel manganese precursor and lithium salt by a three-dimensional inclined mixer, carrying out pretreatment, high-temperature sintering, doping F and/or metal cations, adding metal oxides for wet coating, and finally carrying out low-temperature sintering, airflow crushing and grading to obtain a finished product of lithium nickel manganese oxide.
CN 107742722 a discloses a method for modifying lithium manganate positive electrode material for lithium ion battery, comprising: dissolving La salt, Sr salt and manganese salt in deionized water according to a stoichiometric ratio; adding citric acid under stirring, and adjusting pH to 3-10 with ammonia water or nitric acid to obtain stable sol; adding lithium manganate, heating, stirring until water vapor volatilizes, drying, and coating a layer of gel film on the surface of the base material; and roasting the base material coated with the gel film to obtain the coated modified lithium manganate material.
CN 103066272A discloses Ni2+、Mn4+、Si4+、Zn2+And F-Doped surface modified lithium-rich cathode material and preparation method thereof, wherein the product is Ni2+、Mn4+、Si4+、Zn2+And F-Doped Nasicon solid electrolyte LiTi2(PO4)3The surface modified layer-layer composite lithium-rich cathode material has the surface modified layer with the amount of 1-10% of the cathode material.
The manganese-based positive electrode material prepared by the method has the advantages that the reversible specific capacity, the cycle performance and the high-voltage performance are all required to be improved, and therefore, the positive electrode material of the lithium ion battery and the preparation method thereof are provided, so that the positive electrode material has higher reversible specific capacity and energy density, and the method has important significance for the development of the technical field of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode material, a preparation method and a lithium ion battery, wherein the lithium ion battery anode material utilizes high-price transition metal to partially replace Mn, the valence state of Mn in the anode material is reduced, the Mn exists in the form of divalent Mn, and Mn is utilized2+/Mn4+The reversible redox couple improves the overall energy density of the lithium ion battery anode material; and the lithium ion battery anode material utilizes halogen elements to replace part of O atoms, so that the O content in the lithium ion battery anode material is reduced, and the problem of instability of the electrode material caused by O oxidation reduction is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium ion battery cathode material, wherein the lithium ion battery cathode material has a chemical formula: li2Mn1-yMyO2X/C, wherein, 0<y<1, M is + 4-valent transition metal, X is halogen element, and Mn is + 2-valent; y is preferably 0.5.
The preparation method comprises the following steps:
(1) dissolving a lithium source, a manganese source, an M source and a halogen element source in a solvent according to a stoichiometric ratio, adding a reducing agent and a thickening agent, and uniformly mixing to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to obtain gel, and drying the gel to obtain dry gel;
(3) heating the dried gel obtained in the step (2) and preserving heat to ensure that the dried gel is completely burnt in a self-propagating way to generate fluffy powder;
(4) and (4) carrying out heat treatment on the fluffy powder obtained in the step (3) under a protective atmosphere, and cooling to obtain the lithium ion battery anode material.
The lithium ion battery anode material provided by the invention is a lithium ion battery anode material double-doped with M transition metal and halogen elements. Wherein M is in transitionThe synergistic effect of the metal and the halogen element in the cathode material enables the cathode material provided by the invention to have excellent performance. Specifically, Mn is partially substituted by introducing a + 4-valent transition metal, so that the valence state of Mn in the positive electrode material is reduced, the Mn exists in a divalent Mn form, and Mn is utilized2+/Mn4+The reversible redox couple improves the overall energy density of the material; and the halogen element is used for replacing part of O, so that the content of O is reduced, and the problem that the oxidation reduction of O causes the electrode material to be unstable is solved.
Preferably, the dissolving of the lithium source, the manganese source, the M source and the halogen element source in the solvent according to the stoichiometric ratio in the invention means that the lithium source, the manganese source, the M source and the halogen element source are added in amounts such that the finally prepared lithium ion battery positive electrode slurry satisfies Li2Mn1-yMyO2X/C、0<y<1. M is +4 transition metal, X is halogen element and Mn is +2 valence. Preferably, in order to compensate for the loss of lithium atoms during the heat treatment, the amount of lithium source added needs to be 1-10% more than the theoretical value, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the lithium source of step (1) comprises any one or a combination of at least two of lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate or lithium oxide, typical but non-limiting combinations include a combination of lithium nitrate and lithium carbonate, a combination of lithium carbonate and lithium hydroxide, a combination of lithium hydroxide and lithium acetate, a combination of lithium acetate and lithium oxide, a combination of lithium nitrate and lithium hydroxide, a combination of lithium carbonate and lithium oxide, a combination of lithium nitrate, lithium carbonate and lithium hydroxide, a combination of lithium carbonate, lithium hydroxide and lithium acetate, a combination of lithium carbonate, lithium acetate and lithium oxide or a combination of lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate and lithium oxide; preferably lithium nitrate;
preferably, the manganese source of step (1) comprises any one of manganese nitrate, manganese carbonate, manganese acetate or manganese oxide or a combination of at least two of them, typical but non-limiting combinations include a combination of manganese nitrate and manganese carbonate, a combination of manganese carbonate and manganese acetate, a combination of manganese acetate and manganese oxide, a combination of manganese nitrate and manganese acetate, a combination of manganese carbonate and manganese oxide, a combination of manganese nitrate, manganese carbonate and manganese acetate, a combination of manganese nitrate, manganese acetate and manganese oxide, a combination of manganese carbonate, manganese acetate and manganese oxide or a combination of manganese nitrate, manganese carbonate, manganese acetate and manganese oxide.
Preferably, the M source of step (1) comprises a Ti source and/or a Zr source.
Preferably, the Ti source comprises any one or a combination of at least two of titanyl sulfate, titanium tetrachloride or tetrabutyl titanate, typical but non-limiting combinations include a combination of titanyl sulfate and titanium sulfate, a combination of titanyl sulfate and titanium tetrachloride, a combination of titanyl sulfate and tetrabutyl titanate, a combination of titanium sulfate and titanium tetrachloride, a combination of titanium sulfate and tetrabutyl titanate, a combination of titanium tetrachloride and tetrabutyl titanate, a combination of titanyl sulfate, titanium sulfate and titanium tetrachloride, a combination of titanyl sulfate, titanium tetrachloride and tetrabutyl titanate, a combination of titanium sulfate, titanium tetrachloride and tetrabutyl titanate or a combination of titanyl sulfate, titanium tetrachloride and tetrabutyl titanate.
Preferably, the Zr source comprises zirconium sulfate and/or zirconium nitrate.
Preferably, the halogen element source in step (1) comprises any one or a combination of at least two of lithium chloride, lithium bromide or lithium fluoride, typical but non-limiting combinations include a combination of lithium chloride and lithium bromide, a combination of lithium bromide and lithium fluoride, a combination of lithium chloride and lithium fluoride or a combination of lithium chloride, lithium bromide and lithium fluoride, preferably lithium fluoride.
Preferably, the reducing agent of step (1) comprises citric acid.
Preferably, the thickener of step (1) comprises ethylene glycol and/or glycerol, preferably glycerol.
Preferably, the solvent in step (1) is deionized water.
Preferably, the concentration of the metal ion in the mixed solution in step (1) is 0.01-10mol/L, for example, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, but not limited to the enumerated values, and other unrecited values within the numerical range are equally applicable, preferably 3-6 mol/L.
The concentration of the metal ions in the mixed solution refers to Mn in the mixed solution2+And the total concentration of transition metal ions.
Preferably, the molar ratio of the reducing agent to the transition metal ion in the M source in step (1) is (0.5-4):1, and may be, for example, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, but is not limited to the recited values, and other values within the range of values are equally applicable, preferably (1-3): 1.
Preferably, the molar ratio of thickener to reducing agent in step (1) is (0.1-2):1, and may be, for example, 0.1:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1, but is not limited to the recited values, and other values within the range of values are equally applicable, preferably (0.6-1.5): 1.
Preferably, the heating temperature in step (2) is 50-100 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 60-80 ℃.
Preferably, the temperature of the drying in step (2) is 60-100 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other values in the range of values are also applicable, preferably 70-90 ℃.
According to the invention, the gel is prepared by heating, so that the water in the mixed solution is evaporated to obtain the gel, and then the gel is dried to prepare the dry gel, so that all components in the solution are mixed more uniformly, and the consistency of the material is ensured, so that the obtained lithium ion battery anode material has higher reversible specific capacity and stability.
Preferably, the heating temperature in step (3) is 200-.
Preferably, the incubation time in step (3) is 0.5-10h, for example 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the protective atmosphere in step (4) comprises any one or a combination of at least two of nitrogen, argon or helium, and typical but non-limiting combinations include a combination of nitrogen and argon, a combination of argon and helium, a combination of nitrogen and helium or a combination of nitrogen, argon and helium.
Preferably, the heat treatment method in step (4) is sintering.
Preferably, the temperature rise rate of the sintering in step (4) is 1-30 ℃/min, such as 1 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min, 22 ℃/min, 25 ℃/min, 27 ℃/min or 30 ℃/min, but not limited to the values listed, and other values within the range of values are equally applicable, preferably 5-15 ℃/min.
The material is heated unevenly due to the overhigh heating rate, the energy consumption is overhigh due to the overhigh heating rate, and the preparation cost of the material is increased, so that the heating rate of 1-30 ℃/min is adopted, and the lithium ion battery anode material prepared in the range has higher reversible specific capacity and stability.
Preferably, the sintering temperature in step (4) is 600-1200 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃, but not limited to the cited values, and other values not listed in the numerical range are equally applicable, preferably 800-1000 ℃.
Preferably, the sintering time in step (4) is 5-20h, such as 5h, 7h, 9h, 10h, 12h, 15h, 18h or 20h, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 10-15 h.
Preferably, the cooling in step (4) is to room temperature, preferably 10-30 ℃, for example 10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) dissolving a lithium source, a manganese source, an M source and a halogen element source in deionized water according to a stoichiometric ratio, then adding a reducing agent and a thickening agent, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01-10mol/L, wherein the molar ratio of the reducing agent to transition metal ions in the M source is (0.5-4):1, and the molar ratio of the thickening agent to the reducing agent is (0.1-2): 1;
(2) heating the mixed solution obtained in the step (1) at 50-100 ℃ to obtain gel, and drying the gel at 60-100 ℃ to obtain dry gel;
(3) heating the dried gel obtained in the step (2) at the temperature of 400 ℃ at 200 ℃ and preserving the heat for 0.5-10h to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) under a protective atmosphere, heating to 600-1200 ℃ at the speed of 1-30 ℃/min, sintering the fluffy powder obtained in the step (3) for 5-20h, and cooling to obtain the lithium ion battery anode material.
In a second aspect, the invention provides the lithium ion battery cathode material Li prepared by the preparation method in the first aspect2Mn1-yMyO2X/C, wherein 0<y<1, M is +4 transition metal, X is halogen element, Mn is +2 valence, and y is preferably 1/2.
The lithium ion battery cathode material Li2Mn1-yMyO2The halogen element in X/C includes any one or a combination of at least two of fluorine, chlorine or bromine, and typical but non-limiting combinations include fluorine and chlorine, chlorine and bromine, fluorine and bromine or fluorine, chlorine and bromine.
In a third aspect, the invention provides a lithium ion battery comprising the lithium ion battery cathode material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the positive electrode material of the lithium ion battery provided by the invention reduces the valence state of Mn and the reaction activity of O by introducing + 4-valent cations and halogen elements, so that the stability of the obtained positive electrode material of the lithium ion battery is improved, the obtained positive electrode material of the lithium ion battery has the advantages of high voltage and high reversible specific capacity, the first cyclic discharge specific capacity is more than 220mAh/g under the voltage window of 1.5-5.0V and the current density of 20mA, and the capacity retention ratio of 200 cycles is more than 90%;
(2) the invention realizes the mixing of atomic level by a self-propagating high-temperature synthesis method, and improves the mixing uniformity of the obtained lithium ion battery anode material;
(3) the preparation method provided by the invention needs shorter time, and improves the preparation efficiency of the lithium ion battery anode material; meanwhile, the prepared lithium ion battery anode material has low nickel and cobalt contents, and the production cost of the lithium ion battery anode material is reduced.
Drawings
Fig. 1 is an SEM image of the lithium ion positive electrode material obtained in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate, titanium sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, then adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01mol/L, wherein the molar ratio of the citric acid to the titanium ions is 4:1, and the molar ratio of the glycerol to the citric acid is 0.1: 1;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The SEM image of the obtained lithium ion battery positive electrode material is shown in fig. 1, and it can be seen from fig. 1 that the material is in a loose structure due to the generation of a large amount of gas during the sintering process, and the obtained lithium ion battery positive electrode material is uniform nanoparticles.
Example 2
The embodiment provides a lithium ion battery anode material Li2Mn0.5Zr0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium carbonate, manganese acetate, zirconium sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium carbonate is 5% more than the theoretical amount, then adding citric acid and ethylene glycol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 10mol/L, wherein the molar ratio of the citric acid to the zirconium ion is 2:1, and the molar ratio of the ethylene glycol to the citric acid is 1: 1;
(2) heating the mixed solution obtained in the step (1) at 100 ℃ to obtain gel, and drying the gel at 80 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 400 ℃ and preserving heat for 0.5h to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 1200 ℃ at the speed of 1 ℃/min under the atmosphere of helium, sintering the fluffy powder obtained in the step (3) for 5 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The obtained lithium ion battery anode material is uniform nano-particles.
Example 3
The embodiment provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium acetate, manganese carbonate, titanyl sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium acetate is 1% more than the theoretical amount, then adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.5mol/L, wherein the molar ratio of the citric acid to the titanium ion is 0.5:1, and the molar ratio of the glycerol to the citric acid is 0.6: 1;
(2) heating the mixed solution obtained in the step (1) at 80 ℃ to obtain gel, and drying the gel at 90 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 300 ℃, and preserving heat for 8 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 1000 ℃ at the speed of 30 ℃/min under the argon atmosphere, sintering the fluffy powder obtained in the step (3) for 12 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The obtained lithium ion battery anode material is uniform nano-particles.
Example 4
The embodiment provides a lithium ion battery anode material Li2Mn0.5Zr0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium hydroxide, manganese oxide, zirconium nitrate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium hydroxide is 2% more than the theoretical amount, adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 2mol/L, wherein the molar ratio of the citric acid to the zirconium ions is 3:1, and the molar ratio of the glycerol to the citric acid is 1.5: 1;
(2) heating the mixed solution obtained in the step (1) at 50 ℃ to obtain gel, and drying the gel at 60 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 200 ℃ and preserving heat for 10 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 600 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 20 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The obtained lithium ion battery anode material is uniform nano-particles.
Example 5
The embodiment provides a lithium ion battery anode material Li2Mn0.5Ti0.25Zr0.25O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate, titanium tetrachloride, zirconium nitrate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 8% more than the theoretical amount, then adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 5mol/L, wherein the molar ratio of the citric acid to the zirconium ions is 1:1, and the molar ratio of the glycerol to the citric acid is 2: 1;
(2) heating the mixed solution obtained in the step (1) at 70 ℃ to obtain gel, and drying the gel at 90 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 350 ℃, and preserving heat for 2 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 900 ℃ at the speed of 15 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 15 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The obtained lithium ion battery anode material is uniform nano-particles.
Example 6
The embodiment provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2The preparation method of F/C was the same as that of example 1 except that the temperature increase rate in step (4) was 0.6 ℃/min.
The obtained lithium ion battery anode material is uniform nano-particles.
Example 7
The embodiment provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2The preparation method of F/C was the same as that of example 1 except that the temperature increase rate in step (4) was 35 ℃/min.
Due to the fact that the temperature rising rate is too high, the appearance of the obtained lithium ion battery anode material is not uniform.
Comparative example 1
The comparative example provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate, titanium sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01 mol/L;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
Comparative example 2
The comparative example provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate, titanium sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, then adding citric acid, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01mol/L, wherein the molar ratio of the citric acid to the titanium ions is 4: 1;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
Comparative example 3
The comparative example provides a lithium ion battery anode material Li2Mn0.5Ti0.5O2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate, titanium sulfate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, adding glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01mol/L, wherein the addition amount of the glycerol is the same as that of the glycerol in example 1;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
Comparative example 4
The comparative example provides a lithium ion battery anode material Li2MnTi0.5O3A preparation method of/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate and titanium sulfate in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, then adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01mol/L, wherein the molar ratio of the citric acid to the titanium ion is 4:1, and the molar ratio of the glycerol to the citric acid is 0.1: 1;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
Comparative example 5
The comparative example provides a lithium ion battery anode material Li2MnO2A preparation method of F/C, comprising the following steps:
(1) dissolving lithium nitrate, manganese nitrate and lithium fluoride in deionized water according to a stoichiometric ratio, wherein the addition amount of the lithium nitrate is 1% more than the theoretical amount, then adding citric acid and glycerol, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01mol/L, wherein the molar ratio of the citric acid to the titanium ion is 4:1, and the molar ratio of the glycerol to the citric acid is 0.1: 1;
(2) heating the mixed solution obtained in the step (1) at 60 ℃ to obtain gel, and drying the gel at 100 ℃ to obtain xerogel;
(3) heating the dried gel obtained in the step (2) at 250 ℃ and preserving heat for 5 hours to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, sintering the fluffy powder obtained in the step (3) for 10 hours, and cooling to room temperature to obtain the lithium ion battery anode material.
The lithium ion battery positive electrode materials provided in examples 1 to 7 and comparative examples 1 to 5 were subjected to electrochemical performance tests, and the pole piece ratio was such that the mass ratio of the lithium ion battery positive electrode material, acetylene black and PVDF was 90:5: 5. A CR2025 type button cell is prepared by taking a lithium sheet as a reference electrode, and is tested under the conditions of a voltage window of 1.5-5.0V and a current density of 20mA, and the test results are shown in Table 1.
TABLE 1
Figure BDA0002270026360000151
Figure BDA0002270026360000161
In conclusion, the positive electrode material of the lithium ion battery provided by the invention reduces the valence state of Mn and the reaction activity of O by introducing + 4-valent cations and halogen elements, thereby improving the stability of the obtained positive electrode material of the lithium ion battery; the atomic-level mixing is realized by a self-propagating high-temperature synthesis method, and the mixing uniformity of the obtained lithium ion battery anode material is improved; the preparation method provided by the invention needs shorter time, and improves the preparation efficiency of the lithium ion battery anode material; meanwhile, the prepared lithium ion battery anode material has low nickel and cobalt contents, so that the production cost of the lithium ion battery anode material is reduced; the obtained lithium ion battery anode material has the advantages of high voltage and high reversible specific capacity, the first cycle discharge specific capacity is more than 220mAh/g under the voltage window of 1.5-5.0V and the current density of 20mA, and the capacity retention rate of 200 cycles of the cycle is more than 90%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The preparation method of the lithium ion battery anode material is characterized in that the chemical formula of the lithium ion battery anode material is as follows: li2Mn1-yMyO2X/C, wherein, 0<y<1, M is + 4-valent transition metal, X is halogen element, and Mn is + 2-valent;
the preparation method comprises the following steps:
(1) dissolving a lithium source, a manganese source, an M source and a halogen element source in a solvent according to a stoichiometric ratio, adding a reducing agent and a thickening agent, and uniformly mixing to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to obtain gel, and drying the gel to obtain dry gel;
(3) heating the dried gel obtained in the step (2) and preserving heat to ensure that the dried gel is completely burnt in a self-propagating way to generate fluffy powder;
(4) and (4) carrying out heat treatment on the fluffy powder obtained in the step (3) under a protective atmosphere, and cooling to obtain the lithium ion battery anode material.
2. The production method according to claim 1, wherein the lithium source of step (1) comprises any one of lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate, or lithium oxide, or a combination of at least two thereof, preferably lithium nitrate;
preferably, the manganese source of step (1) comprises any one of manganese nitrate, manganese carbonate, manganese acetate or manganese oxide or a combination of at least two of the same;
preferably, the M source of step (1) comprises a Ti source and/or a Zr source;
preferably, the Ti source comprises any one of titanyl sulfate, titanium tetrachloride or tetrabutyl titanate or a combination of at least two thereof;
preferably, the Zr source comprises zirconium sulfate and/or zirconium nitrate;
preferably, the halogen element source in step (1) comprises any one or a combination of at least two of lithium chloride, lithium bromide or lithium fluoride, preferably lithium fluoride.
3. The production method according to claim 1 or 2, wherein the reducing agent of step (1) comprises citric acid;
preferably, the thickener of step (1) comprises ethylene glycol and/or glycerol, preferably glycerol;
preferably, the solvent in step (1) is deionized water.
4. The production method according to any one of claims 1 to 3, wherein the concentration of the metal ion in the mixed solution of step (1) is 0.01 to 10mol/L, preferably 3 to 6 mol/;
preferably, the molar ratio of the reducing agent in the step (1) to the transition metal ion in the M source is (0.5-4):1, preferably (1-3): 1;
preferably, the molar ratio of the thickener to the reducing agent in the step (1) is (0.1-2):1, preferably (0.6-1.5): 1.
5. The method according to any one of claims 1 to 4, wherein the heating temperature in step (2) is 50 to 100 ℃, preferably 60 to 80 ℃;
preferably, the temperature for drying in the step (2) is 60-100 ℃, preferably 70-90 ℃.
6. The method according to any one of claims 1 to 5, wherein the heating temperature in step (3) is 200-400 ℃, preferably 250-350 ℃;
preferably, the time for the heat preservation in the step (3) is 0.5-10 h.
7. The method according to any one of claims 1 to 6, wherein the protective atmosphere in step (4) comprises any one of nitrogen, argon or helium or a combination of at least two thereof;
preferably, the heat treatment method in step (4) is sintering;
preferably, the temperature rise rate of the sintering in the step (4) is 1-30 ℃/min, preferably 5-15 ℃/min;
preferably, the sintering temperature in the step (4) is 600-1200 ℃, preferably 800-1000 ℃;
preferably, the sintering time in the step (4) is 5-20h, preferably 10-15 h.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) dissolving a lithium source, a manganese source, an M source and a halogen element source in deionized water according to a stoichiometric ratio, then adding a reducing agent and a thickening agent, and uniformly mixing to obtain a mixed solution with the metal ion concentration of 0.01-10mol/L, wherein the molar ratio of the reducing agent to transition metal ions in the M source is (0.5-4):1, and the molar ratio of the thickening agent to the reducing agent is (0.1-2): 1;
(2) heating the mixed solution obtained in the step (1) at 50-100 ℃ to obtain gel, and drying the gel at 60-100 ℃ to obtain dry gel;
(3) heating the dried gel obtained in the step (2) at the temperature of 400 ℃ at 200 ℃ and preserving the heat for 0.5-10h to ensure that the dried gel is completely self-propagating and burnt to generate fluffy powder;
(4) and (3) under a protective atmosphere, heating to 600-1200 ℃ at the speed of 1-30 ℃/min, sintering the fluffy powder obtained in the step (3) for 5-20h, and cooling to obtain the lithium ion battery anode material.
9. The lithium ion battery cathode material Li prepared by the preparation method of any one of claims 1 to 82Mn1- yMyO2X/C, wherein 0<y<1, M is +4 transition metal, X is halogen element, and Mn is +2 valence.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery positive electrode material according to claim 9.
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