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CN107919473B - Preparation method of lithium ion battery electrode active material - Google Patents

Preparation method of lithium ion battery electrode active material Download PDF

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CN107919473B
CN107919473B CN201610881012.9A CN201610881012A CN107919473B CN 107919473 B CN107919473 B CN 107919473B CN 201610881012 A CN201610881012 A CN 201610881012A CN 107919473 B CN107919473 B CN 107919473B
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lithium
electrode active
active material
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metal element
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CN107919473A (en
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何向明
王莉
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Wuxi Huarui Xinneng Battery Material Co ltd
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Tsinghua University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

本发明提供一种锂离子电池电极活性材料的制备方法，包括提供锂源溶液和金属元素源；将该锂源溶液与该金属元素源混合反应；将反应产物干燥，得到前驱体；以及热处理该前驱体。本发明还提供一种锂离子电池电极活性材料的制备方法，该制备方法为固相合成法，该固相合成法在原料混合阶段包括将萘锂与金属元素源在溶剂中进行化学反应的步骤。

Figure 201610881012

The invention provides a method for preparing an electrode active material for a lithium ion battery, which includes providing a lithium source solution and a metal element source; mixing and reacting the lithium source solution with the metal element source; drying the reaction product to obtain a precursor; and heat-treating the Precursor. The present invention also provides a preparation method of an electrode active material for a lithium ion battery, the preparation method is a solid-phase synthesis method, and the solid-phase synthesis method includes the step of chemically reacting lithium naphthalene and a metal element source in a solvent in the raw material mixing stage .

Figure 201610881012

Description

Preparation method of lithium ion battery electrode active material
Technical Field
The invention relates to the field of energy materials, in particular to a preparation method of an electrode active material of a lithium ion battery.
Background
With the rapid development and generalization of portable electronic products, the market demand of lithium ion batteries is increasing day by day. Compared with the traditional secondary battery, the lithium ion battery has the advantages of high energy density, long cycle life, no memory effect, small environmental pollution and the like.
The positive electrode and the negative electrode of the lithium ion battery respectively contain a reversible lithium intercalation material as an active material, wherein the positive electrode active material has a higher potential than the negative electrode active material. The commonly used positive active material is mainly a lithium transition metal composite oxide or a lithium transition metal phosphate, such as lithium cobaltate, lithium manganate, a binary material, a ternary material, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate and the like, and the commonly used negative active material is mainly a carbon material, such as graphite, and in addition, a lithium transition metal composite oxide, such as lithium titanate and the like, is also available.
The above-mentioned lithium transition metal composite oxide and lithium transition metal phosphate can be synthesized by a solid-phase synthesis method, a hydrothermal/solvothermal reaction method, a coprecipitation synthesis method, a sol-gel synthesis method, or the like. Among them, the solid phase synthesis method is the most industrially used synthesis method, and specifically, a precursor containing a transition metal, such as an oxide, a carbonate or a hydroxide, is mechanically mixed with a lithium source, such as lithium carbonate or lithium hydroxide, by ball milling, and then sintered at a high temperature. However, in this preparation method, the precursor is mixed with the lithium source at the level of solid particles, resulting in poor homogeneity of the mixture and unstable material properties of the synthesized product.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing an electrode active material for a lithium ion battery to solve the above problems.
A method for preparing an electrode active material of a lithium ion battery, comprising:
s1, providing a lithium source solution and a metal element source, wherein the lithium source solution comprises a solvent and at least one of lithiated fused cyclic aromatic hydrocarbon and lithiated fused cyclic aromatic hydrocarbon derivatives dissolved in the solvent;
s2, mixing and reacting the lithium source solution with the metal element source;
s3, drying the reaction product obtained in the step S2 to obtain a precursor; and
and S4, heat treating the precursor.
A preparation method of an electrode active material of a lithium ion battery is a solid-phase synthesis method, and the solid-phase synthesis method comprises the step of carrying out chemical reaction on at least one of lithiated fused cyclic aromatic hydrocarbon and derivatives of the lithiated fused cyclic aromatic hydrocarbon and a metal element source in a solvent at a raw material mixing stage.
According to the invention, at least one of lithiated fused cyclic aromatic hydrocarbon and derivatives of lithiated fused cyclic aromatic hydrocarbon is used as a lithium source in solid phase synthesis, and the lithium source and other metal element sources are mixed in a molecular layer by performing a chemical reaction in the step S2 when the lithium source is mixed with the other metal element sources, so that the reaction in the solid phase synthesis in the step S4 is ensured to be more uniform and free from segregation, and the obtained electrode active material has better performance.
Drawings
FIG. 1 is a flow chart of a method of preparing an electrode active material for a lithium ion battery according to an embodiment of the present invention;
FIG. 2 is an XRD test pattern of an electrode active material of a lithium ion battery according to an embodiment of the present invention;
FIG. 3 is a graph comparing the voltage capacity curves of the lithium ion batteries of example 1 of the present invention and the comparative example;
fig. 4 is a graph comparing the cycle performance of the lithium ion batteries of example 1 of the present invention and the comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the following description will be made in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing an electrode active material of a lithium ion battery, including:
s1, providing a lithium source solution and a metal element source, wherein the lithium source solution comprises a solvent and at least one of lithiated fused cyclic aromatic hydrocarbon and lithiated fused cyclic aromatic hydrocarbon derivatives dissolved in the solvent;
s2, mixing and reacting the lithium source solution with the metal element source;
s3, drying the reaction product obtained in the step S2 to obtain a precursor; and
and S4, heat treating the precursor.
The lithium source is at least one of lithiated fused cyclic aromatic hydrocarbon and derivatives of lithiated fused cyclic aromatic hydrocarbon. The lithiated fused ring aromatic hydrocarbon is a compound of lithium and fused ring aromatic hydrocarbon. The derivative of the lithiated fused ring aromatic hydrocarbon has similar properties to the lithiated fused ring aromatic hydrocarbon, and the derivative of the lithiated fused ring aromatic hydrocarbon can be a substance formed by substituting a halogen atom or an alkyl group with 1-6 carbon atoms for a hydrogen atom in the fused ring aromatic hydrocarbon, and the derivative of the lithiated fused ring aromatic hydrocarbon is a compound of the derivative of the fused ring aromatic hydrocarbon and lithium. The general formula of the lithiated fused cyclic aromatic hydrocarbon and the lithiated fused cyclic aromatic hydrocarbon derivative can be written as LiX, wherein X represents at least one of the fused cyclic aromatic hydrocarbon and the lithiated fused cyclic aromatic hydrocarbon derivative. The number of benzene rings of the fused ring aromatic hydrocarbon is preferably 2 to 4.
The lithiated fused ring aromatic hydrocarbon is preferably lithium naphthalene (LiC)10H8) Lithium pyrene (LiC)16H10) Lithium phenanthrene (LiC)14H10) And anthracene Lithium (LiC)14H10) At least one of (1). The solvent can dissolve the lithiated fused cyclic aromatic hydrocarbon, and is chemically stable to the dissolved lithiated fused cyclic aromatic hydrocarbon. For example, the solvent of the lithium naphthalene may be at least one of Tetrahydrofuran (THF), Ethylene Carbonate (EC), diethyl carbonate (DEC), Propylene Carbonate (PC), dimethyl carbonate (DMC) and hexane. The concentration of the lithiated fused cyclic aromatic hydrocarbon in the lithium source solution is preferably 0.05 to 0.6 mol/L. For example, when the lithium source solution is a naphthalene lithium solution, the concentration of naphthalene lithium is0.05 to 0.6 mol/L.
In one embodiment, the lithium naphthalene solution can be prepared by:
s11, dissolving naphthalene in the solvent in vacuum or protective atmosphere; and
and S12, adding metal lithium into the solvent to react with naphthalene to obtain the lithium naphthalene solution.
The step of reacting the metallic lithium with naphthalene may be performed at normal temperature and pressure, for example, at 20 ℃ to 40 ℃ under 1 atmosphere. The addition amount of the naphthalene and the lithium metal in the solvent can be determined by the concentration of the lithium naphthalene solution to be obtained. The molar ratio between the naphthalene and the lithium metal may be 1: 1.
Other lithium source solutions may be prepared by the same or different methods as the above-described lithium naphthalene solutions.
The metal element source is determined by synthesized target electrode active material, which can be positive electrode active material or negative electrode active material, specifically lithium metal composite oxide (Li-M-O) and lithium metal composite phosphate (Li-N-PO)4) At least one of (1). The metal element M includes at least one of nickel, cobalt and manganese, and may further include a doping element in some embodiments. The metal element N includes at least one of nickel, cobalt, manganese, iron, and vanadium, and may further include a doping element in some embodiments. When the electrode active material is a negative electrode active material, the lithium metal composite oxide may also be Li-Ti-O. The electrode active material has reversible charge and discharge performance, and can enable lithium ions to be reversibly inserted and extracted at different potentials.
More specifically, the electrode active material may have a crystal structure of a-NaFeO2At least one of a lithium metal composite oxide and a lithium metal composite phosphate having a layer-type structure, a spinel-type structure, or an olivine-type structure.
The chemical formula of the lithium metal composite oxide may be, for example, LiFe1-yLyPO4，LiMn1-yLyPO4，LiV1-yLyPO4，LiCo1-yLyPO4，LiFe1-yLy(PO4)1-kF3k，LiMn1-yLy(PO4)1-kF3k，LiCo1-yLy(PO4)1-kF3k，LiNi1-yLy(PO4)1-kF3k，LiV1-yLy(PO4)1-kF3k，LiNi1-yLyPO4，LixNi1-yLyO2，LixCo1-yLyO2，LixMn1-yLyO2，LixMn2-zLzO4，LixNii-nMnj-mLnRmO4，LixNii-nCoj-mLnRmO4，LixCoi-nMnj-mLnRmO4，LixNidCoeMnfLgO2And LixNidCoeAlfLgO2At least one of (1).
In the above formula, 0.1. ltoreq. x.ltoreq.1.1, 0. ltoreq. y <1, i + j.2, 0. ltoreq. m <0.2, 0. ltoreq. n <0.2, 0< i-n <2, 0< j-m <2, 0< d <1, 0< e <1, 0< f <1, 0. ltoreq. g.ltoreq.0.2, 0< k <1, d + e + f + g + g.ltoreq.1, 0. ltoreq. z <2, preferably, 0. ltoreq. z <0.1, 0.1< y < 0.5. Wherein, L and R are doping elements and are selected from one or more of alkali metal elements, alkaline earth metal elements, group 13 elements, group 14 elements, transition group elements and rare earth elements, preferably, L and R are selected from at least one of Co, Ni, Mn, Cr, V, Ti, Sn, Cu, Al, Fe, B, Sr, Ca, Nd, Ga and Mg.
More preferably, the positive electrode active material is lithium cobaltate (LiCoO) having a layered structure2) Lithium manganate (LiMnO)2) Lithium nickelate (LiNiO)2) Lithium nickel cobalt manganese oxides, e.g. LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.6Mn0.2Co0.2O2、LiNi0.8Co0.1Mn0.1O2And LiNi0.7Co0.2Mn0.1O2Spinel type lithium manganate (LiMn)2O4) Spinel-type lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Lithium iron phosphate (LiFePO)4) Lithium manganese phosphate (LiMnPO)4) Lithium vanadium phosphate (LiVPO)4) Lithium manganese iron phosphate (LiFe)0.5Mn0.5PO4) Lithium cobalt phosphate (LiCoPO)4) And lithium nickel phosphate (LiNiPO)4) May be lithium titanate (Li), the negative active material may be lithium titanate (Li)4Ti5O12)。
The metal element source is a compound of a source of a metal element other than lithium in the electrode active material, and is used for providing the metal element other than lithium in the electrode active material. The metal element source may be at least one of hydroxide, carbonate, oxalate, phosphate and organic acid salt of one or more metal elements (such as one or more of iron, cobalt, nickel, manganese, titanium, vanadium or other doping elements), for example.
It is to be understood that the step S2 is a step of mixing reaction raw materials for preparing an electrode active material by a solid phase synthesis method, the reaction raw materials depending on the electrode active material to be synthesized, and when the reaction raw materials include other raw materials, the step S2 further includes a step of mixing the lithium source solution, the metal element source, and other raw materials, and reacting at least the lithium source solution with the metal element source. For example, when the electrode active material is a lithium metal composite phosphate, the other raw material may be Phosphate (PO)4 3-) A source, the step S1 further comprising providing a phosphate source, the step S2 further comprising mixing and reacting the lithium source solution, the metal element source and the phosphate source. The phosphate source may be at least one of iron phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, for example.
The source of the metal element that reacts with the lithium source solution is preferably free of water, including free water, adsorbed water, and crystal water. More preferably, the method further includes a step of drying the metal element source before performing step S2. The drying atmosphere is preferably a vacuum or a protective gas. The drying temperature is preferably less than 100 ℃, for example at 60 ℃ to 80 ℃.
In step S2, the lithium source and the metal element source are chemically reacted in the solvent, and the chemical reaction may be performed at normal temperature and normal pressure, for example, at 20 ℃ to 40 ℃ and 1 atmosphere. More preferably, the reaction is carried out in a protective atmosphere. The protective atmosphere is preferably nitrogen or a noble gas, such as argon. The lithium source solution and the metal element source may be mixed and then the reaction may be promoted by stirring. The lithium source and the metal element source may be mixed in a stoichiometric ratio, i.e., a molar ratio of lithium to metal element in the final electrode active material. In a preferred embodiment, the lithium source may be in stoichiometric excess, e.g., 1% to 5% excess, relative to the source of the metal element. In step S2, the original mechanical mixing is changed into a chemical reaction in the solid-phase synthesis reaction method, so that the lithium and the metal element source are mixed at the molecular level, and the lithium and the metal element in the precursor used in the subsequent sintering are more uniformly mixed and are less prone to segregation, thereby obtaining an electrode active material with better performance.
In this step S3, the solvent is removed by drying, and a reaction product of the lithium source and the metal element source is obtained. After this step S3, the product may be further ground to refine the solid particles. The drying temperature is preferably less than 100 ℃, for example at 60 ℃ to 80 ℃.
In the step S4, the temperature of the heat treatment may be 500 to 900 ℃. The heat treatment may be carried out at normal pressure, for example at 1 atmosphere. The heat treatment may be performed in air. The heat treatment time at 500 to 900 ℃ is preferably 200 to 720 minutes. And naturally cooling the product after the heat treatment to room temperature to obtain the electrode active material.
The embodiment of the invention also provides a preparation method of the lithium ion battery electrode active material, which is a solid phase synthesis method, wherein the solid phase synthesis method comprises the step of carrying out chemical reaction on at least one of lithiated fused cyclic aromatic hydrocarbon and lithiated fused cyclic aromatic hydrocarbon derivatives serving as a lithium source and other metal element sources except lithium in a solvent at a raw material mixing stage.
According to the invention, at least one of lithiated fused cyclic aromatic hydrocarbon and derivatives of lithiated fused cyclic aromatic hydrocarbon is used as a lithium source in solid phase synthesis, and the lithium source and other metal element sources are mixed in a molecular layer by performing a chemical reaction in the step S2 when the lithium source is mixed with the other metal element sources, so that the reaction in the solid phase synthesis in the step S4 is ensured to be more uniform and free from segregation, and the obtained electrode active material has better performance.
Example 1: positive electrode active material LiNi1/3Co1/3Mn1/3O2Preparation of
S1, adding Ni as metal element source1/3Co1/3Mn1/3(OH)2Drying in a vacuum drying oven at 60 deg.C for 12 hr; dissolving 0.5-0.74 g of naphthalene in Tetrahydrofuran (THF) in a glove box, adding an excessive stoichiometric lithium sheet (lithium is excessive by about 5 percent relative to a metal element source), and stirring and reacting for 24-48 hours at normal temperature and normal pressure to form a stable naphthalene lithium solution;
s2, taking 5g of dried metal element source Ni1/3Co1/3Mn1/3(OH)2Adding the mixture into the naphthalene lithium solution and continuously stirring to promote the reaction;
s3, after complete reaction, drying to remove THF, and obtaining a solid mixture; and
and S4, grinding the solid mixture, respectively carrying out heat treatment at different temperatures, and heating the solid mixture from room temperature to the heat treatment temperature at a heating rate of 3 ℃/min before the heat treatment. The heat treatment temperature and time are respectively 500 ℃ heat preservation for 200-300 min, 600 ℃, 700 ℃, 800 ℃ and 900 ℃ heat preservation for 480-720 min. The product of step S4 is naturally cooled to room temperature after the heat treatment is finished.
Referring to FIG. 2, XRD tests were conducted on the products obtained by the heat treatment at different temperatures, and the results showed that the product synthesized in the heat treatment temperature range was LiNi1/3Co1/3Mn1/3O2The crystal has obvious layered structure, single crystal phase and no impurity phase, and the crystallinity is improved along with the temperature rise.
LiNi obtained by heat treatment at 800 DEG C1/3Co1/3Mn1/3O2The half cell was assembled as a positive electrode active material. The positive plate adopts acetylene black as a conductive agent, PVDF as a binder, the mass ratio of the positive active material to the acetylene black to the PVDF is 8:1:1, a metal lithium plate is used as a counter electrode, and 1mol/L LiPF is used6And adopting the/EC + DMC + EMC (volume ratio of 1:1:1) as electrolyte, assembling the electrolyte into a CR2032 type button cell in an argon glove box, and standing for 12 hours to perform electrochemical performance test on the cell. Referring to fig. 3, the specific capacity of the battery discharged with a constant current of 0.1C is 152mAhg-1. Referring to fig. 4, the battery was subjected to a constant current charge-discharge cycle test at 1C, and the specific discharge capacity of the battery after 50 cycles was about 117mAhg-1。
Comparative example
Lithium hydroxide as lithium source and Ni as metal element source1/3Co1/3Mn1/3(OH)2Ball milling and mixing for 12 hours to obtain a solid mixture; and
the solid mixture was heat-treated at 800 ℃ at the same rate and for the same holding time as in example 1 to obtain LiNi, a positive electrode active material1/3Co1/3Mn1/3O2。
The positive electrode active material is assembled into a CR2032 button cell by the same method as the embodiment 1, and the cell is subjected to electrochemical performance test after standing for 12 h. Referring to fig. 3, the specific capacity of the battery discharged with a constant current of 0.1C is 145mAhg-1. Referring to fig. 4, the battery was subjected to a constant current charge-discharge cycle test at a current of 1C, and the specific discharge capacity of the battery after 50 cycles was about 108mAhg-1. By comparison, the capacity retention rate of the active material synthesized by the method is about 88% after 50 current cycles of the 1C current cycle in the conventional solid phase method, and the capacity retention rate of the active material synthesized by the method is more than 90% after 50 current cycles of the 1C current cycle.
Example 2: LiFePO as positive electrode active material4Preparation of
S1, mixing the ferric chloride solution with ammonium phosphateFully reacting, adding buffer solution, adjusting pH value to 3-4, reacting for more than 5h, washing with water for two to three times, and drying at 100 deg.C to obtain FePO4The precursor is prepared by using ferric chloride with the concentration of 0.5mol/L, ammonium phosphate with the concentration of 0.5mol/L and the molar ratio of ferric chloride to ammonium phosphate of 1: 1; dissolving 0.38g of naphthalene in Tetrahydrofuran (THF) in a glove box, adding an excessive stoichiometric amount of lithium sheets (lithium is excessive by about 2-3% (molar ratio) relative to a metal element source), and stirring and reacting for 24-48 hours at normal temperature and normal pressure to form a stable naphthalene lithium solution;
s2, the FePO is reacted4Adding the precursor into the stable naphthalene lithium solution and continuously stirring to promote the reaction;
s3, after complete reaction, drying to remove THF, and obtaining a solid mixture; and
s4, mixing the solid mixture with a reducing agent, and then carrying out heat treatment for 8 hours at 700 ℃ in a nitrogen atmosphere to obtain the anode active material LiFePO4The reducing agent may be carbon black, sucrose or glucose.
Example 3: negative electrode active material Li4Ti5O12Preparation of
S1, dissolving 1g of naphthalene in Tetrahydrofuran (THF) in a glove box, adding excessive stoichiometric lithium sheets (Ti: Li ═ 1.22), and stirring and reacting at normal temperature and pressure for 24-48 hours to form a stable lithium naphthalene solution;
s2, mixing TiO2Mixing with naphthalene lithium solution and continuously stirring to promote reaction;
s3, drying to remove THF after complete reaction to obtain a solid mixture; and
s4, heat treating the solid mixture in air at 700 ℃ to obtain Li4Ti5O12。
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1.一种锂离子电池电极活性材料的固相合成制备方法，包括：1. A solid-phase synthesis preparation method of a lithium-ion battery electrode active material, comprising: S1，提供电极活性材料固相合成的原料，包括锂源溶液和金属元素源，该锂源溶液包括溶剂及溶解于该溶剂的锂化稠环芳香烃及锂化稠环芳香烃的衍生物中的至少一种，该金属元素源为所述电极活性材料中除锂外的金属元素来源化合物，该金属元素源不含水；S1, providing raw materials for solid-phase synthesis of electrode active materials, including a lithium source solution and a metal element source, the lithium source solution including a solvent and lithiated fused-ring aromatic hydrocarbons and derivatives of lithiated fused-ring aromatic hydrocarbons dissolved in the solvent At least one of, the metal element source is a metal element source compound other than lithium in the electrode active material, and the metal element source does not contain water; S2，在所述电极活性材料固相合成的原料混合阶段，将该锂源溶液与该金属元素源混合并反应；S2, in the raw material mixing stage of the solid-phase synthesis of the electrode active material, mixing and reacting the lithium source solution with the metal element source; S3，将该步骤S2的反应产物干燥，得到前驱体；以及S3, drying the reaction product of step S2 to obtain a precursor; and S4，在500℃至900℃热处理该前驱体。S4, heat treating the precursor at 500°C to 900°C. 2.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该锂化稠环芳香烃为萘锂、芘锂、菲锂及蒽锂中的至少一种。2. the solid-phase synthesis preparation method of lithium ion battery electrode active material according to claim 1, is characterized in that, this lithiated fused-ring aromatic hydrocarbon is at least one in naphthalene lithium, pyrene lithium, phenanthrene lithium and anthracene lithium . 3.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该锂源溶液包括溶剂及溶解在该溶剂中的萘锂，该溶剂选自四氢呋喃、碳酸乙烯酯、碳酸二乙酯、碳酸丙烯酯、碳酸二甲酯及己烷中的至少一种。3. The solid-phase synthesis preparation method of lithium ion battery electrode active material according to claim 1, wherein the lithium source solution comprises a solvent and lithium naphthalene dissolved in the solvent, and the solvent is selected from tetrahydrofuran, ethylene carbonate At least one of ester, diethyl carbonate, propylene carbonate, dimethyl carbonate and hexane. 4.根据权利要求3所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该锂源溶液中萘锂的浓度为0.05至0.6mol/L。4 . The method for preparing solid-phase synthesis of electrode active materials for lithium ion batteries according to claim 3 , wherein the concentration of lithium naphthalene in the lithium source solution is 0.05 to 0.6 mol/L. 5 . 5.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该电极活性材料是锂金属复合氧化物及锂金属复合磷酸盐中的至少一种。5 . The method for preparing solid-phase synthesis of electrode active materials for lithium ion batteries according to claim 1 , wherein the electrode active materials are at least one of lithium metal composite oxides and lithium metal composite phosphates. 6 . 6.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该电极活性材料是晶体结构为а-NaFeO2型层状结构、尖晶石型结构或橄榄石型结构的锂金属复合氧化物及锂金属复合磷酸盐中的至少一种。6. the solid-phase synthesis preparation method of lithium ion battery electrode active material according to claim 1, is characterized in that, this electrode active material is that the crystal structure is α-NaFeO 2 type layered structure, spinel type structure or olive At least one of lithium metal composite oxides and lithium metal composite phosphates with a stone structure. 7.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该金属元素源为该金属元素的氢氧化物、碳酸盐、草酸盐、磷酸盐及有机酸盐中的至少一种。7. The method for preparing solid-phase synthesis of electrode active materials for lithium ion batteries according to claim 1, wherein the metal element source is hydroxide, carbonate, oxalate, phosphate and At least one of organic acid salts. 8.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，当该电极活性材料为锂金属复合磷酸盐时，该步骤S1进一步包括提供磷酸根源，该步骤S2进一步包括将该锂源溶液、该金属元素源与该磷酸根源混合的步骤。8. The solid-phase synthesis preparation method of lithium ion battery electrode active material according to claim 1, is characterized in that, when this electrode active material is lithium metal composite phosphate, this step S1 further comprises providing phosphate source, this step S2 further includes the step of mixing the lithium source solution, the metal element source and the phosphate source. 9.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该步骤S2在常温常压下进行。9 . The method for preparing solid-phase synthesis of electrode active materials for lithium ion batteries according to claim 1 , wherein the step S2 is carried out at normal temperature and normal pressure. 10 . 10.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，该金属元素源不含水为与该锂源溶液反应的该金属元素源不含自由水、吸附水和结晶水。10. The solid-phase synthesis preparation method of lithium ion battery electrode active material according to claim 1, wherein the metal element source does not contain water because the metal element source reacted with the lithium source solution does not contain free water, adsorption water and crystal water. 11.根据权利要求1所述的锂离子电池电极活性材料的固相合成制备方法，其特征在于，在进行该步骤S2之前，进一步包括将该金属元素源进行干燥的步骤。11 . The solid-phase synthesis preparation method of an electrode active material for a lithium ion battery according to claim 1 , wherein, before the step S2 is performed, it further comprises a step of drying the metal element source. 12 .
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