CN113594459B - Composite negative electrode material with multilayer structure and preparation method and application thereof - Google Patents

Composite negative electrode material with multilayer structure and preparation method and application thereof Download PDF

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CN113594459B
CN113594459B CN202110845150.2A CN202110845150A CN113594459B CN 113594459 B CN113594459 B CN 113594459B CN 202110845150 A CN202110845150 A CN 202110845150A CN 113594459 B CN113594459 B CN 113594459B
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梁慧宇
沈肖楠
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Changzhou Enyuangu New Material Technology Co ltd
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Abstract

The embodiment of the invention discloses a composite negative electrode material with a multilayer structure, which has a three-layer structure comprising an inner core, a middle layer and an outer layer, wherein the inner core is artificial graphite, the middle layer is a composite layer formed by a Ce and Li-containing metal organic framework material and graphene oxide, and the outer layer is a mixture of titanium dioxide and a conductive agent. The composite cathode material is prepared by coating a metal organic framework material containing Ce and Li, graphene oxide and an aluminum-titanium composite coupling agent on artificial graphite and compounding titanium dioxide and a conductive agent on an outer layer. Under the action of the coupling agent, the metal organic framework material and the graphene oxide are easy to form a network structure to form a stable middle layer, and the lithium titanate formed by the outer titanium dioxide is also combined with the coupling agent to form a stable structure, so that the whole composite cathode material not only has higher energy density, but also has good cycle performance and rate capability.

Description

Composite negative electrode material with multilayer structure and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a composite negative electrode material with a multilayer structure, and a preparation method and application thereof.
Background
With the improvement of the energy density and the quick charge performance of the negative electrode material in the market, the graphite negative electrode material used for the lithium ion battery is required to have high energy density and the quick charge performance of the material is also required to be improved. The main ideas for improving the quick charging performance of the high-energy graphite at present are selecting raw materials with high density, graphitizing at high temperature, modifying the surface and optimizing a granulation process thereof. For example, granulation optimization: crushing the carbon material to a certain particle size, kneading to realize secondary granulation, and finally graphitizing to obtain a graphite cathode material with a secondary particle structure; the structure has the defects that the capacity and the quick charging performance are difficult to be considered, and if easily graphitized raw materials are selected, the capacity can be ensured but the quick charging performance is poorer; if the non-graphitizable raw material is selected, the quick charging performance is better but the capacity is lower. Surface modification: crushing a carbon material to a certain particle size, carrying out surface modification, and finally carbonizing to obtain a graphite negative electrode material with a primary particle structure; the structure has the defects that the capacity is difficult to improve without graphitization treatment, and the surface modification can reduce the interface impedance and improve the quick charging performance, but the diffusion path of the primary particle structure is longer, so that the quick charging performance is negatively influenced to a certain extent. Surface coating: materials with high electronic and ionic conductivity, such as N-doped and beta-doped hard carbon materials, are coated, but the rate of the material is increased to a limited extent.
The transition metal organic framework material is a novel organic-inorganic hybrid crystalline porous material, has the advantages of various structures and pore paths, adjustable size, excellent thermal stability, chemical stability and the like, and is applied to batteries at present. While carboxylic acid ligands have significant advantages in building framework structures, such as: the solubility is relatively good, the coordination capacity is relatively strong, the generated framework structure has high thermal stability and a porous structure, more importantly, oxygen atoms in carboxyl participate in coordination, and the coordination mode is various with metal ions, so that various structural framework structures can be formed, the liquid retention capacity and the lithium storage capacity of the material are improved, and the dynamic performance and the cycle performance of the material are improved.
Disclosure of Invention
In order to solve the problem that the energy density and the quick charge performance of the battery cathode material in the prior art can not be considered at the same time, the invention provides the composite cathode material with the multilayer structure, which has higher energy density and excellent quick charge performance.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the technical purpose of the first aspect of the invention is to provide a composite anode material with a multilayer structure, which has a three-layer structure comprising an inner core, an intermediate layer and an outer layer, wherein the inner core is graphite, the intermediate layer is a composite layer formed by a Ce and Li-containing metal organic framework material and graphene oxide, and the outer layer is a mixture of titanium dioxide and a conductive agent.
Furthermore, the thickness of the inner core, the middle layer and the outer layer is 100 (5-20): (5-20), preferably 100 (10-15): 10-15.
Further, the titanium dioxide is beta-type titanium dioxide and has a bronze ore structure.
Further, the weight ratio of the titanium dioxide to the conductive agent in the outer layer is (1-5) to (1-5); the conductive agent is selected from at least one of carbon nano tube, graphene, nano carbon fiber, hollow carbon sphere and super carbon black.
Further, the metal-organic framework material containing Ce and Li is C10H2CeLiO8The catalyst is obtained by carrying out hydrothermal reaction on a mixture of pyromellitic acid, a cerium source, a lithium source and water. In a more specific embodiment, the cerium-containing pyromellitic acid and water.
Furthermore, the mass ratio of the metal organic framework material containing Ce and Li to the graphene oxide in the intermediate layer is (1-5) to (1-5).
Furthermore, the D50 of the composite negative electrode material with the multilayer structure is 5-20 μm, and preferably 10-15 μm.
The technical object of the second aspect of the present invention is to provide a method for preparing a composite anode material having a multilayer structure, comprising the steps of:
preparation of a Ce and Li containing metal organic framework material: mixing pyromellitic acid, a cerium source, a lithium source and water, placing the mixture in a high-pressure reaction kettle, and reacting for 24-72 hours at the temperature of 150-200 ℃ to obtain a Ce and Li-containing metal organic framework material;
preparing a composite anode material precursor: dispersing a Ce and Li metal organic framework material, graphene oxide and an aluminum-titanium composite coupling agent in a medium for ball milling to obtain coating liquid slurry A, adding artificial graphite into the coating liquid slurry A, and performing spray drying after dispersion to obtain a Ce and Li containing metal organic framework material and a graphene oxide coated artificial graphite composite anode material precursor;
preparing a multilayer composite negative electrode material: mixing titanium dioxide and a conductive agent in a dispersion medium to obtain a coating solution C, adding a composite negative electrode material precursor into the coating solution C, drying and carbonizing to obtain the composite negative electrode material with the multilayer structure.
In the preparation method, the prepared metal organic framework material containing Ce and Li is C10H2CeLiO8The weight ratio of pyromellitic acid, cerium source, lithium source and water is (0.5-1): 1-2): 0.1-0.2): 50.
In the preparation method, the preparation process of the metal organic framework material containing Ce and Li further comprises the processes of filtering a product after hydrothermal reaction, washing the product for multiple times by using ethanol and water and drying the product in vacuum.
In the above preparation method, the cerium source is cerium sulfate, and the lithium source is lithium carbonate.
In the preparation method, the particle size D50 of the artificial graphite is 5-12 μm.
In the preparation method, the weight ratio of the Ce-and-Li-containing metal organic framework material to the graphene oxide to the aluminum-titanium composite coupling agent to the artificial graphite is (1-5): 100; wherein the weight ratio of the Ce-and-Li-containing metal organic framework material to the graphene oxide to the aluminum-titanium composite coupling agent is preferably (1-2): 1-2).
In the above production method, the dispersion medium is selected from one of N-methylpyrrolidone, carbon tetrachloride, cyclohexane, N-dimethylformamide and xylene.
In the preparation method, the weight volume ratio of the titanium dioxide, the conductive agent and the dispersion medium is (1-5) g to (1-5) 100mL, and the weight volume ratio of the composite negative electrode material precursor to the coating liquid C is 1g to (1-12) mL, preferably 1g to (1-5) mL.
In the above preparation method, the titanium dioxide is a beta-type titanium dioxide and has a bronze ore structure.
In the above preparation method, the conductive agent is at least one selected from the group consisting of carbon nanotubes, graphene, carbon nanofibers, hollow carbon spheres and super carbon black.
In the preparation method, the carbonization is carried out by heating to 800-1100 ℃ in an inert atmosphere, preserving the heat for 1-12 h, and then naturally cooling in the inert atmosphere.
The technical purpose of the third aspect of the present invention is to provide the application of the composite anode material having a multilayer structure as described above as a battery anode material.
According to the composite cathode material, the artificial graphite is coated with a double-layer structure, and the Ce and Li containing metal organic frame material in the middle layer and the graphene can form a network structure, so that the composite cathode material has the advantage of high material capacity; lithium titanate formed by the titanium dioxide on the outer layer in the charging and discharging process has high ionic conductivity, the three-layer composite structure of the composite negative electrode material exerts the synergistic effect of the three, and the cycle performance and the rate performance of the material can be improved while the energy density of the material is improved.
The embodiment of the invention has the following beneficial effects:
(1) the material of the invention takes artificial graphite as a core, a composite cathode material with a double-layer structure is coated outside the artificial graphite, and a composite layer formed by a Ce and Li-containing metal organic framework material and graphene oxide in the middle layer combines the porous structure and coordination capacity of the metal organic framework material, so that the material has the advantages of high capacity and strong conductivity; the composite cathode material disclosed by the invention exerts a synergistic effect among three-layer structures, and improves the energy density of the material and the cycle performance and rate capability of the material at the same time.
(2) According to the composite cathode material, the coupling effect of the aluminum-titanium composite coupling agent is utilized in the preparation process, so that the metal organic framework material and the graphene form a network structure, a transition layer with a stable structure is formed in the middle of the metal organic framework material, the titanium dioxide is coated on the outer layer, lithium titanate formed by the titanium dioxide in the charging and discharging processes is combined with the aluminum-titanium composite coupling agent to form a stable structure, the binding force between the transition layer and the outer layer is improved, the whole composite cathode material with the multilayer structure has good stability, and high cycle performance is kept.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
FIG. 1 is a flow chart of the preparation steps for examples 1-3;
fig. 2 SEM image of composite material with multilayer structure prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A composite anode material having a multilayer structure was prepared in examples 1 to 3 according to the procedure shown in fig. 1:
example 1
S1: preparation of Ce-and Li-containing Metal-organic framework Material C10H2CeLiO8：
Placing 0.8g of pyromellitic acid, 1.5g of cerium sulfate and 0.15g of lithium carbonate in a reaction kettle, adding 50mL of deionized water, stirring uniformly at room temperature, then transferring to a high-pressure reaction kettle, reacting at 180 ℃ for 48 hours, naturally cooling to room temperature, filtering and separating the mixture to obtain powder and crystals respectively, washing the crystals with ethanol and distilled water for 5 times respectively, and drying in vacuum to obtain C10H2CeLiO8。
S2: preparing a composite anode material precursor:
c prepared from 30g S110H2CeLiO8600mL of a 5 wt% graphene oxide N-methyl pyrrolidone solution and 30g of an aluminum-titanium composite coupling agent (OL-AT1618) are dispersed in 1000mL of dispersion medium N-methyl pyrrolidone and uniformly mixed by a high-energy ball mill to obtain a coated graphene oxide/titanium dioxide/graphene oxide/titanium dioxide composite coating solutionAdding 1000g of artificial graphite into the slurry A, uniformly dispersing, and spray-drying to obtain C10H2CeLiO8A metal organic framework material and graphene oxide coat a composite anode material precursor of artificial graphite;
s3: preparing a multilayer composite negative electrode material:
and (2) placing 30g of beta-type titanium dioxide and 30g of carbon nano tubes in 1000mL of N-methylpyrrolidone dispersion medium, uniformly mixing to obtain a coating solution C, uniformly mixing 500g of the composite negative electrode material precursor prepared by S2 with the coating solution C, drying, transferring to a tubular furnace, heating to 1000 ℃ under an argon inert atmosphere, preserving heat for 6 hours, and naturally cooling to room temperature under the argon inert atmosphere to obtain the composite negative electrode material with the multilayer structure.
Example 2
S1: preparation of Ce-and Li-containing Metal-organic framework Material C10H2CeLiO8：
Placing 0.5g of pyromellitic acid, 1g of cerium sulfate and 0.1g of lithium carbonate in a reaction kettle, adding 50mL of deionized water, stirring uniformly at room temperature, then transferring into a high-pressure reaction kettle, reacting at 150 ℃ for 72 hours, naturally cooling to room temperature, filtering and separating the mixture to obtain powder and crystals respectively, washing the crystals with ethanol and distilled water for 5 times respectively, and drying in vacuum to obtain C10H2CeLiO8。
S2: preparing a composite anode material precursor:
c prepared from 10g S110H2CeLiO8Dispersing 1000mL of 1 wt% graphene oxide solution and 10g of aluminum-titanium composite coupling agent (OL-AT1618) in 500mL of carbon tetrachloride dispersion medium, uniformly mixing by using a high-energy ball mill to prepare coating solution slurry A, adding 1000g of artificial graphite, uniformly dispersing, and spray drying to obtain C10H2CeLiO8A metal organic framework material and graphene oxide coat a composite anode material precursor of artificial graphite;
s3: preparing a multilayer composite negative electrode material:
placing 10g of beta-type titanium dioxide and 10g of graphene conductive agent in 1000mL of carbon tetrachloride dispersion medium, and uniformly mixing to obtain a coating solution C; and (3) uniformly mixing 100g of the precursor of the composite negative electrode material prepared in the step S2 with the coating liquid C, drying, transferring to a tubular furnace, heating to 800 ℃ in an argon inert atmosphere, preserving heat for 12 hours, and naturally cooling to room temperature in the argon inert atmosphere to obtain the composite negative electrode material with the multilayer structure.
Example 3
S1: preparation of Ce-and Li-containing Metal-organic framework Material C10H2CeLiO8：
Placing 1g of pyromellitic acid, 2g of cerium sulfate and 0.2g of lithium carbonate in a reaction kettle, adding 50mL of deionized water, stirring uniformly at room temperature, then transferring to a high-pressure reaction kettle, reacting at 200 ℃ for 24 hours, naturally cooling to room temperature, filtering and separating the mixture to obtain powder and crystals respectively, washing the crystals with ethanol and distilled water for 5 times respectively, and drying in vacuum to obtain C10H2CeLiO8。
S2: preparing a composite anode material precursor:
c prepared from 50g S110H2CeLiO81600mL of graphene oxide solution with the content of 3 wt% and 50g of aluminum-titanium composite coupling agent (OL-AT1618) are dispersed in 2000mL of cyclohexane, uniformly mixed by a high-energy ball mill to prepare coating liquid slurry A, then 1000g of artificial graphite is added into the coating liquid slurry A, and after uniform dispersion, spray drying is carried out to obtain precursor composite negative electrode material BETA of the artificial graphite coated with the transition metal oxide;
s3: preparing a multilayer composite negative electrode material:
and (2) putting 50g of beta-type titanium dioxide and 50g of carbon fiber into 1000mL of cyclohexane dispersion medium, uniformly mixing to obtain a coating solution C, uniformly mixing 500g of the composite negative electrode material precursor prepared in the step S2 with the coating solution C, drying, transferring to a tubular furnace, heating to 1100 ℃ in an argon inert atmosphere, preserving heat for 1h, and naturally cooling to room temperature in the argon inert atmosphere to obtain the composite negative electrode material with the multilayer structure.
Comparative example 1
Dissolving 30g of phenolic resin in 500ml of carbon tetrachloride, uniformly dispersing, adding 100g of artificial graphite, uniformly mixing, spray-drying, transferring to a tube furnace, heating to 700 ℃ under the atmosphere of argon, preserving heat for 6 hours, cooling to room temperature under the atmosphere of argon, and crushing and grading to obtain the hard carbon coated artificial graphite composite negative electrode material.
Comparative example 2
The operation was the same as in example 1 except that no graphene oxide solution was added in step (2).
Comparative example 3
The operation was performed in the same manner as in example 1 except that the aluminum-titanium composite coupling agent was not added in the step (2).
Comparative example 4
The operation was the same as in example 1 except that the graphene oxide in step (2) was replaced with super carbon black.
Performance testing of the materials prepared in the above examples and comparative examples:
(1) SEM test
The composite anode material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the composite negative electrode material prepared in example 1 is granular and has a uniform size distribution, and the particle size D50 is between (8-15) μm.
(2) Testing the powder conductivity:
the composite negative electrode material powder in the examples and the comparative examples is pressed into a block structure, and the conductivity of the powder is tested by adopting a four-probe tester. The test results are shown in table 1.
(3) Powder compaction Density test
The composite anode materials in examples and comparative examples were subjected to a powder compaction density test. During testing, powder with a certain mass is weighed and placed in a mold, 2T pressure pressing is adopted (1 g of powder is placed in a fixed kettle by adopting a powder compaction density instrument, 2T pressure pressing is adopted, the powder is kept still for 10S, then the volume under pressing is calculated, the compaction density is calculated, and the powder compaction density is calculated, wherein the test results are shown in table 1.
TABLE 1
Figure BDA0003180227900000081
As can be seen from table 1, the powder resistivity of the composite negative electrode material prepared by the invention is obviously lower than that of the comparative example, because the surface of the negative electrode material is doped with a metal organic frame material containing Ce and Li with high electronic conductivity, and the metal organic frame material and graphene react to form a stable intermediate transition layer, the resistivity of the composite negative electrode material is reduced; meanwhile, the conductive agent on the outer layer improves the conductivity of the material, and on the other hand, the conductive agent has a lubricating effect and improves the compaction density of the material.
(4) Electricity withholding test
The composite negative electrode materials of the examples and comparative examples were assembled into button cells a1, a2, A3, B1, B2, B3, and B4, respectively. The assembling method comprises the following steps: and adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on copper foil, and drying and rolling to obtain the negative electrode plate. The binder used was LA132 binder, the conductive agent was SP, the negative electrode materials were the composite negative electrode materials in examples and comparative examples, respectively, and the solvent was secondary distilled water. The proportion of each component is as follows: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1g: 4 g: 220 mL; the electrolyte is LiPF6/EC + DEC (LiPF)6The concentration of the lithium ion battery is 1.3mol/L, the volume ratio of EC to DEC is 1:1), the metal lithium sheet is used as a counter electrode, and the diaphragm is a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite membrane. The button cell is assembled in a hydrogen-filled glove box, the electrochemical performance test is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V-2.0V, and the charging and discharging multiplying power is 0.1C. The first discharge capacity and the first efficiency are tested according to the GBT 243333-2009 graphite cathode material for lithium ion batteries, and the test results are shown in Table 2.
And simultaneously taking the negative plate, and testing the liquid absorption capacity of the negative plate, wherein the test method comprises the following steps: and (3) adopting a 1mL burette, sucking the electrolyte VmL, dripping a drop on the surface of the pole piece, timing until the electrolyte is completely absorbed, recording the time t, and calculating the liquid absorption speed V/t of the pole piece. The test results are shown in table 2.
TABLE 2
Figure BDA0003180227900000091
As can be seen from table 2, the first discharge capacity and the first charge-discharge efficiency of the lithium ion battery using the graphite composite negative electrode material obtained in the embodiment are significantly higher than those of the comparative example, because the stable structure formed by the metal organic framework material of the intermediate layer and the graphene has high specific capacity and conductivity, the discharge specific capacity of the material is improved, the first efficiency is further improved, and meanwhile, the high specific surface area of the graphene improves the conductivity and the liquid absorption performance of the material; meanwhile, the metal organic framework material of the middle coating layer of the embodiment is of a porous structure, has a high specific surface area, and improves the liquid absorption capacity of the material.
(5) Pouch cell testing
The composite negative electrode materials in the examples and the comparative examples are used as negative electrode materials to prepare negative electrode plates. With ternary materials (LiNi)1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6Solution (solvent EC + DEC, volume ratio 1:1, LiPF)6Concentration of 1.3mol/L) is used as electrolyte, celegard2400 is used as a diaphragm, and 2Ah soft package batteries A10, A20, A30, B10, B20, B30 and B40 are prepared. And testing the cycle performance and the rate performance of the soft package battery.
Multiplying power performance test conditions: charging rate: 1C/2C/3C/5C, discharge multiplying power of 1C; voltage range: 2.8-4.2V. The test results are shown in Table 3.
TABLE 3
Figure BDA0003180227900000101
As can be seen from table 3, the soft-package battery prepared from the composite negative electrode material has a better constant current ratio, and the reason is that the surface of the material in the embodiment is coated with lithium titanate formed by reduction of titanium dioxide, and a stable structure can be formed between the aluminum-titanium composite coupling agent and the intermediate layer, the aluminum-titanium composite coupling agent has the advantages of stabilizing the structure between the materials, reducing the internal resistance between the materials, improving the quick charging performance of the material due to high electronic conductivity of graphene, improving the high rate charging performance of the material due to high electronic conductivity of graphene, and improving the rate charging performance of the material.
Cycle performance test conditions: 25 +/-3 ℃, 1C/1C, 2.8-4.2V, and the test results are shown in Table 4.
TABLE 4
Figure BDA0003180227900000102
Figure BDA0003180227900000111
As can be seen from table 4, the cycling performance of the pouch cells in the examples is significantly better than that of the comparative examples, the analytical reasons being: the outer layer of the negative electrode material artificial graphite is coated with a layer of transition metal oxide, the transition metal oxide has a porous structure and provides sufficient lithium ions in the charging and discharging processes, the graphene has high electronic conductivity and high specific surface area, the cycle performance is improved, the structure of the coupling agent is stable in structure, the cycle performance is improved, and meanwhile, the outer layer of lithium titanate has the characteristic of stable structure, so that the cycle performance of the material is further improved.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (10)

1. The composite anode material with the multilayer structure is characterized by having a three-layer structure comprising an inner core, an intermediate layer and an outer layer, wherein the inner core is artificial graphite, the intermediate layer is a composite layer formed by a Ce and Li-containing metal organic framework material and graphene oxide, and the outer layer is a mixture of titanium dioxide and a conductive agent.
2. The composite anode material of claim 1, wherein the thickness of the inner core, the middle layer and the outer layer is 100: 5-20.
3. The composite anode material of claim 1, wherein the weight ratio of the titanium dioxide to the conductive agent in the outer layer is 1-5: 1-5; the conductive agent is selected from at least one of carbon nano tube, graphene oxide, nano carbon fiber, hollow carbon sphere and super carbon black.
4. The composite anode material according to claim 1, wherein the Ce and Li containing metal-organic framework material is C10H2CeLiO8The catalyst is obtained by carrying out hydrothermal reaction on a mixture of pyromellitic acid, a cerium source, a lithium source and water.
5. The composite anode material of claim 1, wherein the mass ratio of the metal organic framework material containing Ce and Li to the graphene oxide in the intermediate layer is 1-5: 1-5.
6. The composite anode material according to claim 1, wherein D50 of the composite anode material with the multilayer structure is 5-20 μm.
7. A preparation method of a composite anode material with a multilayer structure comprises the following steps:
preparation of a Ce and Li containing metal organic framework material: mixing pyromellitic acid, a cerium source, a lithium source and water, placing the mixture in a high-pressure reaction kettle, and reacting for 24-72 hours at the temperature of 150-200 ℃ to obtain a Ce and Li-containing metal organic framework material;
preparing a composite anode material precursor: dispersing a Ce and Li metal organic framework material, graphene oxide and an aluminum-titanium composite coupling agent in a medium for ball milling to obtain coating liquid slurry A, adding artificial graphite into the coating liquid slurry A, and performing spray drying after dispersion to obtain a Ce and Li containing metal organic framework material and a graphene oxide coated artificial graphite composite anode material precursor;
preparing a multilayer composite negative electrode material: mixing titanium dioxide and a conductive agent in a dispersion medium to obtain a coating solution C, adding a composite negative electrode material precursor into the coating solution C, drying and carbonizing to obtain the composite negative electrode material with the multilayer structure.
8. The preparation method of claim 7, wherein the weight ratio of the Ce and Li containing metal organic framework material, the graphene oxide, the aluminum-titanium composite coupling agent and the artificial graphite is 1-5: 100.
9. The preparation method of claim 7, wherein the weight volume ratio of the titanium dioxide, the conductive agent and the dispersion medium is 1-5 g:100mL, and the weight ratio of the composite anode material precursor to the coating solution C is 1g: 1-12 mL.
10. Use of the composite anode material having a multilayer structure prepared according to claim 1 or claim 7 as a battery anode material.
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