CN108183225B - Cerium-titanium-oxide cluster/poly-3, 4-ethylene dioxythiophene composite material and preparation method and application thereof - Google Patents

Cerium-titanium-oxide cluster/poly-3, 4-ethylene dioxythiophene composite material and preparation method and application thereof Download PDF

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CN108183225B
CN108183225B CN201711486642.7A CN201711486642A CN108183225B CN 108183225 B CN108183225 B CN 108183225B CN 201711486642 A CN201711486642 A CN 201711486642A CN 108183225 B CN108183225 B CN 108183225B
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cerium
titanium
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ethylenedioxythiophene
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CN108183225A (en
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张�诚
陈钧
吕耀康
王天佑
蒯羽
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Zhejiang University of Technology ZJUT
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material, which is prepared by the following steps: firstly, the cerium-containing titanium-oxygen cluster [ Ti ] is prepared by a hydrothermal method8O7(HOEt)(OEt)21Ce]A crystal; secondly, cerium-titanium-oxygen cluster [ Ti8O7(HOEt)(OEt)21Ce]Dissolving the crystal and EDOT in a dichloromethane solution, adding an initiator p-toluenesulfonic acid, stirring and reacting for 48-56 h, then carrying out suction filtration on the reaction solution, washing a filter cake with deionized water, and placing the filter cake in an oven to carry out vacuum drying at 60-70 ℃ for 20-24 h to obtain the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material; the prepared composite material can be applied to a lithium ion battery cathode material, and has high discharge specific capacity and good cycle stability.

Description

Cerium-titanium-oxide cluster/poly-3, 4-ethylene dioxythiophene composite material and preparation method and application thereof
Technical Field
The invention relates to a cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material and a preparation method and application thereof.
Background
Electrochemical energy storage devices have recently received much attention due to their excellent cycle stability and good durability. The lithium ion battery is a popular research object by virtue of the advantages of light weight, small volume, portability, high energy, high power density, long cycle life, no memory effect, environmental friendliness and the like.
The titanium-oxygen cluster is a monodisperse nano molecular system, the basic framework of the titanium-oxygen cluster is a cage-shaped molecular cluster which is constructed by connecting a plurality of titanium atoms through oxygen bridges, and the diameter of the cage-shaped molecular cluster is between 0.5 and 2.0 nm. The titanium clusters can be regarded as titanium oxide nanocrystals with smaller size and organic functional groups on the surface, have higher electron transmission and ion storage capacities, are rich in chemical composition and controllable in spatial structure, and show wide application prospects in the fields of functional materials such as light, electricity and magnetism.
Conductive polymers have attracted considerable interest to scientists since the discovery of polyacetylene having electrical conductivity. Common conductive polymers include Polyacetylene (PA), polythiophene (PTh), Polyaniline (PANI), polypyrrole (PPy), poly-3, 4-ethylenedioxythiophene (PEDOT), and the like, and are widely researched and applied in many fields due to their special pi-conjugated structures and excellent physicochemical properties. Among them, PEDOT attracts more and more researchers' attention due to its advantages of high conductivity, good film transparency, environmental stability, etc., and shows a wide application prospect in electrochromic, antistatic coatings and lithium ion battery negative electrode materials.
The electrode material is a core material of the lithium battery, and the novel composite material compounded by the cerium-titanium-oxygen cluster and the PEDOT is used as a negative electrode material of the lithium battery, has the advantages of the cerium-titanium-oxygen cluster and a conductive polymer material, and nearly improves the charge-discharge capacity and the cycle stability of the negative electrode of the lithium battery.
Disclosure of Invention
The invention aims to provide a cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material, and a preparation method and application thereof.
The invention adopts the following technical scheme for solving the technical problems:
the invention aims to provide a preparation method of a composite electrode material containing cerium-titanium-oxygen clusters and PEDOT, which is characterized in that the composite material is prepared by the following method:
(1) preparation of cerium-containing titanium-oxygen cluster [ Ti ] by hydrothermal method8O7(HOEt)(OEt)21Ce]Crystal: adding tetraethyl titanate into the polytetrafluoroethylene inner container,Anhydrous cerium chloride and anhydrous ethanol, then placing the polytetrafluoroethylene inner container into a hydrothermal reaction kettle, reacting for 72 hours at 150 ℃, taking the polytetrafluoroethylene inner container out of the reaction kettle after the reaction is finished, cooling to room temperature to obtain a reaction mixed solution, and slowly volatilizing the solvent at the room temperature to obtain the orange cerium-titanium-containing clusters [ Ti ] Ti8O7(HOEt)(OEt)21Ce]A crystal; the volume ratio of the tetraethyl titanate to the absolute ethyl alcohol is 1: 2-7; the addition amount of the anhydrous cerium chloride is 0.5-2 mmol/mL based on the volume of the tetraethyl titanate;
(2) preparing a cerium-containing titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material by using an in-situ polymerization method: taking the cerium-containing titanium-oxygen cluster [ Ti ] obtained in the step (1)8O7(HOEt)(OEt)21Ce]Adding deionized water into the crystal and 3, 4-ethylenedioxythiophene, uniformly stirring, adding an initiator ammonium persulfate, reacting at 30 ℃ for 48-56 hours, and after the reaction is finished, carrying out aftertreatment on the obtained reaction mixture to obtain a cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material; the cerium-containing titanium oxide group [ Ti ]8O7(HOEt)(OEt)21Ce]The mass ratio of the crystal to the 3, 4-ethylenedioxythiophene is 1: 5-9; the mass ratio of the ammonium persulfate to the 3, 4-ethylenedioxythiophene is 1-1.5: 1.
Further, in the step (1), the operation method of the cooling process is as follows: after the reaction is finished, the polytetrafluoroethylene inner container is reduced by 10 ℃ every other hour, and when the temperature is reduced to 60 ℃, the polytetrafluoroethylene inner container is naturally cooled to the room temperature.
Further, in the step (2), the adding amount of the deionized water is 40-50 mL/g based on the mass of the 3, 4-ethylenedioxythiophene.
Still further, in the step (2), the post-treatment method of the reaction mixture comprises: and after the reaction is finished, carrying out suction filtration on the obtained reaction mixture, placing the obtained filter cake in a vacuum drying oven for drying treatment for 24 hours to obtain the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material, and placing the composite material into a dryer for later use.
The cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material is used as an active substance to be applied to preparing a lithium battery cathode material.
Further, the application is as follows: fully and uniformly mixing the obtained cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material with a conductive agent and a binder, stirring to form negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the negative electrode slurry on a cleaned copper foil, tabletting and drying to obtain the lithium ion battery negative electrode material; the mass ratio of the active substance to the conductive agent to the binder is 8:1: 1; the binder is one or a mixture of two or more of polyvinylidene fluoride, polytetrafluoroethylene, polyaniline, polypyrrole and epoxy resin.
Still further, the conductive agent is one or a mixture of two or more of carbon black, graphite, graphene or acetylene black.
Further, the coating thickness of the negative electrode slurry on the copper foil is 30-120 μm.
Still further, the dosage of the N-methyl pyrrolidone is 0.2mol/g based on the mass of the active substance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the titanium-oxygen cage material with high electrochemical activity, electron conduction and ion storage capacity is hung on the main chain of the conductive polymer with a conjugated structure through a covalent bond to generate a synergistic effect;
(2) as the composite material is a macroscopic homogeneous inorganic-organic conductive polymer, has the advantages of both the titanium cage and the conductive polymer material, and is expected to fundamentally solve the problems of heterogeneous interfaces among the components of the conductive polymer composite material and the dispersibility of the inorganic nano material, thereby improving the stability of the internal structure of the electrode material, improving the electron conduction efficiency and prolonging the cycle life.
(3) The first discharge specific capacity of the prepared cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite material composite electrode material reaches 426.2 mAh.g-1Compared with the specific discharge capacity (120.6 mAh.g) of the conductive polymer poly (3, 4-ethylenedioxythiophene)-1) The composite material has the advantages of large improvement, small change range of the discharge specific capacity and good cycle stability.
Drawings
FIG. 1 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is taken as an active substance and is at 100 mA.g-1First charge and discharge curves tested at constant charge and discharge rates.
FIG. 2 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1Cycling performance plots tested at constant charge and discharge rates.
FIG. 3 is a scanning electron microscope image of the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material.
FIG. 4 is a comparison of infrared spectra of poly 3, 4-ethylenedioxythiophene (PEDOT) and composite cerium-titanium-oxide cluster/poly 3, 4-ethylenedioxythiophene.
FIG. 5 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 2.
FIG. 6 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 3.
FIG. 7 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 4.
FIG. 8 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 5.
FIG. 9 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 6.
FIG. 10 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 7.
FIG. 11 is a cerium-titanium-oxide cluster/poly-3, 4-ethylene bisThe oxygen thiophene composite material is taken as an active substance and is at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 8.
FIG. 12 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as an active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 9.
FIG. 13 shows that the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material is used as the active substance at 100 mA.g-1First charge and discharge curves at constant charge and discharge rates and tested under the conditions of example 10.
Detailed Description
Example 1
Preparation of cerium-containing TiOx [ Ti ]8O7(HOEt)(OEt)21Ce]Crystal: adding tetraethyl titanate (1mL, 4.8mmol), anhydrous cerium chloride (0.246g, 1mmol) and anhydrous ethanol (5mL) into a polytetrafluoroethylene inner container, placing the inner container into a hydrothermal reaction kettle, placing the reaction kettle into an oven, heating to 150 ℃ and reacting for 72 hours. Reducing the temperature by 10 ℃ every hour after the reaction is finished, closing the oven when the temperature is reduced to 60 ℃, cooling to room temperature to obtain a yellow solution, and slowly volatilizing the solvent at room temperature to obtain orange crystals [ Ti8O7(HOEt)(OEt)21Ce]。
Preparing a cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite material: : weighing cerium-containing titanium oxide cluster [ Ti ]8O7(HOEt)(OEt)21Ce]0.052g of [ Ti ]8O7(HOEt)(OEt)21Ce]And EDOT, weighing a certain amount of EDOT0.35mL according to the mass ratio of 1:9, taking one clean 50mL round-bottom flask, adding 20mL deionized water, pouring the pre-weighed medicine into the round-bottom flask, uniformly stirring, adding 0.75g of initiator ammonium persulfate (dissolved in 10mL deionized water, and completely dripping within 30 mins), and reacting for 56 h. And after the reaction is finished, carrying out suction filtration, placing the suction filtration product in a vacuum drying oven for drying treatment for 24 hours to obtain a product cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material, and placing the product cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material in a dryer for later use.
Preparing a lithium ion battery negative electrode material: preparation of cerium-titanium-oxide cluster/polymer by coating method-3, 4-ethylenedioxythiophene composite negative electrode for lithium battery: preparing an electrode by using a coating method, taking a cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite material as an active substance, taking carbon black as a conductive agent, taking PVDF as a binder, weighing 0.08g of the cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite material, weighing 0.01g of the carbon black and 0.01g of PVDF according to the mass ratio of 8:1:1, dissolving in 2ml of N-methylpyrrolidone (NMP) serving as a solvent, stirring to form negative electrode slurry, uniformly coating on a clean copper foil by using a scraper (selecting one side with 60 micrometers), and carrying out vacuum drying in an oven at 60 ℃ for 12 hours to obtain the lithium battery negative electrode sheet. The first discharge specific capacity of the lithium battery negative electrode material reaches 426.2 mAh.g-1The cycle performance is basically stable.
Example 2
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (1.mL, 4.8 mmol); anhydrous cerium chloride (0.369g, 1.5 mmol); absolute ethanol (6 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.27mL of quantitative EDOT according to the mass ratio of 1:7 to EDOT; adding 15mL of deionized water and 0.58g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 52 h; preparing a lithium battery negative electrode material, namely selecting graphite as a conductive agent and polyvinylidene fluoride as a binder; the coating thickness of the negative electrode slurry on the copper foil was 30 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 285.1 mAh.g-1The cycle performance is basically stable.
Example 3
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (1.5mL, 7.2 mmol); anhydrous cerium chloride (0.492g, 2 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.20mL of quantitative EDOT according to the mass ratio of 1:5 to EDOT; adding 12mL of deionized water and 0.43g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 48 h; the preparation of the lithium battery cathode material selects graphene as a conductive agent and is bondedThe binder is polyaniline; the coating thickness of the negative electrode slurry on the copper foil was 90 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 270.2 mAh.g-1The cycle performance is basically stable.
Example 4
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (2mL, 9.6 mmol); anhydrous cerium chloride (0.246g, 1 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.35mL of quantitative EDOT according to the mass ratio of 1:9 to EDOT; adding 25mL of deionized water and 0.75g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 48 h; preparing a lithium battery cathode material, wherein acetylene black is selected as a conductive agent, and epoxy resin is selected as a binder; the coating thickness of the negative electrode slurry on the copper foil was 120 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 264.6 mAh.g-1The cycle performance is basically stable.
Example 5
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (2mL, 9.6 mmol); anhydrous cerium chloride (0.246g, 1 mmol); absolute ethanol (5 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.20mL of quantitative EDOT according to the mass ratio of 1:5 to EDOT; adding 15mL of deionized water and 0.43g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 48 h; preparing a lithium battery negative electrode material, wherein a conductive agent is carbon black, and a binder is polytetrafluoroethylene; the coating thickness of the negative electrode slurry on the copper foil was 60 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 140.3 mAh.g-1The cycle performance is basically stable.
Example 6
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (2.5mL, 12.0 mmol); anhydrous cerium chloride (0.369g, 1.5 mmol); absolute ethanol (6 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]And EDOT qualityWeighing 0.24mL of quantitative EDOT at a weight ratio of 1: 6; adding 15mL of deionized water and 0.51g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 52 h; preparing a negative electrode material of a lithium battery, wherein a conductive agent is graphite, and a binder is polyaniline; the coating thickness of the negative electrode slurry on the copper foil was 90 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 118.8 mAh.g-1The cycle performance is basically stable.
Example 7
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (2.5mL, 12.0 mmol); anhydrous cerium chloride (0.369g, 1.5 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.27mL of quantitative EDOT according to the mass ratio of 1:7 to EDOT; adding 20mL of deionized water and 0.58g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 52 h; preparing a negative electrode material of a lithium battery, wherein a conductive agent is carbon black, and a binder is polypyrrole; the coating thickness of the negative electrode slurry on the copper foil was 120 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 276.4 mAh.g-1The cycle performance is basically stable.
Example 8
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (3mL, 14.4 mmol); anhydrous cerium chloride (0.369g, 1.5 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.31mL of quantitative EDOT according to the mass ratio of 1:8 to EDOT; adding 20mL of deionized water and 0.64g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 54 h; preparing a lithium battery cathode material, wherein acetylene black is selected as a conductive agent, and epoxy resin is selected as a binder; the coating thickness of the negative electrode slurry on the copper foil was 30 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 268.7 mAh.g-1The cycle performance is basically stable.
Example 9
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (3.5mL, 16.8 mmol); anhydrous cerium chloride (0.246g, 1 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.35mL of quantitative EDOT according to the mass ratio of 1:9 to EDOT; adding 15mL of deionized water and 0.46g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 56 h; preparing a lithium battery negative electrode material, namely selecting graphene as a conductive agent and polyvinylidene fluoride as a binder; the coating thickness of the negative electrode slurry on the copper foil was 60 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 258.4 mAh.g-1The cycle performance is basically stable.
Example 10
The difference from the embodiment 1 is that the dosage of the raw materials is as follows: tetraethyl titanate (3.5mL, 16.8 mmol); anhydrous cerium chloride (0.246g, 1 mmol); absolute ethanol (7 mL); containing cerium-titanium-oxygen cluster [ Ti ]8O7(HOEt)(OEt)21Ce]Weighing 0.35mL of quantitative EDOT according to the mass ratio of 1:9 to EDOT; adding 20mL of deionized water and 0.55g of initiator ammonium persulfate (dissolved in 10mL of deionized water and completely dripped within 30 mins); EDOT and [ Ti ]8O7(HOEt)(OEt)21Ce]The in-situ polymerization time is 56 h; preparing a lithium battery cathode material, namely selecting graphite as a conductive agent and epoxy resin as a binder; the coating thickness of the negative electrode slurry on the copper foil was 60 μm. The first discharge specific capacity of the lithium battery negative electrode material reaches 202.4 mAh.g-1The cycle performance is basically stable.

Claims (9)

1. The cerium-titanium-oxide cluster/poly-3, 4-ethylene dioxythiophene composite material is characterized by being prepared by the following steps:
(1) preparation of cerium-containing titanium-oxygen cluster [ Ti ] by hydrothermal method8O7(HOEt)(OEt)21Ce]Crystal: adding tetraethyl titanate, anhydrous cerium chloride and anhydrous ethanol into a polytetrafluoroethylene inner container, putting the polytetrafluoroethylene inner container into a hydrothermal reaction kettle, and reacting at 150 ℃ for 72 DEG Ch, after the reaction is finished, taking the polytetrafluoroethylene liner out of the reaction kettle, cooling to room temperature to obtain a reaction mixed solution, and slowly volatilizing the solvent at room temperature to obtain the orange cerium-titanium-containing cluster [ Ti8O7(HOEt)(OEt)21Ce]A crystal; the volume ratio of the tetraethyl titanate to the absolute ethyl alcohol is 1: 2-7; the addition amount of the anhydrous cerium chloride is 0.5-2 mmol/mL based on the volume of the tetraethyl titanate;
(2) preparing a cerium-containing titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material by using an in-situ polymerization method: taking the cerium-containing titanium-oxygen cluster [ Ti ] obtained in the step (1)8O7(HOEt)(OEt)21Ce]Adding deionized water into the crystal and 3, 4-ethylenedioxythiophene, uniformly stirring, adding an initiator ammonium persulfate, reacting for 48-56 h at 30 ℃, and after the reaction is finished, carrying out post-treatment on the obtained reaction mixture to obtain a cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material; the cerium-titanium-oxygen cluster [ Ti8O7(HOEt)(OEt)21Ce]The mass ratio of the crystal to the 3, 4-ethylenedioxythiophene is 1: 5-9; the mass ratio of the ammonium persulfate to the 3, 4-ethylenedioxythiophene is 1-1.5: 1.
2. the cerium-titanium-oxo-3, 4-ethylenedioxythiophene composite material of claim 1, wherein: in the step (1), the operation method of the cooling process comprises the following steps: after the reaction is finished, the polytetrafluoroethylene inner container is reduced by 10 ℃ every other hour, and when the temperature is reduced to 60 ℃, the polytetrafluoroethylene inner container is naturally cooled to the room temperature.
3. The cerium-titanium-oxo-3, 4-ethylenedioxythiophene composite material of claim 1, wherein: in the step (2), the adding amount of the deionized water is 10-20 mL/g based on the mass of the 3, 4-ethylenedioxythiophene.
4. The cerium-titanium-oxo-3, 4-ethylenedioxythiophene composite material of claim 1, wherein: in the step (2), the post-treatment method of the reaction mixture comprises the following steps: and after the reaction is finished, carrying out suction filtration on the obtained reaction mixture, placing the obtained filter cake in a vacuum drying oven for drying treatment for 24 hours to obtain the cerium-titanium-oxygen cluster/poly-3, 4-ethylenedioxythiophene composite material, and placing the composite material into a dryer for later use.
5. The use of the cerium-titanium-oxo-cluster/poly-3, 4-ethylenedioxythiophene composite material of claim 1 as an active material in the preparation of a negative electrode material for a lithium battery.
6. The use of claim 5, wherein: the application is as follows: fully and uniformly mixing the obtained cerium-titanium-oxygen cluster/poly-3, 4-ethylene dioxythiophene composite material with a conductive agent and a binder, stirring to form negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the negative electrode slurry on a cleaned copper foil, tabletting and drying to obtain the lithium ion battery negative electrode material; the mass ratio of the active substance to the conductive agent to the binder is 8:1: 1; the binder is one or a mixture of two or more of polyvinylidene fluoride, polytetrafluoroethylene, polyaniline, polypyrrole and epoxy resin.
7. The use of claim 6, wherein: the conductive agent is one or a mixture of two or more of carbon black, graphite, graphene or acetylene black.
8. The use of claim 6, wherein: the coating thickness of the negative electrode slurry on the copper foil is 30-120 mu m.
9. The use of claim 6, wherein: the dosage of the N-methyl pyrrolidone is 0.2mol/g based on the mass of the active substance.
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