CN110854373B - Composite negative electrode material and preparation method thereof - Google Patents
Composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite negative electrode material and a preparation method thereof. The method comprises the following steps: mixing sodium stannate, cyclodextrin and water, and carrying out a first heating reaction to obtain stannic oxide nanoparticles; dispersing the tin dioxide nano particles in water, adding ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate, and carrying out a second heating reaction to obtain a precursor; mixing the precursor with an aqueous solution of N, N-dimethylformamide, dimethyl imidazole and cobalt salt, and carrying out a third heating reaction to obtain a ZIF 67-coated tin dioxide material; and sintering the ZIF 67-coated tin dioxide material mixture. According to the method, the MOF-derived porous carbon is used for coating the tin dioxide, so that the capacity of the tin dioxide cathode material is exerted more stably, the cycling stability of the battery is improved, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of lithium battery cathode materials, in particular to a composite cathode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high open-circuit voltage, high energy density, long service life, no memory effect, less pollution, low self-discharge rate and the like, is superior to other traditional secondary batteries in overall performance, and is considered as the most ideal power supply for various portable electronic equipment and electric automobiles. Although the traditional lithium ion battery cathode material graphite has good cycling stability and higher cost performance, the traditional lithium ion battery cathode material graphite has lower charge-discharge specific capacity and no advantage in volume specific capacity, and is difficult to meet the requirement of a power system, particularly an electric vehicle and a hybrid electric vehicle on high capacity of the battery.
Among the emerging negative electrode materials, simple substance materials such as silicon, tin, germanium, etc., metal oxides and composite metal oxide materials are attracting more and more attention because of their high theoretical lithium intercalation capacity. If the high-capacity cathode material can reach the practical degree, the application range of the lithium ion battery is necessarily greatly widened. However, most of these high capacity enrichment materials have low conductivity and have severe volume effect under high degree of lithium deintercalation, resulting in poor cycling stability of the electrode. Taking tin dioxide as an example, the volume change of the tin dioxide is large in the charging and discharging process, and the structure is easy to pulverize, so that the cycling stability is poor, and the capacity is rapidly attenuated.
Disclosure of Invention
Based on the method, the MOF-derived porous carbon is used for coating the tin dioxide, so that the capacity of the tin dioxide cathode material is exerted more stably, the cycling stability of the battery is improved, and the service life of the battery is prolonged.
The specific technical scheme is as follows:
a preparation method of the composite anode material comprises the following steps:
mixing sodium stannate, cyclodextrin and water, and carrying out a first heating reaction to obtain stannic oxide nanoparticles;
dispersing the tin dioxide nano particles in water, adding ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate, and carrying out a second heating reaction to obtain a precursor;
mixing the precursor with an aqueous solution of N, N-dimethylformamide, dimethyl imidazole and cobalt salt, and carrying out a third heating reaction to obtain a ZIF 67-coated tin dioxide material;
and sintering the ZIF 67-coated tin dioxide material mixture.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the MOF-derived porous carbon is used for coating tin dioxide, a metal organic framework is grown on the surface of the nano tin dioxide through reaction, the MOF-derived porous carbon is used for effectively buffering the volume expansion of the tin dioxide, the material structure is protected, the cycling stability of the negative electrode material is improved, and the characteristic of high theoretical specific capacity of the tin dioxide is fully exerted. The inventor of the application discovers that the ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate are added into a tin dioxide nanoparticle aqueous solution to prepare a precursor, and under the combined action of the substances, the metal organic framework can be assisted to grow on the surface of tin dioxide, and finally the MOF-derived porous carbon-coated tin dioxide composite negative electrode material is successfully prepared. Meanwhile, in the process of forming the composite cathode material, cobalt doping (adding cobalt salt) is carried out, so that the conductivity of the metal oxide tin dioxide cathode material is effectively improved.
Preferably, the ZIF 67-coated tin dioxide material is sintered under nitrogen gas for nitrogen doping, so that the conductivity of the metal tin dioxide anode material is further improved. The process has the advantages of simple and convenient conditions, easy operation, low cost of raw materials, mild reaction conditions and high repeatability, and is suitable for large-scale production and commercial application.
Drawings
FIG. 1 is an XRD pattern of a ZIF67 coated tin dioxide material made in example 1;
FIG. 2 is a TEM image of a ZIF67 coated tin dioxide material prepared in example 1;
FIG. 3 is an XRD pattern of the ZIF67 coated tin dioxide material prepared in example 2;
FIG. 4 is a TEM image of a ZIF67 coated tin dioxide material prepared in example 2;
FIG. 5 is an XRD pattern of the ZIF67 coated tin dioxide material prepared in example 3;
FIG. 6 is a TEM image of a ZIF67 coated tin dioxide material prepared in example 3;
FIG. 7 is a performance cycle chart of a lithium ion battery blue battery prepared by using commercial tin dioxide as a negative electrode material;
FIG. 8 is a cycle chart of the performance of a lithium ion battery blue battery made of the negative electrode material of example 1;
FIG. 9 is a performance cycle chart of a lithium ion battery blue battery prepared from the negative electrode material of example 2
FIG. 10 is a cycle chart of the performance of a lithium ion battery and a blue battery made of the negative electrode material of example 3;
fig. 11 is a performance cycle chart of a lithium ion battery blue battery prepared from the negative electrode material of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A preparation method of the composite anode material comprises the following steps:
(1) mixing sodium stannate, cyclodextrin and water, and carrying out a first heating reaction to obtain stannic oxide nanoparticles;
(2) dispersing the tin dioxide nano particles in water, adding ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate, and carrying out a second heating reaction to obtain a precursor;
(3) mixing the precursor with an aqueous solution of N, N-dimethylformamide, dimethyl imidazole and cobalt salt, and carrying out a third heating reaction to obtain a ZIF 67-coated tin dioxide material;
(4) and sintering the ZIF 67-coated tin dioxide material mixture.
Specifically, in the step (1), the addition of cyclodextrin is beneficial to keeping the tin dioxide nanoparticles in good morphology and easy to coat the metal organic framework. Preferably, the mass ratio of the sodium stannate to the cyclodextrin is (1-2): (1-4). It is understood that the amount of water added may be added as appropriate depending on the actual reaction conditions.
The heating mode of the first heating reaction may be oil bath heating or water bath heating, and it is further understood that the operation of magnetic stirring is also performed in the heating process. Preferably, the reaction temperature of the first heating reaction is 80-110 ℃, and the reaction time is 2-4 h.
The step (2) is a key step of growing the metal organic framework on the surface of the nano tin dioxide, and directly determines whether the metal organic framework can successfully grow on the surface of the nano tin dioxide or not. Wherein, the reaction temperature of the second heating reaction is preferably 70-100 ℃, and the reaction time is preferably 7-10 h. Similarly, the heating method may be oil bath heating or water bath heating, and it is further understood that the magnetic stirring operation is also performed during the heating process.
In this step, the tin dioxide nanoparticles are first dispersed in an appropriate amount of deionized water, followed by the addition of ascorbic acid, cetyltrimethylammonium bromide, urotropin, and zinc nitrate to prepare the precursor. The preferred weight ratio of the tin dioxide nanoparticles, ascorbic acid, cetyltrimethylammonium bromide, urotropine and zinc nitrate is (0.2-0.8): (0.2-0.8): (2-8): (1-5): (2-8), more preferably (0.2-0.4): (0.2-0.4): (2-4): (1-2.5): (2-4).
In the step (3), a precursor is firstly dispersed in an aqueous solution of N, N-dimethylformamide, preferably, the mass-to-volume ratio of the precursor to the aqueous solution of N, N-dimethylformamide is (3-4) g: 1L, wherein the volume ratio of the N, N-dimethylformamide to the water in the N, N-dimethylformamide aqueous solution is (4-5): 1.
And adding dimethyl imidazole and cobalt salt into the solution, and carrying out heating reaction for the third time to obtain the ZIF 67-coated tin dioxide material. The cobalt salt is preferably cobalt nitrate. The weight ratio of the precursor, the dimethyl imidazole and the cobalt salt is preferably (0.1-0.4): (1.5-3): (0.3-0.8).
The addition of the cobalt salt is beneficial to improving the conductivity of the metal oxide tin dioxide cathode material.
ZIF, a zeolite imidazolate framework material, is a porous crystal material. In which organic imidazolate is cross-linked to a transition metal to form a tetrahedral framework. The metal node of ZIF67 is a Co ion.
The reaction temperature of the third heating reaction is preferably 70-90 ℃, and the reaction time is 24-48 h. The heating method may use a hydrothermal reaction oven.
In the step (4), the sintering is preferably carried out in a tube furnace, the atmosphere of the sintering is preferably nitrogen, and the process parameters are preferably as follows: the sintering temperature is 600-800 ℃, and the sintering time is 2-3 h.
And sintering under nitrogen, namely, carrying out nitrogen doping on the tin dioxide composite negative electrode material, and being beneficial to improving the conductivity of the metal oxide tin dioxide negative electrode material.
The method can successfully react and grow the metal organic framework on the surface of the nano tin dioxide, and utilizes the porous carbon to play an effective buffer role on the volume expansion of the tin dioxide, so that the material structure is protected, the cycling stability of the cathode material is improved, and the characteristic of high theoretical specific capacity of the tin dioxide is fully exerted.
The following is a further description with reference to specific examples.
Example 1
The embodiment provides a composite negative electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding magnetons into a three-neck flask, then adding 2 g of sodium stannate hydrate, 4 g of cyclodextrin and 200 ml of deionized water into the three-neck flask, heating for 3 hours at 80 ℃ under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain the tin dioxide nanoparticles.
(2) Adding magnetons into a large beaker, adding 400 mg of the tin dioxide nanoparticles prepared in the step (1) into the beaker, adding 200 ml of deionized water, performing ultrasonic dispersion, adding 400 mg of ascorbic acid, 4 g of hexadecyl trimethyl ammonium bromide, 2.5 g of urotropine and 4 g of zinc nitrate, heating at 80 ℃ for 8 hours under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain a precursor.
(3) Adding magnetons into a large beaker, adding 250 mg of the precursor prepared in the step (2) and 80 ml of a mixed solution (the mixed solution is formed by mixing deionized water and N, N-dimethylformamide according to the volume ratio of 1: 4) into the beaker, and performing ultrasonic dispersion. Then, 1.5 g of dimethylimidazole and 400 mg of cobalt nitrate hexahydrate are added, magnetic stirring is carried out at room temperature for 10 minutes, then the mixture is transferred into a reaction kettle, the mixture reacts for 24 hours in a hydrothermal oven at the temperature of 80 ℃, and solids are collected by centrifugation to obtain a ZIF 67-coated tin dioxide material. The ZIF 67-coated tin dioxide material was characterized as shown in fig. 1 and 2, which are an X-ray diffraction pattern (XRD pattern) and a transmission electron microscopy pattern (TEM pattern), respectively, of a ZIF 67-coated tin dioxide material.
As can be seen from fig. 1, the XRD pattern includes a peak of ZIF67 metal organic framework, a peak of tin dioxide, a peak of metal cobalt and a small amount of an insignificant impurity peak, and it can be confirmed that the material is a ZIF67 metal framework-coated tin dioxide composite material. As can be seen from fig. 2, ZIF67 completely coated the tin dioxide nanoparticles, and the crystal structure was good.
(4) And (3) sintering the ZIF 67-coated tin dioxide material obtained in the step (3) for 3 hours at 700 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the MOF-derived porous carbon-coated tin dioxide negative electrode material.
Example 2
The embodiment provides a composite negative electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding magnetons into a three-neck flask, then adding 2 g of sodium stannate hydrate, 4 g of cyclodextrin and 200 ml of deionized water into the three-neck flask, heating for 3 hours at 80 ℃ under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain the tin dioxide nanoparticles.
(2) Adding magnetons into a large beaker, adding 600 mg of the tin dioxide nanoparticles prepared in the step (1) into the beaker, adding 200 ml of deionized water, performing ultrasonic dispersion, adding 600 mg of ascorbic acid, 6.0 g of hexadecyl trimethyl ammonium bromide, 3.75 g of urotropine and 4.8 g of zinc nitrate, heating at 80 ℃ for 8 hours under the conditions of water bath heating and magnetic stirring, centrifuging and collecting solids to obtain a precursor.
(3) Adding magnetons into a large beaker, adding 250 mg of the precursor prepared in the step (2) and 80 ml of a mixed solution (the mixed solution is formed by mixing deionized water and N, N-dimethylformamide according to the volume ratio of 1: 4) into the beaker, and performing ultrasonic dispersion. Then, 1.5 g of dimethylimidazole and 400 mg of cobalt nitrate hexahydrate are added, magnetic stirring is carried out at room temperature for 10 minutes, then the mixture is transferred into a reaction kettle, the mixture reacts for 24 hours in a hydrothermal oven at the temperature of 80 ℃, and solids are collected by centrifugation to obtain a ZIF 67-coated tin dioxide material. The ZIF 67-coated tin dioxide material was characterized as shown in fig. 3 and 4, which are an X-ray diffraction pattern (XRD pattern) and a transmission electron microscopy pattern (TEM pattern), respectively, of the ZIF 67-coated tin dioxide material.
As can be seen from fig. 3, the XRD pattern includes a peak of ZIF67 metal organic framework, a peak of tin dioxide, a peak of metal cobalt and a small amount of an insignificant impurity peak, and it can be confirmed that the material is a ZIF67 metal framework-coated tin dioxide composite material. As can be seen from fig. 4, ZIF67 completely coated the tin dioxide nanoparticles, and the crystal structure was good.
(4) And (3) sintering the ZIF 67-coated tin dioxide material obtained in the step (3) for 3 hours at 700 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the MOF-derived porous carbon-coated tin dioxide negative electrode material.
Example 3
The embodiment provides a composite negative electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) adding magnetons into a three-neck flask, then adding 2 g of sodium stannate hydrate, 4 g of cyclodextrin and 200 ml of deionized water into the three-neck flask, heating for 3 hours at 80 ℃ under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain the tin dioxide nanoparticles.
(2) Adding magnetons into a large beaker, adding 400 mg of the tin dioxide nanoparticles prepared in the step (1) into the beaker, adding 200 ml of deionized water, performing ultrasonic dispersion, adding 400 mg of ascorbic acid, 4 g of hexadecyl trimethyl ammonium bromide, 2.5 g of urotropine and 4 g of zinc nitrate, heating at 100 ℃ for 10 hours under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain a precursor.
(3) Adding magnetons into a large beaker, adding 250 mg of the precursor prepared in the step (2) and 80 ml of a mixed solution (the mixed solution is formed by mixing deionized water and N, N-dimethylformamide according to the volume ratio of 1: 4) into the beaker, and performing ultrasonic dispersion. Then, 1.5 g of dimethylimidazole and 300 mg of cobalt nitrate hexahydrate are added, magnetic stirring is carried out at room temperature for 10 minutes, then the mixture is transferred into a reaction kettle, the mixture reacts for 24 hours in a hydrothermal oven at the temperature of 80 ℃, and solids are collected by centrifugation to obtain a ZIF 67-coated tin dioxide material. The ZIF 67-coated tin dioxide material was characterized as shown in fig. 5 and 6, which are an X-ray diffraction pattern (XRD pattern) and a transmission electron microscopy pattern (TEM pattern), respectively, of the ZIF 67-coated tin dioxide material.
As can be seen from fig. 5, the XRD pattern includes a peak of ZIF67 metal organic framework, a peak of tin dioxide, a peak of metal cobalt and a small amount of an insignificant impurity peak, and it can be confirmed that the material is a ZIF67 metal framework-coated tin dioxide composite material. As can be seen from fig. 6, ZIF67 completely coated the tin dioxide nanoparticles, and the crystal structure was good.
(4) And (3) sintering the ZIF 67-coated tin dioxide material obtained in the step (3) for 3 hours at 700 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the MOF-derived porous carbon-coated tin dioxide negative electrode material.
Comparative example 1
This comparative example provides a method for preparing a composite anode material, which is substantially the same as example 1, except that the step of preparing a precursor in step (2) is omitted and an attempt is made to directly grow a metal organic framework on tin dioxide nanoparticles. The method comprises the following specific steps:
(1) adding magnetons into a three-neck flask, then adding 2 g of sodium stannate hydrate, 4 g of cyclodextrin and 200 ml of deionized water into the three-neck flask, heating for 3 hours at 80 ℃ under the conditions of water bath heating and magnetic stirring, and centrifuging to collect solids to obtain the tin dioxide nanoparticles.
(2) Adding magnetons into a large beaker, adding 250 mg of the tin dioxide nanoparticles prepared in the step (1) and 80 ml of a mixed solution (the mixed solution is formed by mixing deionized water and N, N-dimethylformamide according to the volume ratio of 1: 4) into the beaker, and performing ultrasonic dispersion. Then 1.5 g of dimethylimidazole and 400 mg of cobalt nitrate hexahydrate are added, magnetic stirring is carried out at room temperature for 10 minutes, then the mixture is transferred into a reaction kettle, the mixture is reacted for 24 hours in a hydrothermal oven at 80 ℃, and solids are collected by centrifugation.
(3) And (3) sintering the solid material obtained in the step (2) for 3 hours at 700 ℃ in a nitrogen atmosphere by using a tube furnace to obtain the composite anode material.
Performance testing of the cathode Material
Commercial tin dioxide nanoparticle materials, the MOF-derived porous carbon-coated tin dioxide negative electrode materials of examples 1 to 3 and the negative electrode material prepared in comparative example 1 were taken respectively, then mixed with acetylene black and sodium alginate according to a ratio of 7:2:1 to prepare slurry, and coated to prepare 5 kinds of negative electrode sheets, which were respectively assembled into half cells, and the half cells were activated for three cycles at 0.1C and charged and discharged at 0.2C for 100 cycles. The blue cell performance cycle plots are shown in fig. 7-11, where fig. 7 corresponds to a half cell for commercial tin dioxide, fig. 8 corresponds to a half cell for example 1, fig. 9 corresponds to a half cell for example 2, fig. 10 corresponds to a half cell for example 3, and fig. 11 corresponds to a half cell for comparative example 1.
From FIGS. 7 to 11, it can be seen that the capacity of the lithium ion battery using commercial tin dioxide as the negative electrode material is 800mAh g from the beginning-1The temperature is reduced all the time, and the temperature is reduced faster after 40 circles, and the capacity is almost zero when the temperature reaches 100 circles; whereas the lithium ion battery capacity using the MOF-derived porous carbon-coated tin dioxide negative electrode material of example 1 started at 720mAh g-1The capacity is very stable, and 650mAh g is still obtained after 100 circles-1The capacity attenuation is very small; the lithium ion battery capacity using the MOF-derivatized porous carbon-coated tin dioxide negative electrode material of example 2 started at 940mAh g-1The capacity is relatively stable to play, and the capacity is attenuated to 560mAh g after 100 circles-1(ii) a The lithium ion battery capacity using the MOF-derivatized porous carbon-coated tin dioxide negative electrode material of example 3 started at 800mAh g-1The capacity is stably exerted, and the capacity still has 640mAh g after 100 circles-1The capacity attenuation is very small; the lithium ion battery using the negative electrode material prepared in comparative example 1 was seriously damaged during the cycle, and the battery capacity was rapidly attenuated, which indicates that in the negative electrode material, tin dioxide and ZIF-67 were dispersed, and actually, ZIF-67 did not coat the surface of tin dioxide nanoparticles, and the carbon layer did not play a sufficient buffer role. The above results demonstrate that: MOF-derived porous carbon-coated tin dioxide applied to lithium ion battery negative electrode materialThe material can effectively protect the tin dioxide cathode material, so that the capacity of the metal oxide is exerted more stably, the cycling stability of the battery is improved, and the service life of the battery is prolonged.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
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 various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (9)
1. The preparation method of the composite anode material is characterized by comprising the following steps of:
mixing sodium stannate, cyclodextrin and water, and carrying out a first heating reaction at a reaction temperature of 80-110 ℃ for 2-4 h to obtain tin dioxide nanoparticles; wherein the mass ratio of the sodium stannate to the cyclodextrin is (1-2): (1-4);
dispersing the tin dioxide nano particles in water, adding ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate, and carrying out a second heating reaction at the reaction temperature of 70-100 ℃ for 7-10 h to obtain a precursor; wherein the weight ratio of the tin dioxide nanoparticles, ascorbic acid, cetyl trimethyl ammonium bromide, urotropine and zinc nitrate is (0.2-0.8): (0.2-0.8): (2-8): (1-5): (2-8);
mixing the precursor with an aqueous solution of N, N-dimethylformamide, dimethyl imidazole and cobalt salt, and carrying out a third heating reaction at the temperature of 70-90 ℃ for 24-48 h to obtain a ZIF 67-coated tin dioxide material; wherein the weight ratio of the precursor, the dimethyl imidazole and the cobalt salt is (0.1-0.4): (1.5-3): (0.3-0.8);
and sintering the ZIF 67-coated tin dioxide material mixture.
2. The method for preparing the composite anode material according to claim 1, wherein the precursor is dispersed in an aqueous solution of N, N-dimethylformamide, and then dimethylimidazole and cobalt salt are added.
3. The method for preparing the composite anode material according to claim 1, wherein the weight ratio of the tin dioxide nanoparticles, the ascorbic acid, the cetyl trimethyl ammonium bromide, the urotropin and the zinc nitrate is (0.2-0.4): (0.2-0.4): (2-4): (1-2.5): (2-4).
4. The method for preparing the composite anode material according to claim 1, wherein the tin dioxide nanoparticles are dispersed in an appropriate amount of deionized water, and then ascorbic acid, cetyltrimethylammonium bromide, urotropin, and zinc nitrate are added.
5. The method for producing a composite anode material according to any one of claims 1 to 4,
the cobalt salt is cobalt nitrate.
6. The method for producing a composite anode material according to any one of claims 1 to 4,
the mass-volume ratio of the precursor to the N, N-dimethylformamide aqueous solution is (3-4) g: 1L, wherein the volume ratio of the N, N-dimethylformamide to the water in the N, N-dimethylformamide aqueous solution is (4-5): 1.
7. The method for preparing the composite anode material according to any one of claims 1 to 4, wherein the ZIF 67-coated tin dioxide material mixture is sintered under a nitrogen atmosphere.
8. The preparation method of the composite anode material according to claim 7, wherein the sintering temperature is 600-800 ℃, and the sintering time is 2-3 h.
9. A composite anode material produced by the production method described in any one of claims 1 to 8.
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