CN115070056A - Method for uniformly growing superfine aluminum nanocrystals on surface of carbon fiber - Google Patents

Method for uniformly growing superfine aluminum nanocrystals on surface of carbon fiber Download PDF

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CN115070056A
CN115070056A CN202210730148.5A CN202210730148A CN115070056A CN 115070056 A CN115070056 A CN 115070056A CN 202210730148 A CN202210730148 A CN 202210730148A CN 115070056 A CN115070056 A CN 115070056A
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carbon fiber
aluminum
nanocrystals
aluminum chloride
washing
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CN115070056B (en
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杨飘萍
刘志亮
孔祥龙
李至
赵颖
赵旭东
丁鹤
贺飞
赵潇涵
贾卓明
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Harbin Engineering University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/062—Fibrous particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

Abstract

A method for uniformly growing superfine aluminum nanocrystals on the surface of carbon fibers belongs to the technical field of nanomaterial synthesis. The invention aims to solve the problems that the existing synthesis method of the aluminum nano-structure material needs complex multi-step reaction, high-temperature heating, dangerous aluminum precursor and harsh reaction conditions. The method comprises the following steps: firstly, mixing anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material for reaction; secondly, washing and drying the reaction product. The method is used for uniformly growing the superfine aluminum nanocrystals on the surface of the carbon fiber.

Description

Method for uniformly growing superfine aluminum nanocrystals on surface of carbon fiber
Technical Field
The invention belongs to the technical field of nano material synthesis.
Background
As the most abundant metal element in the earth crust, aluminum has wide application in the traditional industrial manufacturing field and has important application value in the fields of alloy manufacturing, industrial cable alloy fuel and the like. But the conventional aluminum metal is difficult to be applied to fields with higher added values. In contrast, nanostructured aluminum exhibits a variety of different novel properties, and thus has been applied to high and new technical fields such as luminescence, ultraviolet optoelectronic devices, photocatalysis, and lithium ion batteries in recent years. Particularly in the field of lithium ion batteries, the nano-aluminum has an ultra-high theoretical specific capacity (2234mAh/g) and a very appropriate working potential (0.5V vs. Li/Li) + ). However, the preparation of nano-structured aluminum is very difficult due to the high chemical activity of aluminum, and the practical application of aluminum is seriously influenced.
The research on the nano-structured aluminum is very limited because the nano-structured aluminum has very high reactivity and is complex to prepare. Few reports have reported that the synthesis of nanostructured aluminum requires a harsh environment at high temperature and pressure, with concomitant high energy consumption. For example, in many organic systems, aluminum nanorods are synthesized by thermal decomposition through multi-step reaction of triisobutylaluminum, but the decomposition temperature of triisobutylaluminum requires a high temperature of 250 ℃ or more, and triisobutylaluminum precursor itself has strong corrosivity and extremely high chemical reactivity (spontaneous combustion in air, strong reaction and explosion in the presence of water, acid, alcohol, and ammonia), and has extremely high operational risk. The other method is to utilize the reducibility of hydrogen to reduce triethyl aluminum on the graphene nano-sheets at a high temperature of 230 ℃ and under extremely high hydrogen pressure (50atm) to prepare the graphene composite aluminum nano-crystalline material, and the method also faces extremely high danger (triethyl aluminum precursor is a highly toxic substance and is easy to cause combustion and explosion when meeting micro oxygen and water), thereby greatly limiting the practical application of the materials. Therefore, various current methods for synthesizing nanostructured aluminum have the following disadvantages: the preparation method is very complex, needs separate multi-step reaction and very high reaction temperature, leads to large energy consumption of the reaction, and the environmental conditions required by synthesis are very dangerous and harsh; the starting material for the synthesis of aluminium nanostructures is an organism of aluminium, which is not only very expensive, but also highly dangerous.
Disclosure of Invention
The invention provides a method for uniformly growing superfine aluminum nanocrystals on the surface of carbon fibers, aiming at solving the problems that the existing synthesis method of an aluminum nanostructure material needs complex multistep reaction, high-temperature heating, dangerous aluminum precursors and harsh reaction conditions.
A method for uniformly growing superfine aluminum nanocrystals on the surface of carbon fibers comprises the following steps:
firstly, adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle in sequence, and reacting for 2-50 h under the condition of argon atmosphere and temperature of 30-180 ℃ to obtain a reaction product;
the mass ratio of the hydroxylated carbon fiber to the anhydrous aluminum chloride is 1 (10-100); the molar ratio of the anhydrous aluminum chloride to the lithium metal material is 1 (1-5);
and secondly, washing and drying the reaction product at room temperature to obtain the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The invention has the beneficial effects that:
different from other high-temperature and high-risk nano-structure aluminum preparation technologies, the invention provides a synthetic method for uniformly growing ultrafine aluminum nanocrystals on the surface of carbon fibers guided by surface groups. The novel synthesis method is characterized in that under the condition of low temperature, uniform self-assembly of metal aluminum on a nanoscale is realized through a surface group-guided self-assembly strategy, and ultrafine aluminum nanocrystals uniformly grow on the surface of carbon fibers are formed on the surface of the carbon fibers. The "surface group-oriented self-assembly strategy" specifically utilizes a specific functional group on the surface of a material to realize self-assembly of atoms or molecules without fixed size to the surface of a target material through a chemical reaction under the orientation of the specific functional group to form a nano product. In an organic solvent containing lithium metal, the method utilizes abundant hydroxyl on the surface of hydroxylated carbon fiber to be converted into-OLi group (H is replaced by Li), and the-OLi group can react with free AlCl in solution 3 The molecules form a tight connection, so that AlCl is formed 3 Under the guidance of-OLi group, metal Al generated after the molecule reacts with Li metal at a lower temperature can be self-assembled on the surface of the carbon fiber in situ to form uniform superfine Al nano-crystal (about 10 nm). The surface-OLi group orientation is the key for constructing the uniform self-assembly composite material of the superfine aluminum nanocrystals and the carbon fibers at low temperature.
In the present invention, AlCl is used 3 Very cheap, safe and non-combustible, low-temp. reduction of AlCl by Li 3 The reaction is very mild, and the guiding effect of the-OLi groups on the surface of the carbon fiber also effectively prevents the Al nanocrystalline from instantaneously and locally growing excessively and agglomerating, so that the superfine Al nanocrystalline is generated. Therefore, the synthetic method has the advantages of low energy consumption, low raw material cost, high safety, high efficiency and the like, and is easy for mass production.
The electrode prepared by uniformly growing the superfine aluminum nanocrystalline material powder on the surface of the carbon fiber has the lithium storage first discharge capacity as high as 1760 mAh/g-2225 mAh/g.
Drawings
FIG. 1 is a schematic view showing the carbon fiber surface prepared in example oneX-ray diffraction pattern of uniformly grown superfine aluminium nanocrystalline material powder is aluminium,
Figure BDA0003712943980000021
is carbon fiber;
FIG. 2 is a transmission electron microscope image of the carbon fiber prepared in the first embodiment in which the ultrafine aluminum nano-crystalline material powder uniformly grows on the surface, wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image;
FIG. 3 is an infrared spectrum, wherein a is hydroxylated carbon fiber, and b is ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber;
FIG. 4 is a diagram showing the lithium storage rate performance of the electrode prepared by uniformly growing ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber according to the first embodiment at a current of 200mA/g, wherein O represents discharge,
Figure BDA0003712943980000022
represents charging;
fig. 5 is a transmission electron microscope image of the aluminum and carbon fiber composite material prepared in the first comparative experiment.
Detailed Description
The first embodiment is as follows: the method for uniformly growing the superfine aluminum nanocrystals on the surface of the carbon fiber comprises the following steps:
firstly, adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle in sequence, and reacting for 2-50 h under the condition of argon atmosphere and temperature of 30-180 ℃ to obtain a reaction product;
the mass ratio of the hydroxylated carbon fibers to the anhydrous aluminum chloride is 1 (10-100); the molar ratio of the anhydrous aluminum chloride to the lithium metal material is 1 (1-5);
and secondly, washing and drying the reaction product at room temperature to obtain the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The beneficial effects of the embodiment are as follows:
unlike other high-temperature and high-risk nanostructured aluminum preparation technologies, the present embodiment provides a surfaceA synthesis method for uniformly growing superfine aluminum nanocrystals on the surface of a group-oriented carbon fiber. The novel synthesis method is characterized in that under the condition of low temperature, uniform self-assembly of metal aluminum on a nanoscale is realized through a surface group-guided self-assembly strategy, and ultrafine aluminum nanocrystals uniformly grow on the surface of carbon fibers are formed on the surface of the carbon fibers. The surface group-oriented self-assembly strategy is to realize self-assembly of atoms or molecules with non-fixed sizes to the surface of a target material through chemical reaction under the orientation of a specific functional group by utilizing the specific functional group on the surface of the material to form a nano product. In an organic solvent containing lithium metal, the method utilizes abundant hydroxyl on the surface of hydroxylated carbon fiber to be converted into-OLi group (H is replaced by Li), and the-OLi group can react with free AlCl in solution 3 The molecules form a tight connection, so that AlCl is formed 3 Under the guidance of-OLi group, metal Al generated after the molecule reacts with Li metal at a lower temperature can be self-assembled on the surface of the carbon fiber in situ to form uniform superfine Al nano-crystal (about 10 nm). The surface-OLi group orientation is the key for constructing the uniform self-assembly composite material of the superfine aluminum nanocrystals and the carbon fibers at low temperature.
In this embodiment, AlCl is used 3 Very cheap, safe and non-combustible, low-temp. reduction of AlCl by Li 3 The reaction is very mild, and the guiding effect of the-OLi groups on the surface of the carbon fiber also effectively prevents the Al nanocrystalline from instantaneously and locally growing excessively and agglomerating, so that the superfine Al nanocrystalline is generated. Therefore, the synthesis method of the embodiment has the advantages of low energy consumption, low raw material cost, high safety, high efficiency and the like, and is easy for mass production.
The electrode prepared by uniformly growing the superfine aluminum nanocrystalline material powder on the surface of the carbon fiber has the lithium storage first discharge capacity as high as 1760 mAh/g-2225 mAh/g.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the anhydrous aluminum chloride to the lithium metal material in the step one is 1 (2-5). The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the mass ratio of the hydroxylated carbon fibers to the anhydrous aluminum chloride in the first step is 1 (24-100). The rest is the same as the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the volume ratio of the mole of the anhydrous aluminum chloride to the tetrahydrofuran in the step one is 1mol (1000-50000) mL. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the volume ratio of the moles of the anhydrous aluminum chloride to the tetrahydrofuran in the step one is 1mol (10000-50000) mL. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the first step, the reaction is carried out for 24 to 50 hours under the condition of argon atmosphere and temperature of 70 to 180 ℃. The rest is the same as the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: in the first step, the reaction is carried out for 24 hours under the condition of argon atmosphere and 70 ℃. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and the washing in the step two is centrifugal washing by taking tetrahydrofuran as a detergent. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the centrifugal washing is specifically to centrifuge for 3-10 min under the condition that the centrifugal rotating speed is 2000-8000 rpm, and the repeated centrifugal washing is 4-8 times. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the drying in the second step is drying for 2 to 30 hours under the condition of argon atmosphere and temperature of 40 to 200 ℃. The other points are the same as those in the first to ninth embodiments.
The following examples were employed to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for uniformly growing superfine aluminum nanocrystals on the surface of carbon fibers comprises the following steps:
firstly, sequentially adding 0.95g of anhydrous aluminum chloride, 0.039g of hydroxylated carbon fiber, 70mL of tetrahydrofuran and 0.1g of lithium sheet into a vertical stainless steel reaction kettle, and reacting for 24 hours under the condition of argon atmosphere and 70 ℃ to obtain a reaction product;
and secondly, washing and drying the reaction product at room temperature to obtain the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The hydroxylated carbon fiber described in step one is produced by Shanghai Aladdin Biotechnology GmbH.
The diameter of the hydroxylated carbon fiber in the first step is about 50 nm.
And the washing in the step two is centrifugal washing by taking tetrahydrofuran as a detergent.
The centrifugal washing is specifically to centrifuge for 5min under the condition that the centrifugal rotating speed is 4000rpm, and the repeated centrifugal washing is 5 times.
And the drying in the second step is drying for 5 hours under the condition of argon atmosphere and the temperature of 80 ℃.
The vertical stainless steel reaction kettle in the step two is a miniature high-pressure reaction kettle with the specification of 100mL, and the manufacturer is Anhui Huapistil experimental equipment Co.
FIG. 1 is an X-ray diffraction diagram of the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber prepared in the first embodiment, wherein the solid is aluminum,
Figure BDA0003712943980000051
is carbon fiber. The diffraction peaks of aluminum and carbon fibers are clearly seen from the figure, and there is no AlCl in the raw material 3 The existence of impurities such as materials, lithium metal and the like shows that the reaction for preparing the aluminum nanocrystals at lower temperature is completely carried out, and the required material components are obtained preliminarily.
Fig. 2 is a transmission electron microscope image of the carbon fiber surface uniformly grown with the ultrafine aluminum nanocrystalline material powder prepared in the first embodiment, wherein a is a low-resolution transmission electron microscope image, and b is a high-resolution transmission electron microscope image. As can be seen from the graph a, the nanocrystals are very uniformly distributed on the surface of the carbon fiber, the nanocrystals are highly dispersed in the nanoscale, and the sizes of the nanocrystals are relatively uniform, about 10 nm. As can be seen from fig. b, the lattice spacing of the uniform nanoparticles on the surface of the carbon fiber is completely matched with the (111) crystal face of aluminum, and the result of fig. 1 shows that the particles on the surface of the carbon fiber are aluminum nanocrystals. Fig. 1 and fig. 2 are combined to prove that the structure of uniformly growing ultrafine aluminum nanocrystals on the surface of carbon fibers has been synthesized.
FIG. 3 is an infrared spectrum, wherein a is hydroxylated carbon fiber, and b is ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber. As is clear from the a-diagram, the hydroxylated carbon fiber is 3445cm -1 Has obvious O-H (hydroxyl) vibration peak. From the b-chart, it can be observed that the O-H vibration peak of the original hydroxylated carbon fiber completely disappears at 446cm -1 A new O-Li oscillation peak appears, which indicates that the hydroxyl group on the surface of the carbon fiber is completely converted into an-OLi group in the lithium-containing reaction system. Thus, the original hydroxylated carbon fiber is completely converted in situ into a carbon fiber with surface-OLi groups.
And (3) testing the performance of the lithium ion battery:
uniformly mixing the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber prepared in the first embodiment, acetylene black and polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone according to the mass ratio of 70:15:15 to form slurry, and uniformly coating the slurry on copper foil to prepare a pole piece. The battery assembly was carried out in a glove box filled with Ar gas, with a metal lithium plate as the counter electrode, a microporous polypropylene membrane Celgard 2400 as the separator, and LiPF 6 The mixed solution of fluoroethylene carbonate, ethylene carbonate and dimethyl carbonate is used as electrolyte; LiPF in the electrolyte 6 The concentration of (A) is L mol/L; the mass percent of fluoroethylene carbonate in the electrolyte is 5%; the volume ratio of the ethylene carbonate to the dimethyl carbonate in the electrolyte is 1: 1. The battery tester is used for testing by a battery tester in Wuhan LAND CT2001A, and the testing voltage range is 0.005V-3.0V.
FIG. 4 is a schematic view ofUnder the current of 200mA/g, the lithium storage rate performance graph of the electrode prepared by uniformly growing the ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber in the first embodiment is used, and O represents discharge,
Figure BDA0003712943980000052
representing charging. The primary discharge capacity of the lithium ion battery is up to 2225mAh/g at a current of 200mA/g, the primary charge capacity of the lithium ion battery is 1316mAh/g, and the lithium ion battery still has the capacity of 480mAh/g and excellent stability at a large current of 8000 mA/g. The Al nanocrystalline loaded on the surface of the carbon fiber is very uniform in the ultrafine aluminum nanocrystalline material uniformly grown on the surface of the carbon fiber, and the two components are strongly combined, so that the ultrafine aluminum nanocrystalline material has the advantages of high nanoscale dispersion and excellent conductivity, and has outstanding lithium storage rate performance and stability.
Comparison experiment one: the comparative experiment differs from the first example in that: and (3) the carbon fiber used in the step one is the carbon fiber without any group on the surface, and finally the aluminum-carbon fiber composite material is prepared. The rest is the same as the first embodiment.
FIG. 5 is a transmission electron microscope image of an aluminum and carbon fiber composite material prepared in comparative experiment one; as can be seen from the figure, the Al nanocrystals in the product did not grow on the carbon fiber having no surface groups, and both exhibited a state of being separated from each other. And the Al nanocrystalline is very serious in agglomeration and larger in size, and is obviously larger than the superfine aluminum nanocrystalline prepared in the first embodiment. This indicates that the uniformly grown ultrafine Al nanocrystals cannot be obtained in the reaction process of the carbon fiber without the surface groups. Therefore, the surface-OLi group orientation of the carbon fiber is the key for constructing the uniform self-assembly composite material of the superfine aluminum nanocrystals and the carbon fiber.

Claims (10)

1. A method for uniformly growing superfine aluminum nanocrystals on the surface of carbon fibers is characterized by comprising the following steps:
firstly, adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle in sequence, and reacting for 2-50 h under the condition of argon atmosphere and temperature of 30-180 ℃ to obtain a reaction product;
the mass ratio of the hydroxylated carbon fiber to the anhydrous aluminum chloride is 1 (10-100); the molar ratio of the anhydrous aluminum chloride to the lithium metal material is 1 (1-5);
and secondly, washing and drying the reaction product at room temperature to obtain the ultrafine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
2. The method of claim 1, wherein the molar ratio of the anhydrous aluminum chloride to the lithium metal material in the step one is 1 (2-5).
3. The method of claim 1, wherein the mass ratio of the hydroxylated carbon fiber to the anhydrous aluminum chloride in the first step is 1 (24-100).
4. The method of claim 1, wherein the molar ratio of anhydrous aluminum chloride to tetrahydrofuran in the first step is 1mol (1000-50000) mL.
5. The method of claim 4, wherein the volume ratio of anhydrous aluminum chloride to tetrahydrofuran is 1mol (10000-50000) mL.
6. The method of claim 1, wherein the step one is carried out in an argon atmosphere at a temperature of 70-180 ℃ for 24-50 h.
7. The method of claim 6, wherein the step one is carried out in an argon atmosphere at 70 ℃ for 24 h.
8. The method of claim 1, wherein the washing step is centrifugal washing with tetrahydrofuran as a washing agent.
9. The method of claim 8, wherein the centrifugal washing is performed for 3-10 min at a centrifugal speed of 2000-8000 rpm, and the repeated centrifugal washing is performed for 4-8 times.
10. The method for uniformly growing the ultrafine aluminum nanocrystals on the surface of the carbon fiber as claimed in claim 1, wherein the drying in the second step is performed in an argon atmosphere at a temperature of 40-200 ℃ for 2-30 h.
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