CN115070056B - Method for uniformly growing ultrafine aluminum nanocrystalline on carbon fiber surface - Google Patents
Method for uniformly growing ultrafine aluminum nanocrystalline on carbon fiber surface Download PDFInfo
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Classifications
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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
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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
- 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
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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
- 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
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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
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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 ultrafine aluminum nanocrystals on the surface of carbon fiber belongs to the technical field of nanomaterial synthesis. The invention aims to solve the problems that the existing aluminum nanostructure material synthesis method requires complex multi-step reaction, high-temperature heating, and extremely dangerous aluminum precursors and harsh reaction conditions. The method comprises the following steps: 1. mixing anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material for reaction; 2. the reaction product was washed and dried. The method is used for uniformly growing ultrafine aluminum nanocrystals on the surface of the carbon fiber.
Description
Technical Field
The invention belongs to the technical field of nano material synthesis.
Background
As the most abundant metal element in the crust, aluminum is widely applied in the traditional industrial manufacturing field, and has important application value in the fields of alloy manufacturing, industrial cable metal fuel and the like. However, conventional aluminum metal is difficult to apply in fields with higher added values. In contrast, nanostructured aluminum exhibits a variety of novel properties, and has been used in recent years in advanced technical fields such as luminescence, uv photoelectrodevices, photocatalysis, and lithium ion batteries. In particular in the field of lithium ion batteries, nano-aluminium has an ultra-high theoretical specific capacity of about 2234mAh/g and a very correct working potential (-0.5V vs. Li/Li) + ). However, the preparation of nanostructured aluminum is very difficult due to the high chemical activity of aluminum, which seriously affects the practical application of aluminum.
The study of nanostructured aluminum is very limited because of its high reactivity and its complex preparation itself. Few reports of nanostructured aluminum synthesis require in a severe environment at high temperature and pressure, with concomitant high energy consumption. For example, in various organic systems, aluminum nanorods are synthesized by performing multi-step reaction on triisobutylaluminum, but the decomposition temperature of triisobutylaluminum needs to be higher than 250 ℃, and triisobutylaluminum precursors have strong corrosivity and extremely high chemical reactivity (spontaneous combustion when encountering air, strong reaction and explosion when encountering water, acid, alcohol and ammonia) and have extremely high operation danger. The other is to prepare the graphene composite aluminum nanocrystalline material by reducing triethylaluminum on graphene nano sheets at a high temperature of 230 ℃ and under extremely high hydrogen pressure (50 atm) by utilizing the reducibility of hydrogen, and the method also faces extremely high risks (triethylaluminum precursors are extremely toxic and are easy to cause combustion explosion when meeting trace oxygen and water), so that the practical application of the triethylaluminum precursors is greatly limited. Thus, the current methods for synthesizing nanostructured aluminum have the following disadvantages: the preparation method is quite complex, multiple steps of reactions are needed to be separated, high reaction temperature is needed, the energy consumption of the reaction is high, and the environmental conditions needed by synthesis are dangerous and harsh; the starting material for synthesizing aluminum nanostructures is an aluminum organism, which is not only very expensive, but also highly dangerous.
Disclosure of Invention
The invention aims to solve the problems that the existing aluminum nanostructure material synthesis method requires complex multi-step reaction, high-temperature heating, and extremely dangerous aluminum precursors and harsh reaction conditions, and further provides a method for uniformly growing ultrafine aluminum nanocrystals on the surface of carbon fibers.
A method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber comprises the following steps:
1. sequentially adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle, 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);
2. and washing and drying the reaction product at room temperature to obtain the superfine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The beneficial effects of the invention are as follows:
unlike other high Wen Gaowei nanometer structure aluminum preparing technology, the present invention provides one kind of synthesis process of surface group oriented superfine aluminum nanometer crystal growing homogeneously on the surface of carbon fiber. The new productThe synthesis method is that under the low temperature condition, the metal aluminum is uniformly self-assembled to the carbon fiber surface on the nanometer scale by a 'surface group-guided self-assembly strategy', so as to form the carbon fiber surface uniformly grown ultrafine aluminum nanocrystalline. The surface group guided self-assembly strategy is to realize that atoms or molecules without fixed size are self-assembled to the surface of a target material to form nano-products through chemical reaction under the guidance of specific functional groups by utilizing the specific functional groups on the surface of the material. In the organic solvent containing lithium metal, the method utilizes the hydroxyl groups rich on the surface of the hydroxylated carbon fiber to be converted into-OLi groups (H is replaced by Li), -the OLi groups can be combined with free AlCl in the solution 3 The molecules form a tight bond such that AlCl 3 The metal Al generated after the molecule reacts with Li metal at a lower temperature under the guidance of an-OLi group can be self-assembled on the surface of the carbon fiber in situ to form uniform superfine Al nanocrystalline (about 10 nm). The 'surface-OLi group guiding' is the key of constructing the ultra-fine aluminum nanocrystalline and carbon fiber uniform self-assembled composite material at low temperature.
In the present invention AlCl is used 3 Very cheap, safe and non-combustible, and low-temperature reduction of Li to AlCl 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 instantaneous local overgrowth and agglomeration of the Al nanocrystalline, thereby generating superfine Al nanocrystalline. Therefore, the synthesis 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 ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber has the first discharge capacity of lithium storage reaching 1760 mAh/g-2225 mAh/g.
Drawings
FIG. 1 is an X-ray diffraction chart of a carbon fiber surface uniformly grown with ultrafine aluminum nanocrystalline material powder, diamond-solid being aluminum,is carbon fiber;
FIG. 2 is a transmission electron microscope image of the carbon fiber surface prepared in the first embodiment in which ultra-fine aluminum nanocrystalline material powder is uniformly grown, a is a low resolution transmission electron microscope image, and b is a high resolution transmission electron microscope image;
FIG. 3 is an infrared spectrogram, wherein a is a hydroxylated carbon fiber, and b is a powder of ultrafine aluminum nanocrystalline material uniformly grown on the surface of the carbon fiber;
FIG. 4 is a graph showing the rate performance of an electrode prepared by uniformly growing ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber of example I at a current of 200mA/g, O represents discharge,representing charging;
fig. 5 is a transmission electron microscope image of an aluminum and carbon fiber composite material prepared in comparative experiment one.
Detailed Description
The first embodiment is as follows: the method for uniformly growing ultrafine aluminum nanocrystalline on the surface of the carbon fiber in the embodiment comprises the following steps:
1. sequentially adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle, 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);
2. and washing and drying the reaction product at room temperature to obtain the superfine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The beneficial effects of this embodiment are:
unlike other high Wen Gaowei nanometer structure aluminum preparation technology, the embodiment provides a synthesis method for uniformly growing superfine aluminum nanocrystalline on the surface of a carbon fiber guided by surface groups. The novel synthesis method is that under the low-temperature condition, metal aluminum is uniformly self-assembled on the nanoscale by a self-assembly strategy guided by surface groups, and ultrafine aluminum nanocrystalline uniformly grows on the surface of carbon fiber formed on the surface of carbon fiber. "surface group directed self-assembly strategy" is specifically directed to utilizing the surface of a materialThe specific functional group realizes that atoms or molecules with no fixed size are self-assembled to the surface of the target material through chemical reaction under the guidance of the specific functional group to form nano-products. In the organic solvent containing lithium metal, the method utilizes the hydroxyl groups rich on the surface of the hydroxylated carbon fiber to be converted into-OLi groups (H is replaced by Li), -the OLi groups can be combined with free AlCl in the solution 3 The molecules form a tight bond such that AlCl 3 The metal Al generated after the molecule reacts with Li metal at a lower temperature under the guidance of an-OLi group can be self-assembled on the surface of the carbon fiber in situ to form uniform superfine Al nanocrystalline (about 10 nm). The 'surface-OLi group guiding' is the key of constructing the ultra-fine aluminum nanocrystalline and carbon fiber uniform self-assembled composite material at low temperature.
In this embodiment, alCl is used 3 Very cheap, safe and non-combustible, and low-temperature reduction of Li to AlCl 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 instantaneous local overgrowth and agglomeration of the Al nanocrystalline, thereby generating superfine Al nanocrystalline. 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 ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber has the first discharge capacity of lithium storage reaching 1760 mAh/g-2225 mAh/g.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the molar ratio of the anhydrous aluminum chloride to the lithium metal material in the first step is 1 (2-5). The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the ratio of the hydroxylated carbon fiber to the anhydrous aluminum chloride in the first step is 1 (24-100). The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the volume ratio of the mol of the anhydrous aluminum chloride to the tetrahydrofuran in the first step is 1mol (1000-50000) mL. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the volume ratio of the mol of the anhydrous aluminum chloride to the tetrahydrofuran in the first step is 1mol (10000-50000) mL. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: in the first step, the reaction is carried out for 24 to 50 hours under the conditions of argon atmosphere and the temperature of 70 to 180 ℃. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: in the first step, the reaction is carried out for 24 hours under the condition of argon atmosphere and 70 ℃. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and step two, washing is centrifugal washing by using tetrahydrofuran as a detergent. The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the centrifugal washing is carried out for 3-10 min under the condition that the centrifugal rotating speed is 2000-8000 rpm, and the repeated centrifugal washing is carried out for 4-8 times. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step two, drying for 2 to 30 hours under the conditions of argon atmosphere and the temperature of 40 to 200 ℃. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one:
a method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber comprises the following steps:
1. 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;
2. and washing and drying the reaction product at room temperature to obtain the superfine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
The hydroxylated carbon fibers described in step one are produced by Shanghai Ala Biochemical technologies Co., ltd.
The diameter of the hydroxylated carbon fiber in the first step is about 50 nm.
And step two, washing is centrifugal washing by using tetrahydrofuran as a detergent.
The centrifugal washing is specifically carried out for 5min under the condition that the centrifugal rotating speed is 4000rpm, and the centrifugal washing is repeated for 5 times.
The drying in the second step is specifically drying for 5 hours under the condition of argon atmosphere and 80 ℃.
The vertical stainless steel reaction kettle in the second step is a miniature high-pressure reaction kettle with the specification of 100mL, and the manufacturer is Anhua Hua stamen experiment equipment Co., ltd.
FIG. 1 is an X-ray diffraction chart of a carbon fiber surface uniformly grown with ultrafine aluminum nanocrystalline material powder, diamond-solid being aluminum,is carbon fiber. The diffraction peaks of aluminum and carbon fibers are evident 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 nanocrystalline at a lower temperature is quite complete, and the required material components are obtained initially.
Fig. 2 is a transmission electron microscope image of the carbon fiber surface prepared in the first embodiment in which ultra-fine aluminum nanocrystalline material powder is uniformly grown, a is a low resolution transmission electron microscope image, and b is a high resolution transmission electron microscope image. From the graph a, the nanocrystals are uniformly distributed on the surface of the carbon fiber, so that the high dispersion of the nanocrystals is realized in the nanoscale, and the size of the nanocrystals is 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 plane of aluminum, and the result of fig. 1 is combined to show that the particles on the surface of the carbon fiber are aluminum nanocrystals. The combination of fig. 1 and fig. 2 demonstrates that the uniform growth of ultrafine aluminum nanocrystalline structures on the surface of carbon fibers has been synthesized.
Fig. 3 is an infrared spectrogram, a is a hydroxylated carbon fiber, and b is a powder of ultrafine aluminum nanocrystalline material uniformly grown on the surface of the carbon fiber. As can be clearly seen from the graph a, the hydroxylated carbon fiber is at 3445cm -1 There is a distinct O-H (hydroxyl) vibration peak. As can be seen from the graph b, the O-H vibration peak of the original hydroxylated carbon fiber completely disappeared, while at 446cm -1 A new O-Li vibration peak appears, which indicates that the hydroxyl groups on the surface of the carbon fiber are completely converted into-OLi groups in the lithium-containing reaction system. Thus, the original hydroxylated carbon fibers are completely converted in situ into carbon fibers with surface-OLi groups.
Lithium ion battery performance test:
uniformly mixing ultrafine aluminum nanocrystalline material powder, acetylene black and polyvinylidene fluoride (PVDF) which are uniformly grown on the surface of the carbon fiber prepared in the first embodiment in N-methylpyrrolidone according to the mass ratio of 70:15:15 to form slurry, and uniformly coating the slurry on a copper foil to prepare the pole piece. The battery assembly is carried out in a glove box filled with Ar gas, a metal lithium sheet is used as a counter electrode, a microporous polypropylene film Celgard 2400 is used as a diaphragm, and LiPF is used 6 The mixed solution of fluoroethylene carbonate, ethylene carbonate and dimethyl carbonate is electrolyte; liPF in the electrolyte 6 The concentration of (2) is L mol/L; the mass percentage 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 the battery with the voltage ranging from 0.005V to 3.0V.
FIG. 4 is a graph showing the rate performance of an electrode prepared by uniformly growing ultrafine aluminum nanocrystalline material powder on the surface of the carbon fiber of example I at a current of 200mA/g, O represents discharge,representing charging. The first discharge capacity of the material reaches 2225mAh/g under the current of 200mA/gThe primary charging capacity is 1316mAh/g, and the battery still has 480mAh/g capacity and excellent stability under the high current of 8000 mA/g. The method shows that Al nanocrystalline in the superfine aluminum nanocrystalline material uniformly grown on the surface of the carbon fiber is uniformly loaded on the surface of the carbon fiber, and the two components are strongly combined, so that the superfine aluminum nanocrystalline material has high dispersion in nanoscale and excellent conductivity, and has outstanding lithium storage rate performance and stability.
Comparative experiment one: the first difference between this comparative experiment and the example is: and C, the carbon fiber used in the step A is carbon fiber without any group on the surface, and finally the aluminum and carbon fiber composite material is prepared. The other is the same as in 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, al nanocrystals in the product did not grow on the carbon fiber with no surface groups, and the two exhibited a state of being separated from each other. Moreover, the agglomeration of Al nanocrystalline is serious, and the size is larger, which is obviously larger than the superfine aluminum nanocrystalline prepared in the first embodiment. This indicates that the uniformly grown ultrafine Al nanocrystalline cannot be obtained in the reaction process of the carbon fiber without the surface groups. Therefore, the carbon fiber surface-OLi group guiding is a key for constructing the superfine aluminum nanocrystalline and carbon fiber uniform self-assembled composite material.
Claims (7)
1. A method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber is characterized by comprising the following steps:
1. sequentially adding anhydrous aluminum chloride, hydroxylated carbon fiber, tetrahydrofuran and lithium metal material into a reaction kettle, and reacting for 24-50 hours under the conditions of argon atmosphere and 70-180 ℃ to obtain a reaction product;
the mass ratio of the hydroxylated carbon fiber to the anhydrous aluminum chloride is 1 (24-100); the molar ratio of the anhydrous aluminum chloride to the lithium metal material is 1 (1-5); the volume ratio of the mol of the anhydrous aluminum chloride to the tetrahydrofuran is 1mol (1000-50000) mL;
2. and washing and drying the reaction product at room temperature to obtain the superfine aluminum nanocrystalline material powder uniformly grown on the surface of the carbon fiber.
2. The method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber according to 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 for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber according to claim 1, wherein the volume ratio of the anhydrous aluminum chloride to tetrahydrofuran in the first step is 1mol (10000-50000) mL.
4. The method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber according to claim 1, wherein the reaction is performed for 24 hours in the argon atmosphere at a temperature of 70 ℃.
5. The method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber according to claim 1, wherein the washing in the second step is centrifugal washing with tetrahydrofuran as a detergent.
6. The method for uniformly growing ultrafine aluminum nanocrystals on the surface of the carbon fiber according to claim 5, wherein the centrifugal washing is performed for 3-10 min under the condition that the centrifugal rotation speed is 2000-8000 rpm, and the repeated centrifugal washing is performed for 4-8 times.
7. The method for uniformly growing ultrafine aluminum nanocrystals on the surface of a carbon fiber according to claim 1, wherein the drying in the second step is specifically performed under the condition of argon atmosphere at 40-200 ℃ for 2-30 h.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450676A (en) * | 2003-04-28 | 2003-10-22 | 振华集团深圳电子有限公司 | Lithium ion positive electrode material and preparation method thereof |
| CN101687710A (en) * | 2008-05-19 | 2010-03-31 | 通用电气公司 | Composite article and related method |
| CN103137974A (en) * | 2011-11-24 | 2013-06-05 | 海洋王照明科技股份有限公司 | Lithium ion battery anode active material, preparation method of the lithium ion battery anode active material, and lithium ion battery |
| CN103165894A (en) * | 2011-12-15 | 2013-06-19 | 海洋王照明科技股份有限公司 | Graphene-hydroxyl lithium composite, and preparation method and application thereof |
| CN103774413A (en) * | 2013-12-05 | 2014-05-07 | 天津大学 | Aluminum and carbon nanotube composite fiber material and preparation method thereof |
| CN106517113A (en) * | 2016-12-27 | 2017-03-22 | 哈尔滨理工大学 | Preparation method of AlN |
| CN108134052A (en) * | 2016-12-01 | 2018-06-08 | 内蒙古欣源石墨烯科技有限公司 | High-volume silicon-carbon negative electrode material and preparation method thereof used in a kind of power battery |
| CN108550817A (en) * | 2018-04-18 | 2018-09-18 | 北京化工大学 | A kind of high performance lithium ion battery aluminium base negative material and preparation method thereof |
| CN109666816A (en) * | 2019-02-02 | 2019-04-23 | 河北工业大学 | The preparation method of Carbon Nanotubes/Magnesiuum Matrix Composite |
| KR20190056484A (en) * | 2017-11-17 | 2019-05-27 | 주식회사 엘지화학 | Positive electrode material for lithium-sulfur battery comprising secondary structure of carbon nanotube and method of manufacturing the same |
| CN110718398A (en) * | 2018-07-13 | 2020-01-21 | 天津大学 | High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof |
| CN112239553A (en) * | 2020-10-15 | 2021-01-19 | 东北林业大学 | Construction method of intelligent reversible self-assembly structure based on core-shell type phase-change cellulose nanocrystals under solid-phase condition |
| CN113336206A (en) * | 2021-07-20 | 2021-09-03 | 哈尔滨工程大学 | Method for synthesizing porous black phosphorus nanosheet for negative electrode material of ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8491698B2 (en) * | 2009-06-16 | 2013-07-23 | The United States Of America, As Represented By The Secretary Of The Navy | Metal-based nanoparticles and methods for making same |
-
2022
- 2022-06-24 CN CN202210730148.5A patent/CN115070056B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450676A (en) * | 2003-04-28 | 2003-10-22 | 振华集团深圳电子有限公司 | Lithium ion positive electrode material and preparation method thereof |
| CN101687710A (en) * | 2008-05-19 | 2010-03-31 | 通用电气公司 | Composite article and related method |
| CN103137974A (en) * | 2011-11-24 | 2013-06-05 | 海洋王照明科技股份有限公司 | Lithium ion battery anode active material, preparation method of the lithium ion battery anode active material, and lithium ion battery |
| CN103165894A (en) * | 2011-12-15 | 2013-06-19 | 海洋王照明科技股份有限公司 | Graphene-hydroxyl lithium composite, and preparation method and application thereof |
| CN103774413A (en) * | 2013-12-05 | 2014-05-07 | 天津大学 | Aluminum and carbon nanotube composite fiber material and preparation method thereof |
| CN108134052A (en) * | 2016-12-01 | 2018-06-08 | 内蒙古欣源石墨烯科技有限公司 | High-volume silicon-carbon negative electrode material and preparation method thereof used in a kind of power battery |
| CN106517113A (en) * | 2016-12-27 | 2017-03-22 | 哈尔滨理工大学 | Preparation method of AlN |
| KR20190056484A (en) * | 2017-11-17 | 2019-05-27 | 주식회사 엘지화학 | Positive electrode material for lithium-sulfur battery comprising secondary structure of carbon nanotube and method of manufacturing the same |
| CN108550817A (en) * | 2018-04-18 | 2018-09-18 | 北京化工大学 | A kind of high performance lithium ion battery aluminium base negative material and preparation method thereof |
| CN110718398A (en) * | 2018-07-13 | 2020-01-21 | 天津大学 | High-capacity carbon nanotube-cobaltosic sulfide nickel composite material and preparation method and application thereof |
| CN109666816A (en) * | 2019-02-02 | 2019-04-23 | 河北工业大学 | The preparation method of Carbon Nanotubes/Magnesiuum Matrix Composite |
| CN112239553A (en) * | 2020-10-15 | 2021-01-19 | 东北林业大学 | Construction method of intelligent reversible self-assembly structure based on core-shell type phase-change cellulose nanocrystals under solid-phase condition |
| CN113336206A (en) * | 2021-07-20 | 2021-09-03 | 哈尔滨工程大学 | Method for synthesizing porous black phosphorus nanosheet for negative electrode material of ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 氧化镍/碳纳米管构筑准固态不对称超级电容器及电化学性能;徐舟;侯程;王诗琴;王佳其;庄严;贾海浪;关明云;;化工进展(第10期);全文 * |
| 炭材料在锂离子电池中的应用及前景;闻雷;宋仁升;石颖;李峰;成会明;;科学通报(第31期);全文 * |
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