CN114835111A - Nano spiral graphite fiber material and preparation method and application thereof - Google Patents
Nano spiral graphite fiber material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a nano spiral graphite fiber material and a preparation method and application thereof. The invention takes methane gas as a precursor, prepares the nano spiral fiber by adopting a vapor deposition process, and prepares the nano spiral graphite fiber by sequentially carrying out a carbonization process and a graphitization process, and the nano spiral graphite fiber has good conductivity, is beneficial to the rapid transportation of lithium ions, and can also be used as a functional material of a conductive additive; the prepared nano spiral graphite fiber carbon layer is of a fold stack structure, is more beneficial to ion storage, has good lithium storage performance and cycle stability, and can be used as a high-performance lithium ion battery cathode material to prepare a high-capacity lithium ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery electrode materials, in particular to a nano spiral graphite fiber material and a preparation method and application thereof.
Background
The negative electrode material of commercial lithium ion batteries generally uses graphite materials, and the graphite materials are still the main force in the field of negative electrode materials at present. The graphite materials are various, including natural crystalline flake graphite, artificial graphite, fibrous carbon materials (with graphite structure) and the like; the non-renewable natural crystalline flake graphite has a natural graphite structure degree, and can be directly used as a lithium ion battery cathode material after high-temperature treatment; the artificial graphite is generally prepared by using natural crystalline flake graphite as an aggregate and combining other materials through a hot pressing process; after long-time circulation, the lithium storage capacity of the natural crystalline flake graphite and the artificial graphite is generally maintained at 320mA h/g; the lithium storage capacity of the graphite material after the improved treatment can be close to the theoretical capacity level (372mA h/g; LiC) in a short time to a certain extent 6 ). Compared with graphite materials, the fibrous carbon material has potential advantages, the carbon fiber is the fibrous carbon material, the carbon element content in the chemical composition of the fibrous carbon material is more than 90%, the carbon fiber has the advantages of higher specific modulus, high heat conduction/electric rate, corrosion resistance, creep resistance, low thermal expansion coefficient and the like, can be used as a structural material and a functional material, and is widely applied to the fields of automobile manufacturing, bridge construction, cultural and sports entertainment products and the like.
With the development of science and technology, the specific capacity provided by the conventional graphite cathode material cannot meet the requirements of power sources, electronic products and the like, and the cathode material with high specific capacity is urgently needed. In the negative electrode material, materials such as silicon, germanium, tin and the like also have higher theoretical lithium storage capacity, wherein the silicon material has extremely high first lithium intercalation specific capacity, the theoretical calculation value is up to 4200mA h/g, and the theoretical calculation value can still reach 3500mA h/g at room temperature, so that the requirements of electronic products and the like on the ion battery can be well met, but in the alloying-dealloying process, the silicon material has violent volume change, so that the structure of the silicon negative electrode material is damaged, the electric contact fails, and the cycle life and the specific capacity of the silicon negative electrode material are reduced.
In the face of the rapid updating and upgrading of consumer electronics equipment and the requirement of electric automobiles on prolonging the endurance mileage, the energy density of batteries is urgently needed to be greatly improved, so that the development of new high-performance batteries is urgently needed; the development of lithium ion batteries with high energy density, high power density and long service life has important application significance for the development of portable electronic equipment and electric automobiles. There is therefore a need for a new material that overcomes the problems of the prior art: (1) the commercial graphite material is prepared by taking non-renewable natural crystalline flake graphite as a main raw material, so that the problem of exhaustion of graphite resources is inevitably faced; (2) most of other novel lithium ion battery cathode materials such as silicon-based and the like are prepared by adopting a harsh and high-difficulty nanotechnology, the yield is low, and no enterprise realizes the production scale of hundreds of tons per year; (3) the preparation process of the commercial artificial graphite cathode material is complex, and the technical requirements are strict.
One of the military and civil dual-purpose materials in the carbon material can be used as a structural material and also can be used as a functional material (high electric conductivity, high thermal conductivity, negative expansion coefficient and the like) for realizing a certain function; the microstructure of the carbon material is further designed and regulated, so that the first specific capacity can be improved, the theoretical numerical limit of 372mAh/g can be broken through, the integral conductivity of the material can be improved, the cycle life and the high specific capacity of the electrode material can be improved, the inherent requirement of the electrode material as a lithium ion battery cathode material can be met, and the novel graphite cathode material of a new generation of lithium ion battery can be expected.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a nano spiral graphite fiber material and a preparation method and application thereof, methane gas is used as a precursor, a vapor deposition process is adopted to prepare nano spiral fibers, and the nano spiral graphite fibers are prepared by a carbonization process and a graphitization process in sequence, so that the nano spiral graphite fiber material has good conductivity, is beneficial to quick transportation of lithium ions, and can also be used as a functional material of a conductive additive; the prepared nano spiral graphite fiber carbon layer is of a fold stack structure, is more beneficial to ion storage, has good lithium storage performance and cycle stability, and can be used as a high-performance lithium ion battery cathode material to prepare a high-capacity lithium ion battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nano spiral graphite fiber material comprises the following steps:
(1) and (3) a vapor deposition process: methane is used as a raw material, a metal catalyst is added, and a vapor deposition method is adopted to prepare the nano spiral fiber;
(2) and (3) a carbonization process: carbonizing the nano spiral fiber in the step (1) for 0.5h at 1000-;
(3) the graphitization process comprises the following steps: graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h under the protection of high-purity argon at the temperature of 2000-3273K to obtain the nano spiral graphite fiber material.
Preferably, the metal catalyst of step (1) is selected from copper powder or nickel powder.
Preferably, when the catalyst is selected from copper powder, the conditions of the vapor deposition method in the step (1) are as follows: placing copper powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-800K at the rate of 1-10K/min, preserving heat for 1-2h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 30-80 mL/min: 50-120 mL/min.
Preferably, when the catalyst is selected from nickel powder, the conditions of the vapor deposition method in step (1) are as follows: putting nickel powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-1000K at the rate of 1-10K/min, preserving heat for 1-1.5h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 20-50 mL/min: 40-100 mL/min.
Preferably, the inert atmosphere of step (2) is selected from a high-purity argon atmosphere or a high-purity nitrogen atmosphere, and the carbonization process of step (2): carbonizing the nano spiral fiber in the step (1) for 0.5h at the temperature rise rate of 3-10K/min and at the temperature of 1100-1573K in an inert atmosphere to obtain the carbonized nano spiral fiber.
Preferably, the graphitization process of step (3): under the protection of high-purity argon, graphitizing the carbonized nano-spiral fiber obtained in the step (2) for 0.5h at the temperature rise rate of 3-10K/min under the temperature rise rate of 2500-3273K, and thus obtaining the nano-spiral graphite fiber material.
The invention also protects the nano spiral graphite fiber material prepared by the preparation method of the nano spiral graphite fiber material.
The invention also protects the application of the nano spiral graphite fiber material in the preparation of lithium ion battery cathode materials or conductive additive materials.
Preferably, the lithium ion battery cathode material prepared from the nano spiral graphite fiber material is prepared according to the following steps:
mixing a nano spiral graphite fiber material, a conductive agent and a binder, then mixing with a solvent to obtain a slurry, uniformly coating the slurry on the surface of a copper foil serving as a substrate, and drying to obtain a lithium ion battery negative electrode material;
wherein the mass ratio of the nano spiral graphite fiber material to the conductive agent to the binder is 7-8: 1-2: 1;
the conductive agent is selected from conductive carbon black, carbon nano tubes or graphene; the binder is selected from polyvinylidene fluoride or carboxymethyl cellulose; the solvent is selected from N-methyl pyrrolidone or deionized water.
The invention also protects the application of the lithium ion battery cathode material in the preparation of the lithium ion battery, and the lithium ion battery is prepared according to the following steps:
preparing a positive electrode material: tabletting and cutting the metal lithium;
preparing an electrolyte: mixing LiPF 6 Dissolving in organic solvent to prepare LiPF with concentration of 1mol/L 6 An electrolyte;
wherein the organic solvent consists of ethylene carbonate, dimethyl carbonate and vinylene carbonate in a volume ratio of 47.5:47.5: 5;
preparing a lithium ion battery: and sequentially assembling the anode material, the Cellgard2400 diaphragm, the electrolyte and the lithium ion battery cathode material to obtain the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts methane gas which is easily purchased in the market as a raw material, adopts a vapor deposition process to prepare the nano spiral fiber, and sequentially adopts carbonization and graphitization processes to prepare the nano spiral graphite fiber. The prepared nano spiral graphite fiber has the characteristics of good electrical conductivity, thermal conductivity, acid resistance, alkali resistance and corrosion resistance, and is beneficial to the rapid transportation of lithium ions; the carbon layer fold stacking structure is richer than the conventional graphite carbon layer structure, and is more beneficial to ion storage; the lithium ion negative electrode material can be used for preparing a high-performance lithium ion battery; in addition, the network structure of the nano spiral graphite fiber can also play a role in enhancing the functions and effects of materials such as silicon-based materials, etc. for relieving volume change and enhancing electrochemical lithium storage.
2. The preparation method of the nano spiral graphite fiber material has no harsh technical requirements, and when the nano spiral graphite fiber material is used as the lithium ion battery cathode material, the method can be matched with the existing lithium ion battery production line for production, does not need equipment transformation, and is suitable for mass enterprise production; the method improves the economic benefit of deep processing of the methane chemical products, simultaneously produces no toxic gas in the preparation process, meets the requirements of green, environmental protection and sustainable development, and is a lithium ion battery cathode material which is expected to replace the natural crystalline flake graphite in the prior art.
3. The specific capacity of lithium storage of the nano spiral graphite fiber material prepared by the invention exceeds the specific capacity of a graphite theory interlayer lithium storage mechanism 372mAh/g, has higher lithium storage potential, can be used as a high-performance lithium ion battery cathode material to prepare a lithium ion battery, and is attributed to the fact that the carbon layer structure of the material presents a stacking and folding shape, and the microstructure of the nano spiral fiber comprises: the carbon layer folds, carbon layer stacks and carbon layer bends, macroscopically presents a spiral structure along the fiber axial direction, and is different from a typical graphite sheet structure and the microstructures of other carbon materials, such as graphene, expanded graphite, porous carbon and the like; therefore, the invention provides a novel lithium storage mechanism with a synergistic structure.
4. The structure of the nano spiral graphite fiber material prepared by the invention is essentially different from the structures of a carbon nano tube and a carbon nano tube spiral material, and is also different from the microstructures of a typical graphite structure and a conventional carbon fiber, and the nano spiral graphite fiber material is a lithium storage material with a new microstructure in the aspect of lithium ion energy storage; the material is graphitized, so that the conductivity is good; the distribution of the carbon layer can be clearly seen in a transmission electron microscope, and the prior similar carbon material does not undergo graphitization process treatment, so that the effect can not be achieved.
5. The invention adopts a vapor deposition method to prepare the nano spiral fiber, so as to promote the specific capacity of lithium storage by the carbon layer structure presenting a stacking and folding shape, and then carbonization and graphitization treatment are carried out in sequence, wherein the carbonization is the conversion of the material from organic to inorganic; graphitization is the transition from a disordered structure to an ordered structure; after graphitization, the microstructure is richer, and the storage and transportation of lithium ions are facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of a nano-helical graphite fiber prepared in example 1 of the present invention, wherein a is a scanning electron microscope image of the fiber, b is a transmission electron microscope image of the fiber, and c is a transmission electron microscope image of a microstructure of a specific carbon layer of the fiber;
FIG. 2 is a graph of the rate capability of the nano spiral graphite fiber prepared in example 2 of the present invention at different current densities of 50mAh/g, 100mAh/g, 200mAh/g, 400mAh/g, 800mAh/g, and 50mAh/g in sequence;
FIG. 3 is a graph of the cycle performance of the nano-spiral graphite fiber prepared in example 3 of the present invention at a current density of 50 mAh/g;
FIG. 4 is a CV performance diagram of nano-helical graphite fibers prepared in example 2 of the present invention under 0.01-2V.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
Example 1
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: putting copper powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 573K at the rate of 3K/min, preserving heat for 1 hour, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.5;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 6K/min, the preset temperature is 1573K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 5K/min, the preset temperature is 3073K, and the constant temperature is kept for 0.5h to prepare the nano spiral graphite fiber.
Example 2
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: placing copper powder on a ceramic substrate, introducing a mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 603K at the speed of 2K/min, preserving heat for 1h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.8;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 4K/min, the preset temperature is 1373K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 3K/min, the preset temperature is 2773K, and the constant temperature is kept for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 3
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: placing copper powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 620K at the speed of 2K/min, preserving heat for 1.5h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.6;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 10K/min, the preset temperature is 1273K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 3K/min, the preset temperature is 2673K, and the temperature is kept for 0.5h to prepare the nano spiral graphite fiber.
Example 4
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: placing copper powder on a ceramic substrate, introducing a mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500K at the speed of 5K/min, preserving heat for 2 hours, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.5;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 8K/min, the preset temperature is 1000K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 10K/min, the preset temperature is 3273K, and the constant temperature is kept for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 5
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: placing copper powder on a ceramic substrate, introducing a mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 800K at the rate of 1K/min, preserving heat for 1h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.55;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 7K/min, the preset temperature is 1773K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 5K/min, the preset temperature is 2000K, and the temperature is kept for 0.5h to prepare the nano spiral graphite fiber.
Example 6
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing the nano spiral fiber by using methane gas as a raw material and copper powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: placing copper powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 800K at the speed of 10K/min, preserving heat for 1h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.65;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 3K/min, the preset temperature is 1100K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 10K/min, the preset temperature is 3273K, and the constant temperature is kept for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 7
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing nano spiral fiber by using methane gas as a raw material and nickel powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: putting nickel powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 1000K at the speed of 2K/min, preserving heat for 1h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.7;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 4K/min, the preset temperature is 1100K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 3K/min, the preset temperature is 3073K, and the constant temperature is kept for 0.5h to prepare the nano spiral graphite fiber.
Example 8
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) preparing nano spiral fiber by using methane gas as a raw material and nickel powder as a catalyst by adopting a vapor deposition technology;
the conditions of the vapor deposition method were: putting nickel powder on a ceramic substrate, introducing a mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500K at the speed of 5K/min, preserving heat for 1.5h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 1: 1.75;
(2) and (3) a carbonization process: under the protection of high-purity nitrogen, the heating rate is 5K/min, the preset temperature is 1573K, and the constant temperature is kept for 0.5 h;
(3) the graphitization process comprises the following steps: under the protection of high-purity argon, the heating rate is 5K/min, the preset temperature is 2500K, and the temperature is kept for 0.5h to prepare the nano spiral graphite fiber.
Results and discussion
The nano spiral graphite fiber materials used for the negative electrode materials of the lithium ion batteries are prepared in the embodiments 1 to 8 of the invention, and the effects are parallel, and the nano spiral graphite fiber materials prepared in the embodiments 1 to 3 are taken as examples for research, and the research methods and results are as follows:
FIG. 1 is a diagram showing the morphology of a nano-spiral graphite fiber prepared in example 1 of the present invention, wherein (a) the nano-spiral graphite fiber is a spiral carbon fiber with high purity and no non-spiral structure is found; the helix extends axially along the fibre with a pitch of about 60 nm. (b) The carbon sheet layer strips are spirally serpentine in a transmission view of a single carbon fiber; (c) the carbon fiber has a local microstructure, and the characteristic structures of carbon layer folds, carbon layer stacking, carbon layer bending and the like are clearly visible; especially, the carbon layer has perfect and clear stripes. As can be seen from FIG. 1, the material is spirally wound along the axial direction, and the section of the material is a solid structure, which is completely different from a hollow structure of the carbon nanotube; meanwhile, the microscopic carbon layer has the appearance of stacking and wrinkling, which is different from the layered stacking mode of typical graphite, but the lattice fringes are clearly visible, which shows that the microscopic carbon layer has good crystal characteristics; the microstructure is a novel carbon structure, and is different from a quasi-two-dimensional atomic crystal structure of graphene and a structure of carbon fiber at a micron level.
Mixing the nano spiral graphite fiber material prepared in the embodiment 1 with conductive carbon black serving as a conductive agent and polyvinylidene fluoride serving as a binder, dissolving the mixture in N-methylpyrrolidone, coating a uniform electrode plate by taking copper foil as a substrate, drying the electrode plate, and cutting the electrode plate into a wafer with the diameter of 16mm to prepare a lithium ion battery cathode material;
respectively assembling the anode material, the Cellgard2400 diaphragm, the electrolyte and the lithium ion battery cathode material in sequence to obtain a lithium ion battery;
and (3) detecting the performance of the battery: circulating under the current density of 50-800mA/g, inspecting the electrochemical performance, and selecting one series of materials as a negative electrode material to perform electrochemical performance test;
as shown in FIG. 2, the first embedding specific capacity can reach 440mAh/g after circulation under the current density of 0.05A/g; after circulation under different current densities, in the final test, the reversible average specific capacity of the material is still maintained to be 380mA h/g and exceeds the theoretical specific capacity of graphite to be 372mA h/g, the coulombic efficiency is very stable in the circulation process, and the excellent electrochemical performance is shown.
As shown in FIG. 3, under the test of small current 0.05A/g, the capacity is still maintained at 335mAh/g after 50 cycles, which shows that the material has better cycling stability.
As shown in fig. 4, in the CV test, the discharge current is gradually increasing from 1.45V; the initial anode peak potential is 0.5V, the peak position is stabilized at 0.48V and 0.49V after circulation, and the electrolyte on the surface of the electrode material is stably generated, thereby being beneficial to the improvement of the later circulation stability.
In conclusion, the prepared nano spiral graphite fiber has good lithium storage performance and cycle stability, and can be used as a high-performance lithium ion battery cathode material to prepare a high-capacity lithium ion battery; in addition, the material has good conductive performance, and can also be used as a functional material of a conductive additive.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a nano spiral graphite fiber material is characterized by comprising the following steps:
(1) and (3) a vapor deposition process: methane is used as a raw material, a metal catalyst is added, and a vapor deposition method is adopted to prepare the nano spiral fiber;
(2) and (3) a carbonization process: carbonizing the nano spiral fiber in the step (1) for 0.5h at 1000-;
(3) the graphitization process comprises the following steps: graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h under the protection of high-purity argon at the temperature of 2000-3273K to obtain the nano spiral graphite fiber material.
2. The method for preparing nano-helical graphite fiber material according to claim 1, wherein the metal catalyst of step (1) is selected from copper powder or nickel powder.
3. The method for preparing nano-helical graphite fiber material according to claim 2, wherein when the catalyst is selected from copper powder, the conditions of the vapor deposition method in the step (1) are as follows: placing copper powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-800K at the rate of 1-10K/min, preserving heat for 1-2h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 30-80 mL/min: 50-120 mL/min.
4. The method for preparing nano-helical graphite fiber material according to claim 2, wherein when the catalyst is selected from nickel powder, the conditions of the vapor deposition method in the step (1) are as follows: putting nickel powder on a ceramic substrate, introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-1000K at the rate of 1-10K/min, preserving heat for 1-1.5h, and cooling to room temperature;
wherein the ratio of the introduced amount of the methane gas to the introduced amount of the hydrogen gas is 20-50 mL/min: 40-100 mL/min.
5. The method for preparing nano spiral graphite fiber material according to claim 1, wherein the inert atmosphere of step (2) is selected from high purity argon atmosphere or high purity nitrogen atmosphere, and the carbonization process of step (2): carbonizing the nano spiral fiber in the step (1) for 0.5h at the temperature rise rate of 3-10K/min and at the temperature of 1100-1573K in an inert atmosphere to obtain the carbonized nano spiral fiber.
6. The method for preparing nano spiral graphite fiber material according to claim 1, wherein the graphitization process of step (3) comprises the following steps: under the protection of high-purity argon, graphitizing the carbonized nano-spiral fiber obtained in the step (2) for 0.5h at the temperature rise rate of 3-10K/min under the temperature rise rate of 2500-3273K, and thus obtaining the nano-spiral graphite fiber material.
7. A nano-helical graphite fiber material obtained by the method for preparing a nano-helical graphite fiber material according to any one of claims 1 to 6.
8. The application of the nano spiral graphite fiber material of claim 7 in preparing lithium ion battery negative electrode materials or conductive additive materials.
9. The lithium ion battery negative electrode material prepared by using the nano spiral graphite fiber material of claim 7 is characterized by being prepared according to the following steps:
mixing a nano spiral graphite fiber material, a conductive agent and a binder, then mixing with a solvent to obtain slurry, uniformly coating the slurry on the surface of a copper foil serving as a substrate, and drying to obtain a lithium ion battery negative electrode material;
wherein the mass ratio of the nano spiral graphite fiber material to the conductive agent to the binder is 7-8: 1-2: 1;
the conductive agent is selected from conductive carbon black, carbon nano tubes or graphene; the binder is selected from polyvinylidene fluoride or carboxymethyl cellulose; the solvent is selected from N-methyl pyrrolidone or deionized water.
10. The application of the lithium ion battery negative electrode material of claim 9 in preparing a lithium ion battery, wherein the lithium ion battery is prepared according to the following steps:
preparing a positive electrode material: tabletting and cutting the metal lithium;
preparing an electrolyte: mixing LiPF 6 Dissolving in organic solvent to prepare LiPF with the concentration of 1mol/L 6 An electrolyte;
wherein the organic solvent consists of ethylene carbonate, dimethyl carbonate and vinylene carbonate in a volume ratio of 47.5:47.5: 5;
preparing a lithium ion battery: and sequentially assembling the anode material, the Cellgard2400 diaphragm, the electrolyte and the lithium ion battery cathode material to obtain the lithium ion battery.
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