CN114835111B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 82
- 239000010439 graphite Substances 0.000 title claims abstract description 82
- 239000002657 fibrous material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000835 fiber Substances 0.000 claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000005087 graphitization Methods 0.000 claims abstract description 9
- 239000002482 conductive additive Substances 0.000 claims abstract description 5
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 24
- 238000007740 vapor deposition Methods 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 230000000630 rising effect Effects 0.000 claims description 20
- 239000010405 anode material Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 238000003860 storage Methods 0.000 abstract description 16
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000007770 graphite material Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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, a preparation method and application thereof. According to the invention, methane gas is used as a precursor, a vapor deposition process is adopted to prepare the nano spiral fiber, and a carbonization process and a graphitization process are sequentially carried out to prepare the nano spiral graphite fiber, so that the nano spiral graphite fiber has good conductivity, is beneficial to rapid transportation of lithium ions, and can be used as a conductive additive functional material; the prepared nano spiral graphite fiber carbon layer is of a fold stacking 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 negative electrode material to prepare a high-capacity lithium ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of lithium ion batteries, in particular to a nano spiral graphite fiber material, a preparation method and application thereof.
Background
The commercial lithium ion battery cathode material is generally made of graphite material, and the graphite material is still the dominant force in the field of cathode materials at present. The graphite materials are of various types, including natural crystalline flake graphite, artificial graphite, fibrous carbon materials (with graphite structures) and the like; the non-renewable natural crystalline flake graphite has natural graphite structural degree, and can be directly used as a lithium ion battery anode material after high-temperature treatment; the artificial graphite is generally prepared by taking natural crystalline flake graphite as 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; while the lithium storage capacity of the modified treated graphite material can be somewhat near the theoretical capacity level (372 mA h/g; liC 6) in a short period of time. Compared with graphite materials, the fibrous carbon material has potential advantages, the carbon fiber is fibrous carbon material, the carbon element content in the chemical composition is more than 90%, and 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 entertainment products and the like.
With the development of technology, the specific capacity provided by conventional graphite anode materials cannot meet the requirements of power sources, electronic products and the like, and the appearance of anode materials 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, theoretical calculation value is up to 4200mA h/g, and 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 severe volume change, so that the structure of the silicon negative electrode material is damaged, and the electrical contact fails, thereby reducing the cycle life and the specific capacity of the silicon negative electrode material.
In the face of rapid updating of consumer electronic devices and the requirement of electric automobiles on prolonging the endurance mileage, the energy density of batteries is urgently required to be greatly improved, so that development of new high-performance batteries is urgently required; the development of lithium ion batteries with high energy density, high power density and long service life has important application significance for developing portable electronic equipment and electric automobiles. There is therefore a need for a new material that overcomes the existing state of the art: (1) Commercial graphite materials are prepared by taking non-renewable natural crystalline flake graphite as a main raw material, so that the problem of exhaustion of graphite resources is necessarily faced; (2) Silicon-based and other novel lithium ion battery cathode materials are prepared by adopting a harsh and high-difficulty nano technology, the yield is low, and no enterprise has realized the production scale of annual production hundred tons; (3) The preparation process of the commercial artificial graphite anode material is complex, and has the technical defect of severe technical requirements.
One of the materials for military and civil use in the carbon material can be used as a structural material and also can be used as a functional material (high electric conduction, high heat conductivity, negative expansion coefficient and the like) for realizing certain functions; further designing and regulating the microstructure of the carbon material is beneficial to improving the first specific capacity, breaking through the theoretical value limit of 372mAh/g, improving the overall conductivity of the material, improving the cycle life and high specific capacity of the electrode material, meeting the inherent requirement of serving as a negative electrode material of a lithium ion battery, and being expected to become a novel graphite negative electrode material of a new generation of lithium ion battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nano spiral graphite fiber material, a preparation method and application thereof, wherein 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 rapid transport of lithium ions, and can also be used as a conductive additive functional material; the prepared nano spiral graphite fiber carbon layer is of a fold stacking 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 negative electrode material to prepare a high-capacity lithium ion battery.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
The preparation method of the nano spiral graphite fiber material comprises the following steps:
(1) Vapor deposition process: methane is used as a raw material, a metal catalyst is added, and a vapor deposition method is adopted to prepare nano spiral fibers;
(2) And (3) carbonization: carbonizing the nano spiral fiber obtained in the step (1) for 0.5h at 1000-1773K in an inert atmosphere to obtain carbonized nano spiral fiber;
(3) And (3) graphitizing: graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h under the protection of high-purity argon gas at 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, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-800K at the speed of 1-10K/min, preserving heat for 1-2h, and then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 30-80mL/min:50-120mL/min.
Preferably, when the catalyst is selected from nickel powder, the conditions of the vapor deposition method in the step (1) are as follows: placing nickel powder on a ceramic substrate, then 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 then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 20-50mL/min:40-100mL/min.
Preferably, the inert atmosphere in the step (2) is selected from a high-purity argon atmosphere or a high-purity nitrogen atmosphere, and the carbonization process in the step (2): carbonizing the nano spiral fiber obtained in the step (1) for 0.5h at 1100-1573K at the temperature rising rate of 3-10K/min in an inert atmosphere to obtain the carbonized nano spiral fiber.
Preferably, the graphitization process of step (3): and (3) graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h at 2500-3273K under the protection of high-purity argon at the temperature rising rate of 3-10K/min to obtain 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 preparing the anode material or the conductive additive material of the lithium ion battery.
Preferably, the lithium ion battery anode 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 slurry, taking copper foil as a substrate, uniformly coating the slurry on the surface, and drying to obtain a lithium ion battery anode material;
wherein, the mass ratio of the nano spiral graphite fiber material, the conductive agent and the binder is 7-8:1-2:1, a step of;
The conductive agent is selected from conductive carbon black, carbon nano tube 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 application of the lithium ion battery cathode material 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;
Preparation of electrolyte: dissolving LiPF 6 in an organic solvent to prepare LiPF 6 electrolyte with the concentration of 1 mol/L;
Wherein the organic solvent consists of ethylene carbonate, dimethyl carbonate and vinylene carbonate in a volume ratio of 47.5:47.5:5;
preparation of a lithium ion battery: and sequentially assembling the anode material, cellgard2400 separator, electrolyte and the lithium ion battery anode material to prepare the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention adopts methane gas which is easy to purchase in the market as a raw material, adopts a vapor deposition process to prepare nano spiral fiber, and prepares nano spiral graphite fiber through carbonization and graphitization processes in sequence. The prepared nano spiral graphite fiber has the characteristics of good electrical conductivity, good thermal conductivity, acid resistance, alkali resistance and corrosion resistance, and is beneficial to 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; as a lithium ion negative electrode material, the material can be used for preparing high-performance lithium ion batteries; in addition, the network structure of the nano spiral graphite fiber can also play roles in enhancing the functions and effects of relieving volume change and enhancing electrochemical lithium storage of materials such as silicon base and the like.
2. The preparation method of the nano spiral graphite fiber material has no strict technical requirements, and when the nano spiral graphite fiber material is used as a lithium ion battery negative electrode material, the method can be matched with the existing lithium ion battery production line for production without equipment transformation, and is suitable for mass enterprises for production; the method improves the economic benefit of the deep processing of the methane chemical product, simultaneously produces no toxic gas in the preparation process, meets the requirements of green, environment-friendly and sustainable development, and is a lithium ion battery anode material which is expected to replace the natural crystalline flake graphite in the prior art.
3. The specific lithium storage capacity of the nano spiral graphite fiber material prepared by the invention exceeds the specific capacity of 372mAh/g of a graphite theoretical interlayer lithium storage mechanism, has higher lithium storage potential, can be used as a high-performance lithium ion battery anode material for preparing a lithium ion battery, and is attributed to the fact that the carbon layer structure of the material presents a stacked and wrinkled shape, and the microstructure of the nano spiral fiber comprises: the folds of the carbon layers, the stacking of the carbon layers and the bending of the carbon layers are macroscopically spiral along the axial direction of the fiber, and are different from typical graphite lamellar structures and 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 nano spiral graphite fiber material prepared by the invention has essential differences from the structures of carbon nano tubes and carbon nano tube spiral materials, is different from typical graphite structures and microstructures of conventional carbon fibers, and provides 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 the transmission electron microscope, and the prior similar carbon material is not subjected to graphitization treatment, so that the effect cannot be achieved.
5. The invention adopts vapor deposition to prepare nano spiral fiber so as to improve the specific capacity of lithium storage by adopting a carbon layer structure to take on stacking and fold shapes, and then carbonization and graphitization treatment are sequentially carried out, wherein the carbonization is the conversion of materials from organic to inorganic; graphitization is the transition from a disordered structure to an ordered structure; after graphitization, the microstructure is more abundant, which is beneficial to the storage and transportation of lithium ions.
Drawings
FIG. 1 is a scanning electron microscope image of a nano-helical graphite fiber prepared in embodiment 1of the present invention, wherein a is a scanning electron microscope image of the fiber, b is a fiber transmission electron microscope image, and c is a transmission electron microscope image of a specific carbon layer microstructure of the fiber;
FIG. 2 is a graph showing the rate performance of the nano-helical 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 showing the cycle performance of the nano-helical graphite fiber prepared in example 3 of the present invention at a current density of 50 mAh/g;
FIG. 4 is a graph showing CV performance of the nano-helical graphite fiber prepared in example 2 of the present invention at 0.01-2V.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
The conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 573K at a rate of 3K/min, preserving heat for 1h, and then cooling to room temperature;
wherein, the ratio of the methane gas to the hydrogen gas is 1:1.5;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 6K/min, the preset temperature is 1573K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 5K/min, the preset temperature is 3073K, and the temperature is kept constant for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 2
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
the conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 603K at the rate of 2K/min, preserving heat for 1h, and then cooling to room temperature;
wherein, the ratio of the methane gas to the hydrogen gas is 1:1.8;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 4K/min, the preset temperature is 1373K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 3K/min, the preset temperature is 2773K, and the temperature is kept constant 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) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
the conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 620K at a rate of 2K/min, preserving heat for 1.5h, and then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 1:1.6;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 10K/min, the preset temperature is 1273K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 3K/min, the preset temperature is 2673K, and the temperature is kept constant for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 4
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
the conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500K at a rate of 5K/min, preserving heat for 2h, and then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 1:1.5;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 8K/min, the preset temperature is 1000K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 10K/min, the preset temperature is 3273K, and the temperature is kept constant 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) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
The conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 800K at a rate of 1K/min, preserving heat for 1h, and then cooling to room temperature;
wherein the ratio of the methane gas to the hydrogen gas is 1:1.55;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 7K/min, the preset temperature is 1773K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 5K/min, the preset temperature is 2000K, and the temperature is kept constant for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 6
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) Using methane gas as a raw material, copper powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
The conditions of the vapor deposition method are as follows: placing copper powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 800K at a rate of 10K/min, preserving heat for 1h, and then cooling to room temperature;
wherein the ratio of the methane gas to the hydrogen gas is 1:1.65;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 3K/min, the preset temperature is 1100K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 10K/min, the preset temperature is 3273K, and the temperature is kept constant 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) Using methane gas as a raw material, nickel powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
the conditions of the vapor deposition method are as follows: placing nickel powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 1000K at the rate of 2K/min, preserving heat for 1h, and then cooling to room temperature;
wherein the ratio of the methane gas to the hydrogen gas is 1:1.7;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 4K/min, the preset temperature is 1100K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 3K/min, the preset temperature is 3073K, and the temperature is kept constant for 0.5h, so that the nano spiral graphite fiber is prepared.
Example 8
The preparation method of the nano spiral graphite fiber comprises the following steps:
(1) Using methane gas as a raw material, nickel powder as a catalyst, and adopting a vapor deposition technology to prepare nano spiral fibers;
The conditions of the vapor deposition method are as follows: placing nickel powder on a ceramic substrate, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500K at a rate of 5K/min, preserving heat for 1.5h, and then cooling to room temperature;
Wherein, the ratio of the methane gas to the hydrogen gas is 1:1.75;
(2) And (3) carbonization: under the protection of high-purity nitrogen, the temperature rising rate is 5K/min, the preset temperature is 1573K, and the temperature is kept constant for 0.5h;
(3) And (3) graphitizing: under the protection of high-purity argon, the temperature rising rate is 5K/min, the preset temperature is 2500K, and the temperature is kept constant for 0.5h, so that the nano spiral graphite fiber is prepared.
Results and discussion
The nano spiral graphite fiber materials for the negative electrode materials of the lithium ion batteries are prepared in the embodiment 1 to the embodiment 8, the effects are parallel, the nano spiral graphite fiber materials prepared in the embodiment 1 to the embodiment 3 are taken as examples for research, and the research method and the result are as follows:
FIG. 1 is a morphology diagram of nano-helical graphite fibers prepared in example 1 of the present invention, (a) is a helical carbon fiber with higher purity, and no non-helical carbon fiber is found; the helical structure extends axially along the fiber with a pitch of about 60nm. (b) The carbon slice strip is spirally wound in a transmission diagram of a single carbon fiber; (c) The carbon fiber has a local microstructure of carbon fiber, and characteristic structures such as folds of the carbon layers, stacking of the carbon layers, bending of the carbon layers and the like are clearly visible; especially, the development of the carbon layer stripes is perfect and clear. As can be seen from fig. 1, the material is in a spiral winding shape along the axial direction, and has a solid structure in section, which is completely different from the hollow structure of the carbon nanotube; meanwhile, the microscopic carbon layer of the graphite has a stacked and wrinkled morphology, which is different from a typical graphite layered stacking mode, but lattice stripes of the graphite are clearly visible, so that the graphite 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 with 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 in N-methyl pyrrolidone, coating a copper foil serving as a substrate into uniform electrode slices, drying, and cutting into wafers with the diameter of 16mm to prepare a lithium ion battery anode material;
Respectively assembling a positive electrode material, cellgard2400 diaphragms, an electrolyte and a lithium ion battery negative electrode material in sequence to obtain a lithium ion battery;
And (3) battery performance detection: cycling under the current density of 50-800mA/g, inspecting electrochemical performance, and selecting one of the series of materials as a negative electrode material for electrochemical performance test;
As shown in FIG. 2, the first embedding specific capacity can reach 440mAh/g by cycling at a current density of 0.05A/g; after cycling at different current densities, the reversible average specific capacity of the lithium ion battery is still maintained at 380mA h/g in the last test, exceeds the theoretical specific capacity of graphite of 372mA h/g, and the coulomb efficiency is very stable in the cycling process and shows excellent electrochemical performance.
As shown in FIG. 3, the capacity is still maintained at 335mAh/g after 50 cycles under the test of small current of 0.05A/g, which shows that the catalyst has better cycle stability.
As shown in fig. 4, in the CV test, starting from 1.45V, the discharge current is gradually increasing; the peak potential of the first anode is 0.5V, the peak position is stabilized at 0.48V and 0.49V after circulation, and electrolyte on the surface of the electrode material is stably generated, so that the improvement of the later circulation stability is facilitated.
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 negative electrode material to prepare a high-capacity lithium ion battery; in addition, the material has good conductivity and can be used as a conductive additive functional material.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The preparation method of the nano spiral graphite fiber material is characterized by comprising the following steps of:
(1) Vapor deposition process: methane is used as a raw material, a metal catalyst is added, and a vapor deposition method is adopted to prepare nano spiral fibers;
(2) And (3) carbonization: carbonizing the nano spiral fiber obtained in the step (1) for 0.5h at 1000-1773K in an inert atmosphere to obtain carbonized nano spiral fiber;
(3) And (3) graphitizing: graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h under the protection of high-purity argon gas at 2000-3273K to prepare a nano spiral graphite fiber material;
the metal catalyst in the step (1) is selected from copper powder or nickel powder;
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, then introducing mixed gas of methane gas and hydrogen gas into the ceramic substrate, heating to 500-800K at the speed of 1-10K/min, preserving heat for 1-2h, and then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 30-80mL/min:50-120mL/min;
When the catalyst is selected from nickel powder, the conditions of the vapor deposition method in the step (1) are as follows: placing nickel powder on a ceramic substrate, then 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 then cooling to room temperature;
Wherein the ratio of the methane gas to the hydrogen gas is 20-50mL/min:40-100mL/min.
2. The method for preparing nano-helical graphite fiber material according to claim 1, wherein the inert atmosphere in the step (2) is selected from high-purity argon atmosphere or high-purity nitrogen atmosphere, and the carbonization process in the step (2): carbonizing the nano spiral fiber obtained in the step (1) for 0.5h at 1100-1573K at the temperature rising rate of 3-10K/min in an inert atmosphere to obtain the carbonized nano spiral fiber.
3. The method of preparing a nano-helical graphite fiber material according to claim 1, wherein the graphitization process of step (3): and (3) graphitizing the carbonized nano spiral fiber in the step (2) for 0.5h at 2500-3273K under the protection of high-purity argon at the temperature rising rate of 3-10K/min to obtain the nano spiral graphite fiber material.
4. A nano-helical graphite fiber material produced by the method for producing a nano-helical graphite fiber material according to any one of claims 1 to 3.
5. Use of the nano-helical graphite fiber material according to claim 4 for preparing a negative electrode material or a conductive additive material of a lithium ion battery.
6. A lithium ion battery anode material prepared by using the nano spiral graphite fiber material as claimed in claim 4, wherein the lithium ion battery anode 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 slurry, taking copper foil as a substrate, uniformly coating the slurry on the surface, and drying to obtain a lithium ion battery anode material;
wherein, the mass ratio of the nano spiral graphite fiber material, the conductive agent and the binder is 7-8:1-2:1, a step of;
The conductive agent is selected from conductive carbon black, carbon nano tube or graphene; the binder is selected from polyvinylidene fluoride or carboxymethyl cellulose; the solvent is selected from N-methyl pyrrolidone or deionized water.
7. Use of the lithium ion battery negative electrode material according to claim 6 for 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;
Preparation of electrolyte: dissolving LiPF 6 in an organic solvent to prepare LiPF 6 electrolyte with the concentration of 1 mol/L;
Wherein the organic solvent consists of ethylene carbonate, dimethyl carbonate and vinylene carbonate in a volume ratio of 47.5:47.5:5;
preparation of a lithium ion battery: and sequentially assembling the anode material, cellgard2400 separator, electrolyte and the lithium ion battery anode material to prepare the lithium ion battery.
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