CN115058794B - Carbon fiber material, preparation method thereof and lithium ion battery - Google Patents
Carbon fiber material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115058794B CN115058794B CN202210683402.0A CN202210683402A CN115058794B CN 115058794 B CN115058794 B CN 115058794B CN 202210683402 A CN202210683402 A CN 202210683402A CN 115058794 B CN115058794 B CN 115058794B
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 87
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011357 graphitized carbon fiber Substances 0.000 claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 238000005087 graphitization Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 230000005496 eutectics Effects 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002028 Biomass Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000003248 quinolines Chemical class 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- -1 choline halide Chemical class 0.000 claims description 7
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229960001231 choline Drugs 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- JJCWKVUUIFLXNZ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCO JJCWKVUUIFLXNZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011874 heated mixture Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 3
- 238000011534 incubation Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000000284 resting effect Effects 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000376 reactant Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- JUZXDNPBRPUIOR-UHFFFAOYSA-N chlormequat Chemical compound C[N+](C)(C)CCCl JUZXDNPBRPUIOR-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
Abstract
本发明公开了一种碳纤维材料、其制备方法和锂离子电池。所述碳纤维材料包括石墨化碳纤维，所述石墨化碳纤维相互搭接形成多孔网络结构，所述石墨化碳纤维表面具有微孔。本发明的碳纤维材料具有多孔网络结构，在碳纤维之间有很多的碳纤维交错形成的纳米结构间隙，非常有利于电解液的扩散和锂离子的脱嵌，有利于提升材料的比表面积和储锂性能，同时，石墨化的碳纤维相比于普通的碳纤维，具有更好的导电性能，石墨化碳纤维表面的微孔有利于锂吸附离子在碳纤维表面和边缘上进行存储从而增加容量。本发明的碳纤维材料应用于锂离子电池，能够显著提升电池的性能。
The present invention discloses a carbon fiber material, a preparation method thereof and a lithium ion battery. The carbon fiber material comprises graphitized carbon fibers, the graphitized carbon fibers are overlapped to form a porous network structure, and the graphitized carbon fibers have micropores on their surface. The carbon fiber material of the present invention has a porous network structure, and there are many nanostructure gaps formed by the interlacing of carbon fibers between the carbon fibers, which is very beneficial for the diffusion of electrolytes and the deintercalation of lithium ions, and is beneficial for improving the specific surface area and lithium storage performance of the material. At the same time, the graphitized carbon fibers have better electrical conductivity than ordinary carbon fibers, and the micropores on the surface of the graphitized carbon fibers are beneficial for the storage of lithium adsorbed ions on the surface and edges of the carbon fibers, thereby increasing the capacity. The carbon fiber material of the present invention is applied to lithium ion batteries, which can significantly improve the performance of the batteries.
Description
Technical Field
The invention relates to the technical field of new energy, and relates to a carbon fiber material, a preparation method thereof and a lithium ion battery.
Background
The carbon fiber has the advantages of light weight, high strength, high temperature resistance, high corrosion resistance and the like, and is widely applied to a plurality of fields of sports equipment, aerospace, rail transit, automobiles and the like. The carbon fiber graphitization can lead the structure to trend to an ideal graphite structure, greatly improves the tensile modulus, has the characteristics of good thermal shock resistance, small thermal expansion coefficient, 3500 ℃ resistance under no oxygen, excellent flame resistance and electrical conductivity, corrosion resistance and the like, and therefore, the graphitization research of the carbon fiber has important significance for popularization and application.
The core of the carbon fiber graphitization technology is to perform high-temperature heat treatment on the carbon fibers, and the graphitization temperature of the carbon material is generally about 2500 ℃, so that the energy consumption is high. For example, CN110409018A discloses a preparation method of dry-jet wet-spinning high-strength die abrasion-resistant polyacrylonitrile-based carbon fiber, which comprises the following steps of 1, graphitizing, namely, performing graphitizing hot stretching treatment on carbonized fiber obtained by pre-oxidizing and carbonizing a dry-jet wet-spinning polyacrylonitrile precursor at 2300-2500 ℃, wherein the graphitizing time is 60-120s, the stretching rate is 1.01-1.04, 2, performing surface treatment on the graphitized carbon fiber obtained in the step 1 by adopting anodic oxidation electrochemical treatment, performing surface treatment on the graphitized carbon fiber, wherein the electric quantity is 50-100C/g, and finally, sizing, drying and the sizing agent content is 1.0-1.5%, thereby obtaining the high-strength high-die abrasion-resistant polyacrylonitrile-based carbon fiber. CN111962287a discloses a process for preparing high-performance low-cost graphitized carbon fiber by using joule heating technology, which prepares high-performance low-cost graphitized carbon fiber by introducing joule heating method, that is, the elastic modulus of the graphitized carbon fiber is higher than 350MPa, and meanwhile, the electrical conduction and resistance properties of the carbon fiber are utilized to directly apply electricity to the carbon fiber, so that the heating temperature of the method for heating the carbon fiber can reach 2800 ℃ at most.
From the above, the prior art generally uses a high-temperature heating mode to make the carbon fiber fibrillate, but has the problem of high energy consumption, and the structure improvement of the graphitized carbon fiber to obtain the graphitized carbon fiber with high performance is a great research difficulty, so that the research of the graphitized carbon fiber with high performance and the preparation and modification methods thereof has important significance.
Disclosure of Invention
The invention aims to provide a carbon fiber material, a preparation method thereof and a lithium ion battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a carbon fiber material, where the carbon fiber material includes graphitized carbon fibers, where the graphitized carbon fibers overlap each other to form a porous network structure, and the surface of the graphitized carbon fibers has micropores.
The carbon fiber material has a porous network structure, a plurality of carbon fibers are staggered to form nano-structure gaps among the carbon fibers, so that the diffusion of electrolyte and the deintercalation of lithium ions are facilitated, the specific surface area and the lithium storage performance of the material are improved, meanwhile, compared with the common carbon fibers, the graphitized carbon fibers have better conductivity, and micropores on the surfaces of the graphitized carbon fibers are favorable for storing lithium adsorption ions on the surfaces and edges of the carbon fibers, so that the capacity is increased.
The carbon fiber material provided by the invention is used as a negative electrode active material and/or a conductive agent to prepare an electrode, and is applied to a lithium ion battery, and has the advantages of high capacity, good conductivity and excellent multiplying power performance.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, the micropores are obtained by etching the fibrous biomass carbon with a flue gas of a eutectic solvent comprising a halogenated choline and a halogenated ferric salt.
Preferably, in the XRD spectrum of the carbon fiber material, the ratio of the main peak intensity of the (002) crystal face to the total peak intensity of the impurity peaks is 2-5:1. The ratio of the main peak to the impurity peak reflects the graphitization degree in the carbon fiber material, and the graphitization degree in the carbon fiber material can be regulated by regulating and controlling the ratio of the main peak to the impurity peak, so that the lithium battery using the carbon fiber material has higher first efficiency, good cycle performance and rate capability. For example, the ratio of main peak to impurity peak can be regulated by regulating the sintering temperature, so as to regulate the graphitization degree in the carbon fiber material.
In a second aspect, the present invention provides a method for preparing a stone carbon fibre material according to the first aspect, the method comprising the steps of:
(1) Heating and mixing halogenated choline and halogenated ferric salt to form a eutectic solvent;
(2) Mixing fiber biomass carbon with the eutectic solvent to obtain a precursor;
(3) Carrying out high-temperature graphitization treatment on the precursor to obtain a carbon fiber material;
The temperature of the high-temperature graphitization treatment is 1400-1800 ℃.
The pore-forming of the carbon fiber can improve the lithium storage capacity on the carbon layer and the surface of the carbon layer, and the pore-forming agent (such as polyvinyl alcohol PVA, polyvinyl butyral PVB and the like) is generally added to form pores on the carbon fiber, but the additional pore-forming agent is required to be added in advance and mixed and stirred, so that the cost and the reaction steps are increased.
According to the method, the halogenated choline and the halogenated ferric salt are heated and mixed to form the eutectic solvent, cellulose in the fibrous biomass carbon is insoluble in water, but can be swelled in the eutectic solvent to form a homogeneous mixture, and the cellulose stripping function can be realized. In the high-temperature graphitization treatment process, the choline carbonized flue gas is alkaline, so that corrosion pore-forming effect is generated, and the specific surface area and lithium storage performance of biomass carbon are improved.
Wherein, due to the addition of iron element in the low-co-solvent, an iron complex is formed in the low-co-solvent, the reactant is adsorbed, carbon can be catalyzed and melted in the high-temperature graphitization treatment process, and when the carbon melting degree reaches saturation or supersaturation, part of melted carbon tends to the graphite crystal form of low energy level and is deposited, thereby reducing the graphitization temperature and obtaining the carbon fiber material.
Unlike available carbon fiber preparing process with petrochemical material and grain material as carbon source, the present invention has fiber biomass carbon as carbon source, environment friendship, controllable reaction process, high industrialization degree and excellent performance.
In the method, as the fiber biomass carbon and the eutectic solvent are directly carbonized, the phenomenon of uneven mixing of reactants in the precursor in the usual carbonization process is avoided, so that the carbonization efficiency and uniformity are improved, and the method is suitable for industrial production.
Preferably, the halogenated choline of step (1) comprises at least one of choline chloride, choline bromide, or a derivative thereof.
Preferably, the halogenated ferric salt of step (1) comprises any one or more of ferric chloride, ferrous bromide, or derivatives thereof.
Preferably, in the step (1), the molar ratio of the halogenated choline to the halogenated ferric salt is (1-3): 2-8, wherein the selection range of the halogenated choline is, for example, 1, 1.5, 1.6, 1.8, 2, 2.4, 2.5, 2.8 or 3, and the selection range of the halogenated ferric salt is, for example, 2, 2.5, 3, 3.5, 4, 4.2, 4.5, 5, 5.5, 6, 6.5, 7 or 8, and the like.
Preferably, the temperature of the heated mixture in step (1) is 40-80 ℃, e.g. 43 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃,70 ℃, 75 ℃ or 80 ℃ and the like, and the time is 2-8 hours, e.g. 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 6 hours, 6.5 hours, 7 hours or 8 hours and the like.
Preferably, the heating and mixing process of step (1) is accompanied by stirring.
Preferably, the fibrous biomass carbon of step (2) is a non-cereal biomass, preferably at least one of bamboo fibres, lignocellulose or derivatives thereof.
Preferably, in the step (2), the mass ratio of the fiber biomass carbon to the eutectic solvent is (1-3): 2-8, wherein the selection range of the fiber biomass carbon is, for example, 1, 1.5, 1.8, 2, 2.5 or 3, and the selection range of the eutectic solvent is, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8, and the like.
Preferably, the temperature of the mixing in step (2) is 40-80 ℃, e.g. 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ etc., and the time is 2-8 hours, e.g. 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours or 8 hours etc.
Preferably, the mixing in step (2) is accompanied by stirring.
Preferably, the step (2) is further followed by steps of ultrasonic vibration and standing in sequence after the mixing.
Preferably, the ultrasonic oscillation is performed at room temperature.
Preferably, the time of the ultrasonic oscillation is 20-60min, for example 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
Preferably, the time of the standing is 1-2 hours, such as 1 hour, 1.3 hours, 1.5 hours, 1.6 hours, 1.8 hours, 2 hours, etc.
Preferably, the precursor is pre-oxidized in advance before the high-temperature graphitization treatment in step (3).
Preferably, the pre-oxidation treatment is carried out at a temperature of 200-300 ℃, e.g. 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃, etc., and a holding time of 1-2 hours, e.g. 1.2 hours, 1.4 hours, 1.6 hours or 2 hours, etc.
Preferably, the pre-oxidation treatment has a temperature increase rate of 2-5 ℃, e.g., 2 ℃,3 ℃,4 ℃,5 ℃, or the like.
Preferably, the pre-oxidation treatment atmosphere is an oxygen-containing atmosphere, preferably an air atmosphere.
Through the pre-oxidation treatment, organic matters in the mixture can be slowly decomposed and evaporated to form air holes, so that the high-performance carbon fiber material is favorably obtained.
The high-temperature graphitization treatment in the step (3) has a temperature of 1400-1800 ℃, such as 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃ or 1800 ℃ and the like, and a heat preservation time of 6-16h, such as 6h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16h and the like.
Preferably, the rate of temperature rise of the high temperature graphitization treatment of step (3) is 2-5 ℃, such as 2 ℃,3 ℃,4 ℃,5 ℃ or the like.
Preferably, the high-temperature graphitization treatment atmosphere in the step (3) is an inert atmosphere, and the gas in the inert atmosphere comprises at least one of nitrogen, helium and argon.
Preferably, the high-temperature graphitization treatment in the step (3) is followed by the steps of acid washing, cleaning, separation, ball milling and sieving in sequence. The separation method of the present invention is not particularly limited, and may be, for example, standing, suction filtration, or the like. The number of cycles may be one or more with the washing and separation performed sequentially as one cycle.
Preferably, the solvent used for pickling is a pickling solvent, and the pickling solvent comprises at least one of hydrochloric acid, sulfuric acid and acetic acid.
Preferably, the solvent used for the washing is absolute ethanol.
Preferably, the rotation speed of the ball mill is 500-1000r/min, such as 500r/min, 600r/min, 750r/min, 800r/min, 900r/min or 1000r/min, etc., and the time is 4-6h, such as 4h, 4.5h, 5h, 5.5h or 6h, etc.
Preferably, the number of the screened meshes is 180-400 meshes, such as 200 meshes, 300 meshes or 400 meshes, and the like, and the screened undersize is taken after screening.
As a further preferable technical scheme of the preparation method of the carbon fiber material, the method comprises the following steps:
1) Weighing halogenated choline and halogenated ferric salt according to a molar ratio of 1-3:2-8, and stirring for 2-8 hours at a temperature of 40-80 ℃ in a constant-temperature magnetic stirrer to obtain a eutectic solvent;
2) Weighing a non-grain biomass carbon source and a eutectic solvent according to the mass ratio of 1-3:2-8, and stirring for 2-8 hours at 40-80 ℃ in a constant temperature magnetic stirrer to obtain a mixture;
3) Ultrasonically oscillating the mixture obtained in the step 2) for 20-60min at room temperature by using an ultrasonic machine, and then standing for 1-2h to obtain a precursor;
4) Heating the precursor obtained in the step 3) to 200-300 ℃ at a heating rate of 2-5 ℃ per min under an air atmosphere, preserving heat for 1-2h, heating to 1400-1800 ℃ at a heating rate of 2-5 ℃ per min under a nitrogen atmosphere, and preserving heat for 6-16h to obtain a reactant;
5) Washing the reactant obtained in the step 4) with acid washing and absolute ethyl alcohol for a plurality of times, filtering, ball milling for 4-6 hours in a ball mill at 500-1000r/min, and screening with a 180-400 mesh screen to obtain the carbon fiber material.
In a third aspect, the present invention provides a lithium ion battery, where the lithium ion battery includes the carbon fiber material according to the first aspect.
In one embodiment, the negative electrode active material and the conductive agent in the negative electrode of the lithium ion battery at least partially adopt the carbon fiber material according to the first aspect, wherein the mass ratio of the carbon fiber material is 20-40%, such as 20%, 22.5%, 25%, 28%, 30%, 33%, 35%, 36%, 38%, 40%, or the like, based on the total weight of the negative electrode active material layer. The formula adopting the technical scheme is used for preparing the lithium ion battery without adding other conductive agents. The negative electrode active material other than the carbon fiber material described above is a negative electrode material common in the prior art, and for example, one or more of graphite, silicon oxide, carbon-coated silicon oxide, and the like may be selected.
The carbon fiber material has the advantage of high conductivity, and can be used as a negative electrode active material and a conductive agent for a lithium ion battery, so that the step of adding the conductive agent can be omitted, and the rate capability of the lithium battery can be improved.
In another embodiment, the negative electrode conductive agent in the negative electrode of the lithium ion battery employs the carbon fiber material according to any one of claims 1 to 7, wherein the mass ratio of the carbon fiber material is 2% -5%, such as 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, based on the total weight of the negative electrode active material layer.
The carbon fiber material has high conductivity, is suitable for being applied to the preparation of a negative electrode as a conductive agent, can completely or partially replace the traditional conductive carbon materials such as ketjen black, acetylene black, SP and the like, and improves the electrochemical performance of a battery.
By way of example and not limitation, the present invention provides the use of the carbon fiber material described above in a negative electrode of a lithium ion battery:
The negative electrode plate of the lithium ion battery is prepared by taking the carbon fiber material as a negative electrode conductive agent and an active substance. The lithium ion battery negative electrode plate comprises the following components of (20-40) of carbon fiber material, (5-20) of adhesive polyvinylidene fluoride (PVDF) and (40-65) of graphite, wherein the selection range of active substance carbon fiber material is 20-40 such as 20, 25, 30, 35 or 40, the selection range of PVDF is 5-20 such as 5, 8,10, 12, 15, 18 or 20, and the like, and the selection range of conductive agent acetylene black is 40-65 such as 40, 45, 50, 55, 60 or 65, and the like.
The type of lithium ion battery is not particularly limited in the present invention, and may be a liquid battery or a solid battery. For liquid batteries, a positive electrode, a negative electrode, a separator, and an electrolyte are typically included, and for solid batteries, a positive electrode, a negative electrode, and a solid electrolyte layer are typically included.
In some embodiments, the lithium ion battery is a flexible battery. The carbon fiber material prepared by the invention has a porous network structure, so that the negative electrode has mechanical strength and higher electrochemical performance, a large number of nano-voids exist in the negative electrode, and the flexible battery has a thinner size and higher capacity.
Compared with the prior art, the invention has the following beneficial effects:
(1) The graphitized carbon fiber material has a porous network structure, is favorable for improving the specific surface area and lithium storage performance of the material, and can lead lithium ions to rapidly shuttle, thereby improving the conductivity and the multiplying power performance of the graphitized carbon fiber material. Micropores on the surface of the carbon fiber are used for facilitating the storage of lithium adsorption ions on the surface and the edge of the carbon fiber so as to increase the capacity.
The carbon fiber material provided by the invention is used as a negative electrode active material for a lithium ion battery, and has the advantages of high capacity, good conductivity and excellent rate performance.
(2) According to the method, due to the addition of the iron element in the low-co-dissolution solvent, the graphitization temperature can be reduced, so that the carbon fiber with high graphitization degree can be prepared, meanwhile, the corrosion pore-forming effect is generated in the high-temperature graphitization treatment process by utilizing the choline chloride, and the specific surface area and the lithium storage performance of the carbon fiber are improved.
In the method, as the fiber biomass carbon and the eutectic solvent are directly carbonized, the phenomenon of uneven mixing of reactants in the precursor in the usual carbonization process is avoided, so that the carbonization efficiency and uniformity are improved, and the method is suitable for industrial production.
Drawings
FIGS. 1 and 2 are SEM images of different magnifications of a carbon fiber material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the carbon fiber material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the density of the negative electrode sheets of application example 1 and comparative application example 1 of the present invention under different pressures;
Fig. 5 is a graph showing the conductivity of the negative electrode sheets of application example 1 and comparative application example 1 according to the present invention under different pressures.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
Example 1
1) 13.96G of choline chloride and 21.20g of ferric chloride are weighed according to a molar ratio of 3:5 and stirred for 2 hours at 70 ℃ in a constant temperature magnetic stirrer to obtain a eutectic solvent;
2) 17.28g of lignocellulose and 17.28g of eutectic solvent are weighed according to the mass ratio of 1:1, and stirred for 6 hours at 80 ℃ in a constant-temperature magnetic stirrer to obtain a mixture;
3) Ultrasonically oscillating the mixture obtained in the step 2) for 30min at room temperature by using an ultrasonic machine, and then standing for 2h to obtain a precursor;
4) Heating the precursor obtained in the step 3) to 200 ℃ at a heating rate of 2 ℃ per min under an air atmosphere, and preserving heat for 2 hours, heating to 1600 ℃ at a heating rate of 5 ℃ per min under a nitrogen atmosphere, and preserving heat for 12 hours to obtain a reactant;
5) Washing the reactant obtained in the step 4) with dilute sulfuric acid and absolute ethyl alcohol for a plurality of times, filtering, ball-milling for 6 hours in a ball mill at 800r/min, and screening with a 270-mesh screen to obtain the carbon fiber material.
Fig. 1 and 2 are SEM images of different magnifications of the carbon fiber material prepared in example 1 of the present invention.
Fig. 3 is an XRD pattern of the carbon fiber material prepared in example 1 of the present invention, and it is seen from the figure that the carbon fiber material 002 peak of example 1 is distinct and high in intensity and low in background signal, and high in graphitization degree on the XRD pattern.
Example 2
Unlike example 1, in step 4, the temperature was raised to 1400℃at a temperature raising rate of 3℃/min under a nitrogen atmosphere, and the temperature was maintained for 12 hours, to obtain a reactant.
In this example, compared with example 1, the pre-oxidation step was not performed, and the temperature of the temperature increase rate and the heat preservation was lowered.
Example 3
Unlike example 1, in step 4, the temperature was raised to 1800℃at a temperature raising rate of 5℃/min under a nitrogen atmosphere, and the reaction was kept for 8 hours, to obtain a reactant.
In this example, compared with example 1, the pre-oxidation step was not performed, and the temperature of the heat preservation was adjusted to be high and the time of the heat preservation was adjusted to be low.
Example 4
In this example 1, compared with the example, the pre-oxidation step was not performed, and the temperature rise rate, the temperature of the heat preservation and the time were the same.
Example 5
The difference from example 1 is that in step1, the chlorocholine and ferric chloride are weighed in a molar ratio of 1:9.
Example 6
The difference from example 1 is that in step1, the chlorocholine and ferric chloride are weighed in a molar ratio of 2:1.
Example 7
The embodiment provides a carbon fiber material and a preparation method thereof, wherein the method comprises the following steps:
1) Weighing choline chloride and ferrous chloride according to a molar ratio of 2:3, and stirring for 3 hours at 70 ℃ in a constant-temperature magnetic stirrer to obtain a eutectic solvent;
2) Weighing lignocellulose and eutectic solvent according to the mass ratio of 3:4, and stirring for 5 hours at 50 ℃ in a constant-temperature magnetic stirrer to obtain a mixture;
3) Ultrasonically oscillating the mixture obtained in the step 2) for 40min at room temperature by using an ultrasonic machine, and then standing for 1h to obtain a precursor;
4) Heating the precursor obtained in the step 3) to 280 ℃ at a heating rate of 4 ℃ per minute under an air atmosphere, and preserving heat for 2 hours, heating to 1550 ℃ at a heating rate of 5 ℃ per minute under a nitrogen atmosphere, and preserving heat for 10 hours to obtain a reactant;
5) Washing the reactant obtained in the step 4) with dilute sulfuric acid and absolute ethyl alcohol for a plurality of times, filtering, ball-milling for 5 hours in a ball mill at 800r/min, and screening with a 300-mesh screen to obtain the carbon fiber material.
Comparative example 1
Unlike example 1, 13.96g of choline chloride and 150g of urea were weighed in a molar ratio of 3:5 and stirred in a constant temperature magnetic stirrer at 70℃for 2 hours to obtain a eutectic solvent.
Application examples 1-7 and comparative application example 1:
The carbon fiber materials obtained in examples 1-7 and comparative example 1 are used as a conductive agent, part of negative electrode active materials, polyvinylidene fluoride (PVDF) and graphite are weighed according to a mass ratio of 35:15:50, then N-methyl pyrrolidone (NMP) is added, the mixture is stirred uniformly to form slurry, the slurry is coated on the surface of copper foil, the slurry is dried in a drying box at 80 ℃ for 12 hours to obtain a prefabricated electrode sheet, the prefabricated electrode sheet is rolled and cut into electrode sheets, and the electrode sheets are dried in the drying box at 120 ℃ for 8 hours, so that the negative electrode sheets of application examples 1-7 and comparative application example 1 are obtained.
The method for testing the compaction density comprises the steps of cutting the pole piece rolled under different pressures into square blocks with the weight of 1cm and the thickness of the active substance, and obtaining the corresponding compaction density by the weight of the active substance/(the thickness of the active substance) and the thickness of the active substance.
The conductivity test method is based on the principle of Kelvin four-wire method, and the conductivity is tested by using a four-probe method powder conductivity tester. The test is carried out by using a powder resistance test system MCP-PD51 and a Loresta-GXMCP-T700 low resistance tester.
The results of the tests of the compacted density and the electrical conductivity under different pressures of the negative electrode tabs of application example 1 and comparative application example 1 are shown in fig. 4 and 5. It can be seen that the conductivity and the compacted density of application example 1 are superior to those of comparative application example 1.
Application example 8
The carbon fiber material obtained in the example 1 is taken as a conductive agent, polyvinylidene fluoride (PVDF) and graphite are weighed according to the mass ratio of 5:15:85, then N-methyl pyrrolidone (NMP) is added, the mixture is stirred uniformly to form slurry, the slurry is coated on the surface of copper foil, the surface of the copper foil is dried for 12 hours at 80 ℃ in a drying box to obtain a prefabricated pole piece, the prefabricated pole piece is cut into pole pieces after being rolled, and the pole pieces are dried for 8 hours at 120 ℃ in the drying box to obtain the negative pole piece of the application example 8.
Comparative application example 2
Unlike application example 8, the negative electrode sheet of comparative application example 2 was obtained using acetylene black as a conductive agent.
Performance testing
The pole piece is assembled into a lithium ion half battery, lithium metal is used as a counter electrode, electrolyte is diethyl carbonate (DEC) +ethylene carbonate (EC) solution containing 1mol/L lithium hexafluorophosphate (volume ratio DEC: EC=7:3), and the diaphragm is assembled by using polypropylene Celgard2300 in a glove box.
And standing the assembled half-cell at normal temperature for 12 hours, then performing constant-current charge and discharge test, wherein the charge and discharge voltage is 0-3V, performing constant-current charge and discharge test (consistent charge and discharge current) at 25 ℃ and current density of 100mA/g, and testing the electrical properties of the obtained cell, wherein the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the capacity and first effect of application example 1 are larger than those of application examples 2,3 and 4, because the carbonyl group which is beneficial to electrochemical energy storage can be introduced and the crosslinking degree of the material can be enhanced in the air pre-oxidation process, and meanwhile, the reactant can be further dried and easily oxidized impurities can be removed in the pre-oxidation process.
Application example 1 is superior to application examples 5 and 6 because the ratio of lignocellulose and the low co-solvent in the mixture is different, and the etching effect generated when the choline cations in the low co-solvent are decomposed during sintering is different. The smaller proportion of choline cations in application example 5 results in less micropores generated by sintering, which reduces the lithium storage performance, and the larger proportion of choline cations in application example 6 increases the solubility of lignocellulose to result in higher granulation degree of the final product, increases the specific surface area and increases the consumption of lithium in the formation process, thereby reducing the first effect.
As can be seen from fig. 3,4 and 5, the graphitization degree of the application example 1 is far greater than that of the comparative application example 1, the compaction density is close to 2.3g/cm 3 of the true density of graphite under high pressure, and the conductivity is also superior to that of the comparative application example 1, because the application example 1 uses the eutectic solvent of halogenated ferric salt, the graphitization temperature can be reduced, so that the graphitization degree of the carbon fiber anode material prepared in the application example 1 is high, the conductivity is better than that of the comparative example 1, and the compression performance of the particle level is better than that of the comparative application example 1.
The rate performance of application example 8 is significantly better than that of comparative application example 2 because the carbon fiber material has good conductivity.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (32)
1. The carbon fiber material is characterized by comprising graphitized carbon fibers, wherein the graphitized carbon fibers are mutually overlapped to form a porous network structure, nano-structure gaps formed by carbon fiber interlacing are formed among the graphitized carbon fibers, and micropores are formed on the surfaces of the graphitized carbon fibers;
in the XRD spectrum of the carbon fiber material, the ratio of the main peak intensity of the 002 crystal face to the total peak intensity of the impurity peaks is 2-5:1;
The carbon fiber material is obtained by adopting a preparation method, which comprises the following steps:
(1) Heating and mixing halogenated choline and halogenated ferric salt according to the mol ratio of (1-3) (2-8) to form a eutectic solvent;
(2) Mixing fiber biomass carbon with the eutectic solvent to obtain a precursor;
(3) Carrying out high-temperature graphitization treatment on the precursor to obtain the carbon fiber material;
the temperature of the high-temperature graphitization treatment is 1550-1800 ℃.
2. The carbon fiber material of claim 1, wherein the micropores are etched from the fibrous biomass carbon using a flue gas of a eutectic solvent comprising a choline halide and an iron halide.
3. A method for preparing a carbon fiber material according to claim 1 or 2, characterized in that the method comprises the steps of:
(1) Heating and mixing halogenated choline and halogenated ferric salt according to the mol ratio of (1-3) (2-8) to form a eutectic solvent;
(2) Mixing fiber biomass carbon with the eutectic solvent to obtain a precursor;
(3) Carrying out high-temperature graphitization treatment on the precursor to obtain the carbon fiber material;
the temperature of the high-temperature graphitization treatment is 1550-1800 ℃.
4. A method according to claim 3, wherein the halogenated choline of step (1) comprises at least one of choline chloride, choline bromide, or a derivative thereof.
5. A method according to claim 3, wherein the halogenated ferric salt of step (1) comprises any one or more of ferric chloride, ferrous bromide or derivatives thereof.
6. A method according to claim 3, wherein the temperature of the heated mixture in step (1) is 40-80 ℃ for a period of 2-8 hours.
7. A method according to claim 3, wherein the heating and mixing of step (1) is accompanied by agitation.
8. A method according to claim 3, wherein the fibrous biomass carbon of step (2) is a non-grain biomass.
9. The method of claim 8, wherein the non-grain biomass of step (2) is at least one of bamboo fiber, lignocellulose, or derivatives thereof.
10. The method of claim 3, wherein in step (2), the mass ratio of the fibrous biomass carbon to the eutectic solvent is (1-3): 2-8.
11. A method according to claim 3, wherein the temperature of the mixing in step (2) is 40-80 ℃ for a period of 2-8 hours.
12. A method according to claim 3, wherein the mixing of step (2) is accompanied by agitation.
13. A method according to claim 3, wherein the mixing in step (2) is followed by the steps of ultrasonic agitation and standing in that order.
14. The method of claim 13, wherein the ultrasonic oscillation is performed at room temperature.
15. The method of claim 13, wherein the time of the ultrasonic oscillation is 20-60 minutes.
16. The method of claim 13, wherein the time of resting is 1-2 hours.
17. A method according to claim 3, wherein the precursor is pre-oxidized prior to the high temperature graphitization treatment of step (3).
18. The method of claim 17, wherein the pre-oxidation treatment is performed at a temperature of 200-300 ℃ for a holding time of 1-2 hours.
19. The method of claim 17, wherein the pre-oxidation treatment is at a ramp rate of 2-5 ℃ per minute.
20. The method of claim 17, wherein the pre-oxidation treatment atmosphere is an oxygen-containing atmosphere.
21. The method of claim 20, wherein the pre-oxidation treatment atmosphere is an air atmosphere.
22. A method according to claim 3, wherein the incubation time for the high temperature graphitization treatment of step (3) is 6 to 16 hours.
23. A method according to claim 3, wherein the elevated temperature of the high temperature graphitization treatment of step (3) is at a rate of 2-5 ℃ per minute.
24. A method according to claim 3, wherein the atmosphere of the high temperature graphitization treatment of step (3) is an inert atmosphere, and the gas in the inert atmosphere comprises at least one of nitrogen, helium and argon.
25. A method according to claim 3, wherein the high temperature graphitization treatment of step (3) is followed by the steps of acid washing, separation, ball milling and sieving in that order.
26. The method according to claim 25, wherein the solvent used for the acid washing in the step (3) is an acid washing solvent selected from one or more of hydrochloric acid, sulfuric acid and acetic acid.
27. The method of claim 25, wherein the solvent used for the washing is absolute ethanol.
28. The method of claim 25, wherein the ball milling is performed at a rotational speed of 500-1000r/min for a period of 4-6 hours.
29. The method of claim 25, wherein the screened mesh is 180-400 mesh and the undersize is removed after screening.
30. A lithium ion battery, characterized in that the carbon fiber material according to claim 1 or 2 is included in the lithium ion battery.
31. The lithium ion battery according to claim 30, wherein the negative electrode active material and the conductive agent in the negative electrode of the lithium ion battery at least partially adopt the carbon fiber material according to claim 1 or 2, wherein the mass ratio of the carbon fiber material is 20 to 40% based on the total weight of the negative electrode active material layer, or
The carbon fiber material according to claim 1 or 2 is used as a negative electrode conductive agent in a negative electrode of the lithium ion battery, wherein the mass ratio of the carbon fiber material is 2% -5% based on the total weight of the negative electrode active material layer.
32. The lithium ion battery of claim 30 or 31, wherein the lithium ion battery is a flexible battery.
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