CN116288923A - Porous carbon fiber felt, preparation method thereof and potassium ion battery anode - Google Patents
Porous carbon fiber felt, preparation method thereof and potassium ion battery anode Download PDFInfo
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- CN116288923A CN116288923A CN202211544014.0A CN202211544014A CN116288923A CN 116288923 A CN116288923 A CN 116288923A CN 202211544014 A CN202211544014 A CN 202211544014A CN 116288923 A CN116288923 A CN 116288923A
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- carbon fiber
- porous carbon
- fiber felt
- magnesium
- ion battery
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 108
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 108
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 33
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- -1 nitrogenous organic compound Chemical class 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002121 nanofiber Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229940091250 magnesium supplement Drugs 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 16
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229960002337 magnesium chloride Drugs 0.000 claims description 3
- 239000001755 magnesium gluconate Substances 0.000 claims description 3
- 229960003035 magnesium gluconate Drugs 0.000 claims description 3
- 235000015778 magnesium gluconate Nutrition 0.000 claims description 3
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 43
- 239000002131 composite material Substances 0.000 description 34
- 238000005554 pickling Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 102000020897 Formins Human genes 0.000 description 5
- 108091022623 Formins Proteins 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/413—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
- D04H1/43916—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres microcellular fibres, e.g. porous or foamed fibres
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- D—TEXTILES; PAPER
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a porous carbon fiber felt, a preparation method thereof and a potassium ion battery cathode, wherein the preparation method comprises the following steps: s1, dissolving a high molecular polymer, a magnesium salt and a nitrogenous organic compound in a solvent, and stirring to obtain a precursor; s2, preparing a nanofiber membrane by electrostatic spinning of the precursor obtained in the step S1; s3, performing pre-oxidation and calcination treatment on the nanofiber membrane obtained in the step S2 to obtain a carbon fiber felt embedded with magnesium nitride; s4, carrying out acid washing, water washing and drying on the carbon fiber felt with the embedded magnesium nitride obtained in the step S3 to obtain a porous carbon fiber felt, wherein the porous carbon fiber felt can promote the reaction kinetics of the battery when being used for the anode of the potassium ion battery and provide rich active sites, so that the potassium ion battery with high ploidy, long service life and high capacity is obtained.
Description
Technical Field
The invention relates to the technical field of potassium ion batteries, in particular to a porous carbon fiber felt, a preparation method thereof and a potassium ion battery cathode.
Background
At present, lithium ion batteries are widely applied to the fields of portable electronic equipment, large energy storage equipment and the like, so that the demand of lithium is in a trend of rapid annual growth, the global reserve of lithium is very limited and unevenly distributed, the price of raw materials is rapidly increased, and the rapid development of the fields of low-cost and high-performance energy storage devices in China is severely restricted. The potassium element has similar physical and chemical properties as the lithium element, is abundant in reserve, low in cost and easy to recycle, and has a lower oxidation-reduction potential (-2.91V) than sodium (-2.71V), namely a higher output potential, so that a secondary battery system based on potassium ions is receiving a great deal of attention. However, the defects of large volume, slow dynamics and the like of potassium ions lead to poor rate capability, low specific capacity and cycling stability of the potassium ion battery. Therefore, it is important to design and prepare an electrode material having good electrochemical properties.
Among the negative electrode materials of a plurality of potassium ion batteries, the carbon material is still considered to be the most promising electrode material of the commercial potassium ion battery because of the advantages of better chemical stability, higher conductivity, environmental friendliness and the like. However, current studies on carbon materials have shown that although a higher energy density (273 mA h.g -1 Theoretical value: 279 mAh.g -1 ) But the cycle stability and rate performance are poor mainly because the larger ionic radius of potassium ions causes the carbon electrode to undergo multiple volume expansion/contraction during charge and discharge, thereby resulting in structural collapse.
Disclosure of Invention
The invention provides a porous carbon fiber felt, a preparation method thereof and a potassium ion battery anode, which are used for solving the technical problems that the rate performance and the cycle stability of a potassium ion battery are poor due to the fact that the structure of the existing carbon material is easy to collapse when the existing carbon material is used as the potassium ion battery anode material.
According to an aspect of the present invention, there is provided a method for preparing a porous carbon fiber mat, comprising the steps of:
s1, dissolving polyacrylonitrile, magnesium salt and nitrogen-containing organic matters in an N, N-dimethylformamide solvent, stirring to obtain a precursor,
wherein the mass percentage concentration of the polyacrylonitrile in the N, N-dimethylformamide solvent is 35-48%; the mass percentage concentration of the magnesium salt in the N, N-dimethylformamide solvent is 4-16%; the mass percentage concentration of the nitrogen-containing organic matters in the N, N-dimethylformamide solvent is 2-14%;
s2, preparing a nanofiber membrane by electrostatic spinning of the precursor obtained in the step S1;
s3, performing pre-oxidation and calcination treatment on the nanofiber membrane obtained in the step S2 to obtain a carbon fiber felt embedded with magnesium nitride;
and S4, carrying out acid washing, water washing and drying on the carbon fiber felt with the embedded magnesium nitride obtained in the step S3 to obtain the porous carbon fiber felt.
Further, the magnesium salt in step S1 includes magnesium acetate, magnesium chloride, magnesium nitrate or magnesium gluconate.
Further, the nitrogen-containing organic matter in step S1 includes melamine, urea or biuret.
Further, the electrospinning conditions in step S2 are as follows: the working voltage is 10-20 kV, the collecting distance is 8-20 cm, and the flow rate of the spinning liquid is 0.3-2.0 mL.h -1 。
Further, the pre-oxidation treatment in step S3 includes: heating from room temperature to 230-280 ℃ in air, and preserving heat for 1-6 h, wherein the heating rate is 1-5 ℃ and min -1 。
Further, the calcining process in step S3 includes: under the protection of the mixed gas of argon and hydrogen, the secondary chamberHeating to 900-1000 ℃, and preserving heat for 3-6 hours, wherein the volume fraction of hydrogen is 6-10%; the temperature rising rate is 1-5 ℃ min -1 。
Further, the pickling in the step S4 comprises pickling for 1 to 5 hours by using hydrochloric acid or sulfuric acid, wherein the mass concentration of the hydrochloric acid or the sulfuric acid is 5 to 15 percent.
According to another aspect of the present invention, there is also provided a porous carbon fiber mat manufactured by the above method.
Further, the diameter of the carbon fiber in the porous carbon fiber felt is 220-260 nm, and the aperture is 20-30 nm.
According to an aspect of the present invention, there is also provided a potassium ion battery anode comprising the porous carbon fiber felt described above.
The invention has the following beneficial effects:
the preparation method of the porous carbon fiber felt provided by the invention firstly utilizes an electrostatic spinning technology to prepare the polyacrylonitrile composite fiber membrane with uniformly distributed magnesium salt and nitrogen-containing organic matters; then pre-oxidizing the prepared composite fiber membrane; then high-temperature calcination treatment is carried out to obtain carbon fiber with uniformly embedded magnesium nitride, in the process, polyacrylonitrile is carbonized into carbon fiber, magnesium salt and nitrogen-containing organic matters generate uniformly distributed magnesium nitride (Mg) in situ in the carbon fiber 3 N 2 ) The method comprises the steps of carrying out a first treatment on the surface of the And finally, carrying out dilute acid washing, water washing and drying on the uniformly embedded carbon fibers of the magnesium nitride to finally obtain the porous carbon fiber felt potassium ion battery anode material. In the process, magnesium nitride reacts with dilute acid to generate soluble magnesium salt and volatile ammonia gas, and the carbon skeleton is kept as it is, so that the porous carbon fiber felt is obtained.
The diameter of the carbon fiber in the porous carbon fiber felt prepared by the method is 220-260 nm, the aperture is 20-30 nm, the pore distribution is more uniform, and the porous carbon fiber felt has the following advantages when being used for the anode of a potassium ion battery: (1) The complete one-dimensional fibrous structure of the porous fiber mat is beneficial to electrons/K + The rapid transfer promotes the reaction kinetics, and provides a guarantee for obtaining high-rate performance of the battery; (2) The porous structure in the porous carbon fiber mat will help maintain the structural integrity of the electrode during repeated cycling and provideThe active sites are enriched, and obvious pseudocapacitance behaviors are caused, so that a long-life and high-capacity potassium ion battery is obtained; (3) The carbon fiber felt can be directly used as an electrode material without using a binder, so that the internal resistance of the battery is reduced, and the capacity and the multiplying power performance of the battery are improved; (4) The relatively uniform pores in the porous carbon fiber felt can ensure the stability of the structure in the circulation process, thereby providing a guarantee for the stability of the battery.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is an optical digital photograph of the porous carbon fiber felt obtained in example 1;
FIG. 2 is a scanning electron microscope image of the porous carbon fiber felt obtained in example 1;
FIG. 3 is a transmission electron micrograph of the porous carbon fiber felt obtained in example 1;
FIG. 4 is a transmission electron micrograph of the porous carbon fiber felt obtained in example 2;
FIG. 5 is a transmission electron micrograph of the porous carbon fiber felt obtained in example 3;
FIG. 6 is a transmission electron micrograph of the carbon fiber felt obtained in comparative example 1;
FIG. 7 shows the current density of the porous carbon fiber felt obtained in example 1 and the carbon fiber felt obtained in comparative example 1 as potassium ion anode at 0.1 A.g -1 A comparison chart of potassium storage cycle performance;
fig. 8 is a graph showing potassium storage capacity of the porous carbon fiber felt obtained in example 1 and the carbon fiber felt obtained in comparative example 1 as a negative electrode for potassium ions.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
An embodiment of a first aspect of the present application provides a method for preparing a porous carbon fiber mat, including the steps of:
s1, dissolving polyacrylonitrile, magnesium salt and nitrogen-containing organic matters in an N, N-dimethylformamide solvent, stirring to obtain a precursor,
wherein the mass percentage concentration of the polyacrylonitrile in the N, N-dimethylformamide solvent is 35-48%; the mass percentage concentration of the magnesium salt in the N, N-dimethylformamide solvent is 4-16%; the mass percentage concentration of the nitrogen-containing organic matters in the N, N-dimethylformamide solvent is 2-14%;
s2, preparing a nanofiber membrane by electrostatic spinning of the precursor obtained in the step S1;
s3, performing pre-oxidation and calcination treatment on the nanofiber membrane obtained in the step S2 to obtain a carbon fiber felt embedded with magnesium nitride;
and S4, carrying out acid washing, water washing and drying on the carbon fiber felt with the embedded magnesium nitride obtained in the step S3 to obtain the porous carbon fiber felt.
The preparation method of the porous carbon fiber felt provided by the invention firstly utilizes an electrostatic spinning technology to prepare a high polymer composite fiber membrane with evenly distributed magnesium salt and nitrogenous organic matters; then pre-oxidizing the prepared composite fiber membrane; and then high-temperature calcination treatment is carried out to obtain carbon fiber with uniformly embedded magnesium nitride, in the process, the high-molecular polymer is carbonized into carbon fiber, and magnesium salt and nitrogen-containing organic matters generate uniformly distributed magnesium nitride (Mg) in situ in the carbon fiber 3 N 2 ) The method comprises the steps of carrying out a first treatment on the surface of the And finally, carrying out dilute acid washing, water washing and drying on the uniformly embedded carbon fibers of the magnesium nitride to finally obtain the porous carbon fiber felt potassium ion battery anode material. In the process, magnesium nitride reacts with dilute acid to generate soluble magnesium salt and volatile ammonia gas, and the carbon skeleton is kept as it is, so that the porous carbon fiber felt is obtained. The method has the advantages of low processing cost, simple and easily controlled process, short period, high efficiency, energy conservation and convenience for further expanding production.
According to the embodiment of the invention, the mass percentage concentration of the magnesium salt in the solvent is 4-16%; the mass percentage concentration of the nitrogen-containing organic matters in the solvent is 2-14%. The magnesium salt and the nitrogen-containing organic are mainly used for generating magnesium nitride embedded in the carbon fiber, and if the content is too high, excessive magnesium nitride particles are precipitated on the surface of the carbon fiber, so that the magnesium nitride does not contribute to the generation of a porous structure in the subsequent carbon fiber; if the content is too low, the formation of a porous structure is not favored.
In an embodiment of the present invention, the magnesium salt in step S1 comprises magnesium acetate, magnesium chloride, magnesium nitrate or magnesium gluconate.
In an embodiment of the invention, the nitrogen-containing organic matter in step S1 comprises melamine, urea or biuret.
In an embodiment of the present invention, the electrospinning conditions in step S2 are as follows: the working voltage is 10-20 kV, the collecting distance is 8-20 cm, and the flow rate of the spinning liquid is 0.3-2.0 mL.h -1 . The carbon fiber obtained by the working voltage, the collecting distance and the spinning liquid flow rate in the range is directly beneficial to obtaining better potassium storage performance, if the diameter is too large, the carbon fiber is not beneficial to K + And e - And the potassium storage kinetics is reduced, if the diameter is too small, the flexibility of the electrode is not facilitated, and a complete carbon fiber felt cannot be obtained.
In an embodiment of the present invention, the pre-oxidation treatment in step S3 includes: heating from room temperature to 230-280 ℃ in air, and preserving heat for 1-6 h, wherein the heating rate is 1-5 ℃ and min -1 。
In an embodiment of the present invention, the calcining process in step S3 includes: under the protection of the mixed gas of argon and hydrogen, the temperature is raised to 900-1000 ℃ from room temperature, and the temperature is kept for 3-6 hours, wherein the volume fraction of the hydrogen is 6-10%; the temperature rising rate is 1-5 ℃ min -1 。
In an embodiment of the present invention, the pickling in step S4 comprises pickling with hydrochloric acid or sulfuric acid for 1 to 5 hours, wherein the mass concentration of the hydrochloric acid or sulfuric acid is 5 to 15%.
In the embodiment of the invention, the atmosphere in the drying process in the step S4 is one of air, nitrogen or argon, the temperature is 50-80 ℃, and the drying time is 5-12 h.
Embodiments of the second aspect of the present application provide a porous carbon fiber mat prepared by the above method.
The diameter of the carbon fiber in the porous carbon fiber felt is 220-260 nm, and the aperture is 20-30 nm.
The preparation method has the following advantages when being used for preparing the anode of the potassium ion battery:
(1) The complete one-dimensional fibrous structure of the porous fiber mat is beneficial to electrons/K + The rapid transfer promotes the reaction kinetics and provides guarantee for obtaining high-rate performance of the battery.
(2) The porous structure in the porous carbon fiber mat will help to maintain the structural integrity of the electrode during repeated cycling and provide a rich active site, causing significant pseudocapacitive behavior, resulting in a long life, high capacity potassium ion battery. Pseudocapacitive behavior caused by ion adsorption on the electrode surface has been demonstrated to give better rate performance and cycling stability, mainly because the pseudocapacitive behavior does not damage the electrode material structure.
(3) The carbon fiber felt can be directly used as an electrode material without using a binder, so that the internal resistance of the battery is reduced, and the capacity and the multiplying power performance of the battery are improved.
(4) The relatively uniform pores in the porous carbon fiber felt can ensure the stability of the structure in the circulation process, thereby providing a guarantee for the stability of the battery.
Embodiments of the third aspect of the present application provide a potassium ion battery anode made of the porous carbon fiber felt described above.
In the examples, the porous carbon fiber felt was assembled as a negative electrode to form a potassium ion battery having a current density of 0.1 A.g -1 Under the condition of (1) 120 cycles, the specific charge capacity is still kept at 270 mAh.g -1 The above method has good circulation stability.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
S1, respectively weighing 7g of Polyacrylonitrile (PAN), 3g of magnesium chloride and 1.5g of melamine, adding into 10mL of N, N-Dimethylformamide (DMF) solution, and stirring at room temperature for 12h to obtain a transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 12kV, collecting the precursor solution at a collecting distance of 15cm and setting the solution flow rate to be 0.4 mL.h -1 And (3) obtaining the smooth composite fiber membrane after the precursor solution is completely spun.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 230 ℃ for pre-oxidation treatment for 1 hour at a heating rate of 1 ℃ for min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 8% 2 The mixed gas provides protection, and the temperature is raised from room temperature to 900 ℃ with the temperature raising rate of 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Fig. 1 is an optical digital photograph of the obtained porous carbon fiber mat, and it is apparent from fig. 1 that the carbon fiber mat prepared by example 1 has a complete sheet structure and can be freely bent at 180 degrees, indicating that the carbon fiber mat can be directly used as an electrode material.
Fig. 2 is a scanning electron microscope image of the obtained porous carbon fiber felt, and as can be seen from fig. 2, the carbon fiber felt is composed of one-dimensional carbon fibers with the diameter of about 240nm, and larger pores are reserved among the fibers, so that the transmission of electrons and the diffusion of potassium ions are facilitated, and the reaction kinetics is improved.
Fig. 3 is a transmission electron microscope image of the obtained porous carbon fiber felt, and as can be seen from fig. 3, a large number of mesopores with diameters of about 30nm exist in the carbon fiber felt, which can effectively relieve the problem of structural collapse and the like caused by volume change in the charge and discharge process, thereby improving the electrochemical performance.
After the porous carbon fiber felt obtained in the present example 1 was directly assembled into a potassium ion battery, the current density was 0.1 A.g -1 Under the condition of (2) the specific charge capacity is still 276 mAh.g after 120 cycles -1 (as shown in FIG. 7), and when the current density is raised to 2A.g -1 Still has 188 mAh.g -1 As shown in fig. 8).
Example 2
S1, respectively weighing 7g of PAN, 3g of magnesium nitrate and 1.5g of melamine, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 12kV, collecting the precursor solution at a collecting distance of 15cm and setting the solution flow rate to be 0.4 mL.h -1 To the full of precursor solutionAnd after the partial spinning is finished, obtaining the smooth composite fiber membrane.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 230 ℃ for pre-oxidation treatment for 1 hour at a heating rate of 1 ℃ for min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 8% 2 The mixed gas provides protection, and the temperature is raised from room temperature to 900 ℃ with the temperature raising rate of 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Fig. 4 is a transmission electron microscopic image of the obtained porous carbon fiber felt, and it is apparent from fig. 4 that a large number of mesopores having a diameter of about 30nm exist inside the carbon fiber.
Example 3
S1, respectively weighing 7g of PAN, 3g of magnesium nitrate and 2g of urea, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 12kV, collecting the precursor solution at a collecting distance of 15cm and setting the solution flow rate to be 0.4 mL.h -1 And (3) obtaining the smooth composite fiber membrane after the precursor solution is completely spun.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 230 ℃ for pre-oxidation treatment for 1 hour at a heating rate of 1 ℃ for min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 8% 2 The mixed gas provides protection, and the temperature is raised from room temperature to 900 ℃ with the temperature raising rate of 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Fig. 5 is a transmission electron microscopic image of the obtained porous carbon fiber felt, and it is apparent from fig. 5 that a certain amount of mesopores with a diameter of about 20nm exist inside the carbon fibers.
Example 4
S1, respectively weighing 7g of PAN, 3g of magnesium nitrate and 1.5g of melamine, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 15kV, collecting the precursor solution at a collection distance of 18cm and setting the solution flow rate to be 0.6 mL.h -1 And (3) obtaining the smooth composite fiber membrane after the precursor solution is completely spun.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 230 ℃ for pre-oxidation treatment for 1 hour at a heating rate of 1 ℃ for min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 8% 2 The mixed gas provides protection, and the temperature is raised from room temperature to 900 ℃ with the temperature raising rate of 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Example 5
S1, respectively weighing 7g of PAN, 3g of magnesium nitrate and 1.5g of melamine, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 12kV, collecting the precursor solution at a collecting distance of 15cm and setting the solution flow rate to be 0.4 mL.h -1 And (3) obtaining the smooth composite fiber membrane after the precursor solution is completely spun.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 260 ℃ for pre-oxidation treatment for 1 hour, wherein the heating rate is 1 ℃ and min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 8% 2 The mixed gas provides protection, and rises from room temperature to 900 ℃ at a rapid rateRate 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Example 6
S1, respectively weighing 7g of PAN, 3g of magnesium nitrate and 1.5g of melamine, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
S2, placing the precursor solution into spinning equipment, setting the spinning voltage to be 12kV, collecting the precursor solution at a collecting distance of 15cm and setting the solution flow rate to be 0.4 mL.h -1 And (3) obtaining the smooth composite fiber membrane after the precursor solution is completely spun.
S3, drying the composite fiber membrane in a vacuum drying oven for 12 hours, and then placing the composite fiber membrane in a muffle furnace, and heating the composite fiber membrane from room temperature to 230 ℃ for pre-oxidation treatment for 1 hour at a heating rate of 1 ℃ for min -1 . Subsequently, the composite fiber membrane is placed in a tube furnace, and H is introduced 2 Ar/H at 6% 2 The mixed gas provides protection, the temperature is raised to 1000 ℃ from room temperature, and the temperature raising rate is 2 ℃ min -1 And (3) preserving the heat for 2 hours, and naturally cooling to room temperature under the protection of gas to obtain the magnesium nitride embedded carbon fiber felt.
S4, immersing the fiber felt in 10% hydrochloric acid, pickling for 5 hours, taking out, washing to be neutral, and drying in a 60 ℃ oven to obtain the porous carbon fiber felt.
Comparative example 1
S1, respectively weighing 7g of PAN, adding into 10mL of DMF solution, and stirring at room temperature for 12h to obtain transparent precursor solution.
The other steps were the same as in example 1, to obtain a carbon fiber felt.
Fig. 6 is a transmission electron microscope image of the obtained carbon fiber mat, and as can be seen from fig. 6, when no magnesium salt and no nitrogen-containing organic matter are added to the precursor, the inside of the obtained carbon fiber is solid, which is disadvantageous in obtaining a potassium ion battery with a high specific capacity.
After the carbon fiber felt obtained in the comparative example 1 is directly assembled into a potassium ion battery, the current is measuredDensity of 0.1 A.g -1 Under the condition of (1) 120 cycles, the specific charge capacity is only 155 mAh.g -1 (as shown in FIG. 7), and when the current density is raised to 2A.g -1 The specific charge capacity is only 89 mAh.g -1 (as shown in fig. 8).
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention, and in particular, the technical features set forth in the various embodiments may be combined in any manner so long as there is no structural conflict. The present invention is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The preparation method of the porous carbon fiber felt is characterized by comprising the following steps:
s1, dissolving polyacrylonitrile, magnesium salt and nitrogen-containing organic matters in an N, N-dimethylformamide solvent, stirring to obtain a precursor,
wherein the mass percentage concentration of the polyacrylonitrile in the N, N-dimethylformamide solvent is 35-48%; the mass percentage concentration of the magnesium salt in the N, N-dimethylformamide solvent is 4-16%; the mass percentage concentration of the nitrogen-containing organic matters in the N, N-dimethylformamide solvent is 2-14%;
s2, preparing a nanofiber membrane by electrostatic spinning of the precursor obtained in the step S1;
s3, performing pre-oxidation and calcination treatment on the nanofiber membrane obtained in the step S2 to obtain a carbon fiber felt embedded with magnesium nitride;
and S4, carrying out acid washing, water washing and drying on the carbon fiber felt with the embedded magnesium nitride obtained in the step S3 to obtain the porous carbon fiber felt.
2. The method of claim 1, wherein the magnesium salt in step S1 comprises magnesium acetate, magnesium chloride, magnesium nitrate or magnesium gluconate.
3. The method of producing a porous carbon fiber mat according to claim 1, wherein the nitrogen-containing organic matter in step S1 includes melamine, urea or biuret.
4. The method for preparing a porous carbon fiber mat according to claim 1, wherein the electrospinning conditions in step S2 are as follows: the working voltage is 10-20 kV, the collecting distance is 8-20 cm, and the flow rate of the spinning liquid is 0.3-2.0 mL.h -1 。
5. The method of producing a porous carbon fiber mat according to claim 1, wherein the pre-oxidation treatment in step S3 comprises: heating from room temperature to 230-280 ℃ in air, and preserving heat for 1-6 h, wherein the heating rate is 1-5 ℃ and min -1 。
6. The method of producing a porous carbon fiber mat according to claim 1, wherein the calcination treatment in step S3 includes: under the protection of the mixed gas of argon and hydrogen, the temperature is raised to 900-1000 ℃ from room temperature, and the temperature is kept for 3-6 hours, wherein the volume fraction of the hydrogen is 6-10%; the temperature rising rate is 1-5 ℃ min -1 。
7. The method of producing a porous carbon fiber mat according to claim 1, wherein the acid washing in step S4 comprises acid washing with hydrochloric acid or sulfuric acid for 1 to 5 hours, wherein the mass concentration of the hydrochloric acid or sulfuric acid is 5 to 15%.
8. A porous carbon fiber mat produced by the production method of any one of claims 1 to 7.
9. The porous carbon fiber mat according to claim 8, wherein the carbon fibers in the porous carbon fiber mat have a diameter of 220 to 260nm and a pore diameter of 20 to 30nm.
10. A negative electrode for a potassium ion battery, characterized in that the negative electrode for a potassium ion battery comprises the porous carbon fiber felt according to claim 8 or 9.
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