CN115058793A - Carbon fiber, carbon fiber negative electrode material and preparation method - Google Patents
Carbon fiber, carbon fiber negative electrode material and preparation method Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 94
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 14
- 239000002134 carbon nanofiber Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910001414 potassium ion Inorganic materials 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of electrode pole pieces, in particular to a carbon fiber and a preparation method thereof, wherein the (002) crystal face orientation of the carbon fiber is vertical to the axial direction, so that the diffusion distance of ions in the embedding/removing process can be effectively shortened, the reaction kinetics is accelerated, the multiplying power performance of a negative electrode material under high current density is improved, and the reversible capacity of the material is improved. The carbon fiber is prepared by a high-temperature hydrothermal molten salt method, and raw materials used in the whole technological process are clean, pollution-free, simple and easy to control, and have extremely high popularization value.
Description
Technical Field
The invention belongs to the technical field of electrode plates, and particularly relates to carbon fibers and a preparation method thereof.
Background
The carbon material is the most commonly used active main body material for preparing the cathode of the ion battery, and can be divided into carbon nano sheets, carbon nano tubes, carbon nano fibers, carbon nano spheres and the like according to different morphological structures. Among these carbon materials having different morphologies, carbon nanofibers having a 1D structure are superior in electron conductivity and mechanical toughness to other materials, and are increasingly favored in the market because they can be directly used as a potassium ion negative electrode material without using a binder, a conductive additive, a metal current collector, etc., thereby simplifying the battery assembly process, reducing the overall weight of the battery, reducing the production cost, etc.
The preparation method of the carbon nanofiber is single, and is mainly obtained by high-temperature carbonization after electrostatic spinning, the preparation process has certain defects, firstly, N-N Dimethylformamide (DMF) harmful to human bodies is used as a solvent to dissolve high polymers in the preparation process, the operation difficulty is high, secondly, the (002) crystal face orientation of the prepared carbon nanofiber is highly parallel to the axial direction of the carbon nanofiber, the structure can enable potassium ions to need long-distance body diffusion in the embedding/removing process, the reaction kinetics is slow, the multiplying power performance of a negative electrode material under high current density is affected, and the (002) crystal face parallel orientation enables the number of potassium ions embedded in the interlayer spacing to be small, and the reversible capacity of an electrode is poor.
Disclosure of Invention
Aiming at the defects of rate capability and reversible capacity difference of an electrode under high current density and the like of the nano carbon fiber prepared by adopting an electrostatic spinning method in the prior art, the invention provides the carbon fiber and the preparation method thereof, wherein (002) crystal face of the carbon fiber is oriented to be vertical to the axial direction of the fiber, and the rate capability and the reversible capacity of the electrode under high current density are obviously superior to those of the carbon fiber with the (002) crystal face parallel to the axial direction in the market.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
in one aspect, embodiments of the present invention provide a carbon fiber, where a (002) crystal plane of the carbon fiber is oriented perpendicular to a fiber axial direction of the carbon fiber.
Compared with the prior art, the (002) crystal face of the carbon fiber provided by the invention is oriented to be vertical to the axial direction of the carbon fiber, so that the required distance for ions to diffuse in the material is shortened, the diffusion efficiency of the ions is improved, and the multiplying power performance of the electrode material under high current density is improved; meanwhile, the number of ions embedded into the interlayer space of the carbon fiber material is increased, and the reversible capacity of the carbon material is improved.
On the other hand, the embodiment of the invention also provides a preparation method of the carbon fiber, which comprises the following steps:
s1: dipping a carbon source into a mixed solution containing phosphate and chloride to obtain a mixed reaction solution, wherein the mass ratio of the carbon source to the phosphate in the mixed solution is 1.5-3.5: 1.8-2.8, wherein the carbon source is a carbon material with a fibrous morphology structure;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) to a high-pressure reaction device in a closed anhydrous ultrapure environment filled with inert gas, uniformly heating to 500-700 ℃, reacting at a constant temperature, and cooling to obtain the carbon fiber.
Compared with the prior art, the preparation method of the carbon fiber provided by the invention takes the salt template as a reaction medium, the uniform reaction system is favorable for the diffusion of reactants and products, the uniformity of the reaction and growth environment is kept, the shape uniformity of the target product is favorably controlled, and phosphate can be decomposed to generate NH 3 And a phosphorus-based compound, wherein the phosphorus-based compound can form a strong P-C bond with a C element in a carbon source to promote and induce the growth of (002) crystal plane orientation towards a direction perpendicular to the axis of the carbon fiber; NH (NH) 3 Can be used as an N source to generate nitrogen doping defects in carbon nanofibers, can cause charge arrangement around C atoms due to the introduction of the N atoms, reduces an energy barrier required by the formation of P-C bonds, improves the generation quantity of the P-C bonds, realizes the control of the content of the P-C bonds by adjusting the mass ratio of phosphate to the C source and other factors, and avoids the condition that the (002) crystal face orientation is parallel to the carbon fiber axis or forms any non-right angleAnd the carbon fiber with the (002) crystal face oriented perpendicular to the axial direction of the carbon fiber is prepared. The raw materials used in the whole process are clean and pollution-free, are simple and easy to control, and have extremely high popularization value.
Preferably, the carbon material in S1 is rice paper, carbon cloth or carbon felt.
Preferably, the phosphate is ammonium dihydrogen phosphate, ammonium hydrogen phosphate or ammonium phosphate.
Preferably, the chloride in S1 is sodium chloride or zinc chloride, and the mass ratio of the chloride to the carbon source is 3-5: 1 to 2.
As a reaction medium, the chloride with proper dosage can provide sufficient reaction space for the reaction, improve the reaction rate, shorten the reaction time, avoid the reaction pressure brought by excessive reaction medium and ensure the reaction safety.
Preferably, the temperature rise rate in S3 is 2-5 ℃/min.
The optimized heating rate can ensure that phosphate is fully decomposed and simultaneously promote efficient carbon conversion reaction, so that the finally obtained product has high carbon content.
Preferably, the time for the heat preservation reaction in S3 is 8-12 h. Preferably, the preparation method further comprises S3: and (4) repeatedly washing the product obtained in the step (S2) with an aqueous solution of distilled water and ethanol, and drying to obtain the purified carbon fiber.
The embodiment of the invention also provides a carbon fiber cathode material, wherein the carbon fiber in the carbon fiber cathode material is the carbon fiber with the (002) crystal plane oriented perpendicular to the axial direction of the carbon fiber, or the carbon fiber prepared by the preparation method.
Drawings
Fig. 1 is a schematic view of diffusion paths of potassium ions in a carbon fiber in which (002) crystal plane orientation is parallel to the axial direction and perpendicular to the axial direction;
FIG. 2 is a graph showing P-C bond contents in carbon fibers obtained in example 1 and comparative examples 2 and 3;
FIG. 3 is an axial orientation of the carbon fibers obtained in example 1 and comparative examples 1 to 3;
FIG. 4 shows (002) plane orientations of the carbon fibers obtained in example 1 and comparative examples 1 to 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The carbon material is the most commonly used active main body material of the potassium ion battery cathode, and can be divided into carbon nano sheets, carbon nano tubes, carbon nano fibers, carbon nano spheres and the like according to the morphological structure, and in the carbon materials, the carbon nano fibers can be directly used as the potassium ion battery cathode material without using a binder, a conductive additive, a metal current collector and the like due to the high electronic conductivity and high mechanical toughness of the carbon nano fibers, so that the battery assembly procedure is simplified, the overall weight of the battery is reduced, the production cost is reduced and the like, and the carbon fibers with the 1D structure are widely applied to the potassium ion battery cathode material.
The existing carbon nanofiber electrode plate is mainly prepared by high-temperature carbonization after electrostatic spinning, N-dimethylformamide solution is usually adopted to dissolve high polymer, which is not beneficial to human health, and the crystal face orientation of the obtained carbon nanofiber (002) is highly parallel to the axial direction of the carbon nanofiber, so that the position relation greatly prolongs the diffusion path of potassium ions in the process of embedding/removing a negative electrode, the reaction kinetics is slow, and the rate capability of a battery under high current density is reduced; in addition, this positional relationship also reduces the number of potassium ions inserted between layers, resulting in poor reversible capacity.
In order to solve the defects of the existing carbon nanofiber in structure and preparation process, the inventor conducts deep research on the structure and preparation process of the carbon fiber, and finds that when the (002) crystal face of the carbon fiber is oriented to be vertical to the axial direction, the distance required by the diffusion of ions in the material can be shortened, the diffusion efficiency of the ions can be improved, the rate capability of the electrode material under high current density can be further enlarged, the structure can also improve the quantity of ions embedded in the carbon fiber, and the reversible capacity of the carbon fiber can be improved.
In order to prepare the carbon fiber with the (002) crystal face orientation vertical to the axial direction, the inventor researches the forming process of the carbon fiber, and finds that a high-temperature hydrothermal molten salt method adopts a salt template as a reaction medium, so that a uniform system can be formed, the uniform dispersion of a product is facilitated, the uniformity of a reaction and growth environment can be kept, the appearance of a target product is controllable, and the method is an ideal method for preparing the carbon fiber; however, the energy barrier required by the formation of the P-C bond is higher, and how to enable the content of the P-C bond to reach the degree that the (002) crystal face can be promoted to grow towards the direction vertical to the axial direction is also the key for preparing the material.
On the basis of the research findings, the carbon fiber with the (002) crystal face oriented perpendicular to the axial direction is finally prepared; the preparation method of the carbon fiber specifically comprises the following steps:
s1: dipping a carbon source into a mixed solution containing phosphate and chloride to obtain a mixed reaction solution, wherein the mass ratio of the carbon source to the phosphate is (1.5-3.5): 1.8-2.8, wherein the carbon source is a carbon material with a fibrous morphology structure;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) to a high-pressure reaction device in a closed anhydrous ultrapure environment filled with inert gas, raising the temperature to 500-700 ℃ at a constant speed, reacting at a constant temperature, and cooling to obtain a reaction product, namely the carbon fiber.
1.5-3.5: the mass ratio of the carbon source to the phosphate of 1.8-2.8 can control the content of P-C bonds in the carbon fiber, so that the content of the P-C bonds can induce (002) crystal plane orientation to be vertical to the direction of the carbon fiber axis, and the corresponding carbon fiber is prepared.
The invention will now be further illustrated in the following examples.
Example 1
The embodiment provides a carbon fiber with a (002) crystal plane oriented perpendicular to an axial direction, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 3g of rice paper, and soaking the rice paper in a mixed solution containing 2.0g of ammonium hydrogen phosphate and 8g of zinc chloride to obtain a mixed reaction solution;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) into a high-pressure reaction kettle under the condition of ensuring no water, oxygen and dust in a glove box filled with argon, heating to 600 ℃ at the heating rate of 4 ℃/min, carrying out heat preservation reaction for 12 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Example 2
The embodiment provides a carbon fiber with a (002) crystal plane oriented perpendicular to an axial direction, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 1.5g of carbon cloth, and soaking the carbon cloth in a mixed solution containing 1.8g of diammonium phosphate and 7g of zinc chloride to obtain a mixed reaction solution;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) into a high-pressure reaction kettle under the condition of ensuring no water, oxygen and dust in a glove box filled with argon, heating to 600 ℃ at the heating rate of 4 ℃/min, carrying out heat preservation reaction for 12 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Example 3
The embodiment provides a carbon fiber with a (002) crystal plane oriented perpendicular to an axial direction, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 3.5g of carbon felt, and soaking the carbon felt in a mixed solution containing 2.8g of ammonium dihydrogen phosphate and 8g of zinc chloride to obtain a mixed reaction solution;
s2: and (2) transferring the mixed reaction solution obtained in the step (S1) to a high-pressure reaction kettle in a glove box filled with argon under the condition of ensuring no water, oxygen and dust, heating to 600 ℃ at the heating rate of 4 ℃/min, carrying out heat preservation reaction for 12 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Example 4
The present embodiment provides an electrode plate, and a negative electrode material of the electrode plate is the carbon fiber prepared in any one of embodiments 1 to 3.
Comparative example 1
The comparative example provides a carbon fiber, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 3g of carbon cloth, and soaking the carbon cloth in a sodium chloride solution containing 8g of sodium chloride to obtain a mixed reaction solution;
s2: and (2) transferring the mixed reaction solution obtained in the step (S1) to a high-pressure reaction kettle in a glove box filled with argon under the condition of ensuring no water, oxygen and dust, heating to 600 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation reaction for 10 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Comparative example 2
The comparative example provides a carbon fiber, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 3g of carbon cloth, and soaking the carbon cloth in a mixed solution containing 1.0g of ammonium hydrogen phosphate and 8g of sodium chloride to obtain a mixed reaction solution;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) into a high-pressure reaction kettle under the condition of ensuring no water, oxygen and dust in a glove box filled with argon, heating to 600 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation reaction for 10 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Comparative example 3
The comparative example provides a carbon fiber, and the preparation method of the carbon fiber specifically comprises the following steps:
s1: weighing 3g of carbon felt, and soaking the carbon felt in a mixed solution containing 6.0g of ammonium hydrogen phosphate and 8g of sodium chloride to obtain a mixed reaction solution;
s2: and (3) transferring the mixed reaction solution obtained in the step (S1) into a high-pressure reaction kettle under the condition of ensuring no water, oxygen and dust in a glove box filled with argon, heating to 600 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation reaction for 8 hours, naturally cooling, collecting a black product in the high-pressure reaction kettle, washing with distilled water and ethanol for multiple times, and carrying out vacuum drying to obtain the carbon fiber.
Example of detection
The schematic diagram of the diffusion path of potassium ions in the (002) plane oriented parallel to the axial direction and perpendicular to the axial direction is shown in fig. 1, and it can be seen that the diffusion path of potassium ions in the carbon fiber in which the (002) plane oriented perpendicular to the axial direction is significantly shorter than that of the carbon fiber in which the (002) plane oriented parallel to the axial direction.
Detecting the P-C bond content in the carbon fibers prepared in the examples 1-3, the comparative example 2 and the comparative example 3, wherein the results obtained in the examples 1-3 are similar; the test results of example 1, comparative example 2 and comparative example 3 are shown in fig. 2, and it can be seen that the P — C bond content of the carbon fiber produced in example 1 was the highest at 88%.
Observing the axial orientation and the (002) crystal plane orientation of the carbon fibers prepared in the examples 1-3 and the comparative examples 1-3 by using an electron microscope, wherein the results of the examples 1-3 are consistent, the observation results of the examples 1 and the comparative examples 1-3 are shown in figures 3 and 4, and the (002) crystal plane orientation of the carbon fiber prepared in the example 1 is vertical to the axial direction as can be seen by combining the figures 3 and 4; the (002) plane orientation of the carbon fibers prepared in comparative examples 2 and 3 forms an arbitrary non-perpendicular angle with the axial direction, and the (002) plane orientation of the carbon fiber prepared in comparative example 1 is parallel to the axial direction.
The multiplying power capacity, specific capacity and circulating capacity of the carbon fibers prepared in examples 1-3 and comparative examples 1-3 were tested by using a blue testing system, and the obtained results are shown in table 1:
| 2A/g rate capacity | 1A/g specific capacity | Capacity of 2000 cycles of 5A/g | |
| Example 1 | 218mAh/g | 296mAh/g | 196mAh/g |
| Example 2 | 216mAh/g | 294mAh/g | 194mAh/g |
| Example 3 | 217mAh/g | 295mAh/g | 195mAh/g |
| Comparative example 1 | 145mAh/g | 180mAh/g | 89mAh/g |
| Comparative example 2 | 172mAh/g | 213mAh/g | 122mAh/g |
| Comparative example 3 | 188mAh/g | 248mAh/g | 128mAh/g |
As can be seen from the data in the table I, the carbon fiber prepared by the preparation method of the carbon fiber provided by the invention has the multiplying power performance of 2A/g which is more than or equal to 200mAh/g, the specific capacity of 1A/g which is more than or equal to 280mAh/g, and the capacity after 5A/g circulation for 2000 times which is still more than or equal to 180mAh/g, so that the multiplying power performance and reversible capacity of the carbon fiber with the (002) crystal face oriented to be vertical to the axial direction provided by the invention are outstanding, and the preparation method has remarkable progress.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A carbon fiber characterized in that the (002) crystal plane of the carbon fiber is oriented perpendicular to the fiber axial direction thereof.
2. The method for producing carbon fibers according to claim 1, characterized by specifically comprising the steps of:
s1: dipping a carbon source into a solution containing phosphate and chloride to obtain a mixed reaction solution; wherein the mass ratio of the carbon source to the phosphate in the mixed solution is 1.5-3.5: 1.8-2.8, wherein the carbon source is a carbon material with a fibrous morphology structure;
s2: and transferring the mixed reaction solution to a high-pressure reaction device in a closed anhydrous ultrapure environment filled with inert gas, raising the temperature to 500-700 ℃ at a constant speed, reacting at a constant temperature, and cooling to obtain the carbon fiber.
3. The method for producing a carbon fiber according to claim 2, wherein the carbon material of S1 is rice paper, carbon cloth, or carbon felt.
4. The method for producing a carbon fiber according to claim 2, wherein the phosphate at S1 is diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or ammonium phosphate.
5. The method for producing carbon fibers according to claim 2, wherein the chloride salt in S1 is zinc chloride or sodium chloride, and the mass ratio of the chloride salt to the carbon source is 3-5: 1 to 2.
6. The preparation method of the carbon fiber according to claim 2, wherein the temperature rise rate of the uniform temperature rise in S2 is 2-5 ℃/min.
7. The method for preparing carbon fiber according to claim 2, wherein the isothermal reaction time in S2 is 8-12 hours.
8. The method for producing a carbon fiber according to claim 2, further comprising S3: and (4) repeatedly washing the product obtained in the step (S2) with an ethanol aqueous solution, and drying to obtain the purified carbon fiber.
9. The carbon fiber of claim 1 or the carbon fiber prepared by the preparation method of any one of claims 2 to 8 is used as a negative electrode material of an electrode plate.
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| US5698341A (en) * | 1995-08-18 | 1997-12-16 | Petoca, Ltd. | Carbon material for lithium secondary battery and process for producing the same |
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| US20080045413A1 (en) * | 2006-08-16 | 2008-02-21 | Feng Chia University | Method for manufacturing activated carbon fiber products |
| JP2008248457A (en) * | 2007-03-30 | 2008-10-16 | Nano Carbon Technologies Kk | Carbon fiber composite and method for producing the carbon fiber composite |
| JP2010114042A (en) * | 2008-11-10 | 2010-05-20 | Nec Corp | Secondary battery, and manufacturing method thereof |
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| US5698341A (en) * | 1995-08-18 | 1997-12-16 | Petoca, Ltd. | Carbon material for lithium secondary battery and process for producing the same |
| US6120841A (en) * | 1997-03-14 | 2000-09-19 | Messier-Bugatti | Method of making an activated fabric of carbon fibers |
| JP2007042620A (en) * | 2005-07-04 | 2007-02-15 | Showa Denko Kk | Negative electrode for lithium secondary battery, manufacturing method of negative electrode composition, and lithium secondary battery |
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