CN116695287A - Preparation method and application of soft and hard heterogeneous carbon fiber composite material - Google Patents
Preparation method and application of soft and hard heterogeneous carbon fiber composite material Download PDFInfo
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- CN116695287A CN116695287A CN202310605969.0A CN202310605969A CN116695287A CN 116695287 A CN116695287 A CN 116695287A CN 202310605969 A CN202310605969 A CN 202310605969A CN 116695287 A CN116695287 A CN 116695287A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 58
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 46
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003830 anthracite Substances 0.000 claims abstract description 45
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 23
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000004146 energy storage Methods 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract 3
- 239000012744 reinforcing agent Substances 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000012300 argon atmosphere Substances 0.000 claims description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000004804 winding Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 abstract description 22
- 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 abstract description 21
- 229910052708 sodium Inorganic materials 0.000 abstract description 21
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 19
- 239000007773 negative electrode material Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000009987 spinning Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 25
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 7
- 239000007833 carbon precursor Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- -1 rare earth compound Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Textile Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of preparation of carbon fiber composite materials and energy storage of sodium ion batteries. The invention discloses a preparation method and application of a soft and hard heterogeneous carbon fiber composite material, which comprises the steps of carbonizing pretreated anthracite at high temperature, dissolving the anthracite and polyacrylonitrile in a dispersing agent, heating in water bath, and adding a reinforcing agent to obtain thick liquid; and injecting the thick liquid into a spinning needle tube, and obtaining the soft and hard heterogeneous carbon fiber composite material through an electrostatic spinning process and a high-temperature pyrolysis process. The soft and hard heterogeneous carbon fiber composite material prepared by the method has the advantages of excellent electronic conductivity and multiplying power performance of soft carbon, high reversible sodium storage capacity of hard carbon, and synergistic sodium storage effect of a coupling soft and hard carbon heterogeneous interface, and is applied to a negative electrode material of a sodium ion battery to show excellent reversible capacity and multiplying power performance. The method has simple process and wide raw material sources, can realize the controllable construction of the soft and hard carbon heterogeneous interface, and is easy to realize the development of mass production of the negative electrode material for the sodium ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of advanced carbon materials and sodium ion battery energy storage, in particular to a controllable preparation method of a soft and hard heterogeneous carbon fiber composite material for a negative electrode of a sodium ion battery.
Technical Field
The lack of lithium resources has led to a continuous rise in the cost of future lithium ion batteries, and the search for an alternative low-cost electrochemical energy storage device has become a problem to be solved. Sodium has abundant reserves (23000 ppm) in the crust, wide distribution and similar physical and chemical properties as lithium, and the working principle and the battery components of a sodium ion battery and a lithium ion battery are similar, so that the sodium ion battery and the lithium ion battery become one of the energy storage technologies for competitive development of countries around the world.
However, due to Na + Radius ratio Li + />The following key scientific and technical problems are still faced with the sodium ion battery: 1) The negative electrode slowly removes the dynamic process of intercalation of sodium ions, inhibit the multiplying power performance of the sodium ion battery; 2) Serious volume change and structural collapse of the negative electrode, and shortening the circulation of the sodium ion batteryThe service life is prolonged; 3) The complex physicochemical process of the cathode has no clear mechanism of sodium storage under the real-time working condition. Therefore, in order to realize the excellent sodium storage kinetics behavior and the cycling stability of the sodium ion battery anode material, research on the sodium storage characteristic and mechanism of the novel sodium storage anode material with high-efficiency electron transmission/ion transfer rate and excellent cycling performance is focused on, and the research is becoming a basic research hotspot in the current sodium ion battery field.
In the sodium ion battery cathode material, the carbon material has the advantages of low sodium storage potential, moderate sodium storage capacity, small volume deformation after sodium intercalation, good cycling stability, abundant reserves, low price, environmental friendliness and the like, and is paid attention to widely. The carbon material can be divided into hard carbon and soft carbon according to the graphitization difficulty, and the single amorphous carbon material has advantages and disadvantages when being used for the sodium storage cathode. Hard carbon (highly disordered) has an amorphous structure, has abundant active sites and high reversible capacity for sodium storage, but lower conductivity and more intrinsic defects lead to low first-turn coulombic efficiency and poor rate capability. Soft carbon (highly ordered) has a high degree of crystallinity compared to hard carbon, rich sp 2 Carbon brings about higher electron conductivity and rate capability, but its carbon layers are regularly arranged and the interlayer space is narrow, resulting in lower sodium storage capacity (typically below 100mA h/g). Anthracite is the carbon source with the lowest cost and highest carbon content in the nature, and anthracite cracked at high temperature is a soft carbon material, and compared with other asphalt carbon sources, the anthracite has high unordered degree below 1600 ℃, the carbon yield is up to 90%, and the theoretical capacity of sodium storage is up to 220mA h/g.
Therefore, based on the advantages of the hard carbon and the soft carbon, how to design the advanced soft and hard heterogeneous carbon composite material, and the organic combination of the two can provide opportunities for developing the carbon-based sodium storage anode material with low cost and high performance, thereby having great significance for commercialization of sodium ion batteries.
In the prior art, a preparation method of a soft and hard carbon composite nano material is disclosed in CN 114516627A. The method utilizes pore-regulating agent to combine with soft and hard carbon source, and prepares the soft and hard carbon composite material through two-step high-temperature reaction. The method prepares the porous structure-enriched and stable physical structure. However, the method needs to undergo two-step high-temperature reaction, the process is complex, and the heating energy consumption cost is high.
In the prior art, a hard carbon-metal oxide-soft carbon composite material as disclosed in CN107240680A, and a preparation method and application thereof. Preparing a hard carbon precursor by using hydrocarbon in a reaction kettle through a hydrothermal method, pre-coating the hard carbon precursor and titanium salt, and placing asphalt in a muffle furnace for low-temperature pyrolysis reaction to obtain a soft carbon precursor; and finally, fully mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain the hard carbon-metal oxide-soft carbon composite material. The composite material prepared by the invention has the advantages of large reversible capacity, high coulomb efficiency for the first charge and discharge, good cycle performance and the like. However, the treatment process of the precursor of soft carbon and hard carbon is complex, and the cost for obtaining the composite material is high.
In the prior art, a preparation method of a hard carbon-soft carbon-fast ion conductor composite material is disclosed in CN 115520851A. According to the invention, the fast ion conductor and the soft carbon material are sequentially coated on the outer layer of the hard carbon doped rare earth compound by a hydrothermal method, so that the hard carbon-soft carbon-fast ion conductor composite material with high specific capacity, high first efficiency and good power performance is prepared. However, the hard carbon precursor of the invention has the defects of complex materials, including rare earth coupling agent and cross-linking agent, difficult material collection and high preparation cost.
Based on the problems, the invention provides an electrostatic spinning method, which utilizes polyacrylonitrile and anthracite to prepare a soft and hard heterogeneous carbon fiber composite material, and then performs a sodium storage performance test. The carbon composite material prepared by the process not only has excellent electrochemical performance of sodium storage, but also has the advantages of simple process, low cost, controllable components and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a soft and hard heterogeneous carbon fiber composite material, which is characterized in that a soft and hard heterogeneous carbon fiber structure composite material is controllably constructed on the same interface through a simple process, and the soft and hard heterogeneous carbon fiber structure composite material has higher specific capacity and excellent cycle stability when being used as a negative electrode material of a sodium ion battery.
A preparation method of a controllable structure of a soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: 2-4g of anthracite is ground uniformly by a ball mill and passes through a 150-mesh screen. Wherein the ball milling rotating speed is 100-300r/min, and the ball milling time is 4-7 h.
S2: and (3) removing metal impurity ions in the S1 product through hydrochloric acid and hydrofluoric acid respectively, washing with water to obtain filtrate which is neutral solution, and finally drying to obtain anthracite powder.
S3: the powder of S2 is placed in a tube furnace, heated to 800-1200 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, and kept at the temperature range of 800-1200 ℃ for 2h.
S4: the anthracite and polyacrylonitrile obtained in the step S3 are dissolved in 24mL of N, N-dimethylformamide according to a certain proportion, water bath is carried out to 60 ℃, and 0.2g of polymethyl methacrylate is added to obtain black liquid with certain concentration.
S5: and adding the liquid into a needle tube, and obtaining the carbon film with a certain thickness through electrostatic spinning.
Preferably, in the step S1, the rotation speed of ball milling is 150-250 r/min, and the ball milling time is 2-5h.
Preferably, the anthracite coal has a particle size in the range of 10-50 μm.
Preferably, in the step S2, the concentration of hydrochloric acid is 10%, the concentration of hydrofluoric acid is 5-10wt.%, the pickling time is about 24 hours, and the water washing solution is neutral.
Preferably, in S3, the carbonization temperature is 1000 ℃.
Preferably, in the step S4, the ratio of anthracite to polyacrylonitrile is 2:5.
Preferably, in the step S5, 6-8mL of the fiber is added into 10mL of disposable medical needle tube, the electrostatic spinning voltage parameter is 18kV, the winding speed is 0.5mL/h, and the collecting distance is 10-15cm.
The carbon fiber composite material prepared by the invention has the structural characteristics of soft carbon and hard carbon, so that the carbon fiber composite material has good electronic conductivity and excellent stability when being used as a negative electrode material of a sodium ion battery, and the controllably constructed carbon fiber interface can cooperatively improve the sodium storage performance.
The invention has the following beneficial effects:
1. according to the invention, anthracite and polyacrylonitrile are used as carbon source precursors, and the carbon anode material of the sodium ion battery with larger interlayer spacing, multiple active sites and rapid ion migration channels is prepared by an electrostatic spinning and high-temperature carbonization process. Compared with the traditional chemical method, the invention is used as a continuous synthesis technology, can realize lower consumption of raw materials and solvents, has lower running cost, only needs one tester in continuous operation for 16 hours, and has simple and convenient equipment and good safety.
2. The invention overcomes the limitation of the traditional synthesis method in preparing the carbon cathode material, proposes an electrostatic spinning strategy to prepare the controllable carbon cathode material, breaks through the problem of low capacity of the traditional anthracite in a sodium ion battery, and can show the discharge specific capacity of 236mA h/g at 0.1A/g.
3. The invention develops a carbon fiber preparation technology with excellent sodium storage performance, which can be synthesized in a large scale from practical benefits, promotes the development of the current sodium ion battery, and deeply researches the key technical problems in the preparation technology of the soft and hard heterogeneous carbon fiber composite material.
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 principles of the invention.
FIG. 1 is an X-ray diffraction analysis chart of the soft and hard heterogeneous carbon fiber composite material prepared in examples 1-3 of the present invention; wherein, the hard carbon fiber is adopted in the embodiment 1, the soft and hard heterogeneous carbon fiber is adopted in the embodiment 2, and the soft carbon anthracite is adopted in the embodiment 3.
Fig. 2 is a scanning electron microscope image of the soft and hard heterogeneous carbon fiber composite material prepared in example 2 of the present invention.
FIG. 3 is a graph showing the performance of the soft and hard heterogeneous carbon fiber composite material prepared in example 2 of the present invention at a current density of 0.1A/g for 100 cycles.
Description of the preferred embodiments
The present invention will be further described with reference to specific examples and drawings, but the present invention is not limited to the following examples.
Example 1
The embodiment discloses a method for controllably constructing a polyacrylonitrile hard carbon fiber composite material, which comprises the following steps:
s1: 2g of polyacrylonitrile is added into 24mL of N, N-dimethylformamide, the temperature of the water bath is raised to 60 ℃, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s2: 8mL of S1 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s3: and (3) putting the product of the step (S2) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 2
In this embodiment, a method for controllably constructing a soft and hard heterogeneous carbon fiber composite material is disclosed:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 3:
in this embodiment, a method for controllably constructing soft carbon anthracite is disclosed:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr
S2: and (3) heating the product in the step (S1) to 1000 ℃ at a heating rate of 5 ℃/min in argon atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery. The method comprises the steps of carrying out a first treatment on the surface of the
The carbon fiber composite materials prepared in the above examples 1 to 3 are respectively hard carbon fibers prepared in example 1, soft and hard heterogeneous carbon fibers prepared in example 2, and soft carbon anthracite prepared in example 3;
for three prepared materials, as can be seen from the X-ray diffraction diagram of fig. 1, the soft and hard heterogeneous carbon fiber prepared in example 2 has two wide and weak diffraction peaks at 2θ=22-26 ℃ and 2θ=43 ℃, and the (002) crystal face and the (001) crystal face of the corresponding graphite show that the carbon fiber with a certain graphitization degree is prepared; compared with the examples 1 and 3, the method has the advantages of high regularity of the carbon layer, larger specific surface area and relatively better rate capability;
in the scanning electron microscope image of the prepared soft and hard heterogeneous carbon fibers, as can be seen from fig. 2, the sample mainly has carbon fibers with different diameters connected into a carbon network.
Example 4:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr
S2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 5:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 6:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 16kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: the obtained spinning fiber is extremely small in quantity and insufficient for carbonization to be used as a negative electrode material of a sodium ion battery.
Example 7:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with the voltage of 20kV, the winding speed of 0.5mL/h and the collecting distance of 10 cm;
s5: the obtained spinning fiber is extremely small in quantity and insufficient for carbonization to be used as a negative electrode material of a sodium ion battery.
Example 8:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 1.0mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 9:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 2.0mL/h and collection distance of 10 cm;
s5: less spun fibers are obtained and the yield is lower.
Example 10:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.8g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.3mL/h and collection distance of 10 cm;
s5: less spun fibers are obtained, the collection rate is too slow, and the loss and the required time of the instrument are more.
Example 11:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 0.6g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
Example 12:
in this embodiment, the method for controllably constructing the soft and hard heterogeneous carbon fiber composite material comprises the following steps:
s1: pulverizing anthracite into powder with particle size of 10-60 μm by ball mill, treating impurity metal ions with hydrochloric acid and hydrofluoric acid respectively, and drying in vacuum oven at 60deg.C for 12 hr;
s2: heating the product in the step S1 to 1000 ℃ in an argon atmosphere at a heating rate of 5 ℃/min, and preserving heat for 2 hours;
s3: 1.0g of the S2 product is added into 24mL of N, N-dimethylformamide and 2g of polyacrylonitrile, the temperature is raised to 60 ℃ in a water bath, 0.2g of polymethyl methacrylate is added, and the mixture is stirred for 2h;
s4: 8mL of S3 sample is taken and added into a disposable sampler, and is spun for 16 hours by an electrostatic spinning instrument with voltage of 18kV, winding speed of 0.5mL/h and collection distance of 10 cm;
s5: and (3) putting the product of the step (S4) into a tubular furnace in high-purity argon atmosphere for heating and carbonizing, wherein the heating mode is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the carbon negative electrode material of the sodium ion battery.
The comparison of the parameters of the different examples described above is summarized as follows (table 1):
TABLE 1 comparison of parameters for the different examples
Example 1 is a comparison sample, experiment example 3 is soft carbon anthracite, examples 2, 4 and 5 explore the influence of different carbonization temperatures on carbon fibers, and the lower temperature is not beneficial to the removal of non-carbon atoms and the formation of carbon fibers, and the higher temperature can damage the structure of the carbon fibers.
Examples 2, 6 and 7 explore the influence of spinning voltage on spinning fibers, and the phenomenon of liquid leakage can occur when the voltage is low, part of the solution does not form carbon cloth, and fibers with high voltage can be randomly spun and cannot be effectively collected.
Examples 2, 8, 9, 10 explored the effect of different spinning rates on collection efficiency, with slower spinning rates collecting less output, which is detrimental to experimental development. Whereas a faster rate results in a lower collection rate.
Examples 2, 11, 12 explore the effect of different proportions of anthracite and polyacrylonitrile on carbon fibers, with too little anthracite reducing the sodium storage capacity and too much anthracite causing caking of the carbon fibers, resulting in a reduction in sodium storage capacity.
The comparison of the performance of the different examples described above is summarized below (table 2):
TABLE 2 comparison of the Performance of the different examples
While there have been described and shown what are at present considered to be the primary examples of the invention, it will be understood by those skilled in the art that various changes, modifications and combinations may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the soft and hard heterogeneous carbon fiber composite material is characterized by comprising the following steps of:
s1: grinding, sieving, pickling, suction filtering and vacuum drying the blocky anthracite to obtain pretreated anthracite;
s2: carbonizing the pretreated anthracite at high temperature in argon atmosphere, cooling the reaction to room temperature, and grinding the product to obtain an anthracite-derived soft carbon material;
s3: dissolving an anthracite derived soft carbon material and polyacrylonitrile in a dispersing agent, and adding an enhancer to obtain black thick liquid;
s4: adding the black thick liquid into a needle tube, and obtaining a carbon fiber precursor through an electrostatic spinning process;
s5: and pyrolyzing the carbon fiber precursor at a high temperature to obtain the target product of the soft and hard heterogeneous carbon fiber composite material.
2. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps:
the pretreatment of the S1 anthracite is as follows: 2-4g of anthracite is selected, and is ground for 4-7 hours by a ball mill with the rotating speed of 100-300r/min, and is sieved by a 150-mesh sieve, and the particle size range of the obtained anthracite is 10-60 mu m; and then pickling the anthracite for 24 hours by hydrochloric acid with the concentration of 10% and hydrofluoric acid with the concentration of 5-10wt.% respectively, removing metal impurity ions in the anthracite, filtering and washing until the filtrate is neutral solution, and finally drying in vacuum to obtain the anthracite powder.
3. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps: the high-temperature carbonization conditions of the S2 anthracite are as follows: in an argon atmosphere, the temperature is raised to 800-1200 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 2 hours at a temperature range of 800-1200 ℃, and the carbonization temperature is preferably 1000 ℃.
4. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps: and the S3 anthracite precursor and polyacrylonitrile are dispersed in N, N-dimethylformamide according to a proportion, and an enhancer polymethyl methacrylate is added after water bath heating to obtain black liquid with a certain concentration.
5. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps: the ratio of the S3 anthracite to the polyacrylonitrile is 2:5, 3:10 and 1:2, the dispersing agent is N, N-dimethylformamide, the dosage is 24mL, the heating in a water bath is carried out at 60 ℃, and 0.2g of polymethyl methacrylate is added as a reinforcing agent.
6. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps: and S4, adding 6-8mL of thick liquid into 10mL of disposable medical needle tube, wherein the electrostatic spinning voltage parameter is 18kV, the winding speed is 0.5mL/h, and the collecting distance is 10-15cm.
7. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to claim 1, wherein the method comprises the following steps: the high-temperature pyrolysis heating condition of the S5 carbon fiber precursor is as follows: in an air atmosphere, the temperature is raised to 250 ℃ at a heating rate of 2 ℃/min, the temperature is kept for 2 hours, and then in an argon atmosphere, the temperature is raised to 800 ℃ at 5 ℃/min, and the temperature is kept for 2 hours.
8. A soft and hard heterogeneous carbon fiber composite material is characterized in that: the soft and hard heterogeneous carbon fiber composite material is prepared by any one of claims 1-7.
9. The method for preparing the soft and hard heterogeneous carbon fiber composite material according to any one of claims 1 to 7 and application of the prepared soft and hard heterogeneous carbon fiber composite material in the field of sodium ion battery energy storage.
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