CN117658099A - Novel pore carbon sphere and preparation method and application thereof - Google Patents
Novel pore carbon sphere and preparation method and application thereof Download PDFInfo
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- CN117658099A CN117658099A CN202311492957.8A CN202311492957A CN117658099A CN 117658099 A CN117658099 A CN 117658099A CN 202311492957 A CN202311492957 A CN 202311492957A CN 117658099 A CN117658099 A CN 117658099A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 239000011148 porous material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 14
- 229910021385 hard carbon Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims 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 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 9
- 108091006146 Channels Proteins 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 238000009831 deintercalation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 108010052164 Sodium Channels Proteins 0.000 description 2
- 102000018674 Sodium Channels Human genes 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 discloses a novel pore carbon sphere and a preparation method and application thereof, and belongs to the technical field of carbon preparation. The method comprises the following steps: (1) Respectively dissolving high molecular polymer in solvent to obtain corresponding inner layer solution and outer layer solution for standby; (2) The inner layer solution and the outer layer solution are subjected to coaxial electrostatic spinning to prepare fiber filaments with a core-shell structure for later use; (3) Adding the fiber filaments into a solvent, mixing, filtering and collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor for later use; (4) And presintering the carbon sphere precursor in an air atmosphere, carbonizing under the protection of inert gas, and finishing treatment to obtain the pore channel carbon sphere. The carbon sphere with the central pore canal structure is prepared by a soft template method, is applied to sodium batteries, and can improve the sodium storage capacity and the multiplying power performance by the special pore canal structure.
Description
Technical Field
The invention relates to the technical field of carbon preparation, in particular to a novel pore carbon sphere and a preparation method and application thereof.
Background
Sodium ion batteries are considered to be an electrochemical system that is well suited for use in large-scale energy storage applications due to the advantages of large sodium resource reserves, low cost, and high safety. And because the radius of the sodium ions is larger than that of the lithium ions, the sodium ions cannot be effectively deintercalated in the graphite cathode. Among all sodium ion battery anode materials, hard carbon is most likely to be put into practical use as a sodium-electricity anode material due to its characteristics of abundant carbon source, low cost, low sodium storage potential, and the like. However, in the practical application process, the hard carbon anode also has the problems of poor rate capability, insufficient long-cycle stability and the like.
Hard carbon is carbon that is difficult to graphitize even at high temperatures above 2500 ℃. The graphitization degree of the hard carbon material is smaller, and the conductivity of the material is lower, so that the rate performance of the battery is poorer. The conventional method is to reduce the hard carbon particle size to shorten the deintercalation path of sodium ions, so as to improve the rate performance. However, the most immediate problem is that the hard carbon particle size is reduced, which brings more specific surface area, resulting in degradation of battery cycle performance.
CN201710195233 discloses a negative electrode material of lithium ion battery carbon sphere, which is prepared by dissolving carbon source in water, hydrothermal reacting, sintering, and doping cobalt element on the surface of carbon sphere. By the scheme of the nano-scale carbon spheres, the multiplying power performance of the hard carbon cathode can not be effectively improved. However, the extra active surface brought by the undersize of the negative electrode only causes the reaction area of the negative electrode SEI film to be larger, consumes more sodium ions, and finally leads to the deterioration of the cycle performance.
With the recent shortage of lithium resources and the price increase of lithium ores, the demand for new low-cost chemical systems is becoming greater. How to solve the problem that the multiplying power performance and the cycle performance of the sodium ion hard carbon cathode become one of the special for the development of sodium ion batteries. There is therefore an urgent need to solve the above problems by means of some new materials or processes.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, a method for preparing a porous carbon sphere with a simple process is provided, and a coaxial electrospinning process is adopted, which includes the following steps:
(1) Respectively dissolving high molecular polymers in solvents to respectively obtain corresponding inner layer solution and outer layer solution;
(2) The inner layer solution and the outer layer solution are subjected to coaxial electrostatic spinning to prepare fiber filaments with a core-shell structure;
(3) Dissolving the core of the fiber yarn with the core-shell structure by a solvent to form a shell layer with a hollow pore canal, filtering and collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor;
(4) And presintering the carbon sphere precursor in an air atmosphere, carbonizing under the protection of inert gas, and finishing treatment to obtain the pore channel carbon sphere.
Preferably, in the step (1), the high molecular polymer in the inner layer solution includes at least one of polymethyl methacrylate, polyethylene, polystyrene, and polyvinyl acetate.
Further preferably, the concentration of the inner layer solution is 7wt.% to 20wt.%.
Preferably, in the step (1), the high molecular polymer in the outer layer solution includes at least one of polyamide, polyacrylonitrile, polyvinyl alcohol and polyvinyl chloride.
Further preferably, the concentration of the outer layer solution is 7wt.% to 30wt.%.
The choice of solvent in step (1) is varied and can be dissolved using organic solvents which are correspondingly suitable in the art. Based on the type of the polymer of the inner and outer layer solutions adopted in the invention, in order to achieve better dissolution effect, it is further preferable that the solvent for dissolving the polymer comprises at least one of N, N-dimethylformamide, dimethylfuran, dimethylsulfoxide and N-methylpyrrolidone.
In addition, in order to improve the uniformity of the finished product, the high molecular polymer should be fully dissolved in the solvent in the preparation process of the inner layer solution and the outer layer solution, preferably, in the step (1), the dissolution is promoted by heating and stirring, the temperature of heating and stirring is 60-100 ℃, the rotating speed is 500-2000 rpm, and the treatment time is 5-60 min.
Preferably, in the step (2), the voltage of the coaxial electrostatic spinning is 10-30 kV, the advancing rate of the inner layer solution is 20-500 mL/min, the advancing rate of the outer layer solution is 25-250 mL/min, and the electrode distance is 15-30 cm.
The advancing rate ratio of the inner and outer layer solutions affects the specific gravity of the high molecular polymer in the outer layer solution, and the larger the specific gravity is, the smaller the pore channels are, the fewer the active surface is, and the better the circulation performance is. In order to obtain a finished product with better performance, it is further preferable that the ratio of the advancing rates of the inner layer solution and the outer layer solution is 0.2-2.0.
The choice of solvent in step (3) is likewise varied and organic solvents correspondingly suitable in the art can be used, preferably in step (3) the solvent comprises at least one of toluene, tetrahydrofuran, xylene, amyl acetate.
The step (3) may be performed by heating and stirring, and preferably, the step (3) is performed by heating and stirring at a temperature of 60 to 100 ℃, a rotational speed of 200 to 1000rpm, and a treatment time of 1 to 5 hours.
The presintering can prevent the high polymer material from being sintered into blocks in the sintering process. Preferably, in the step (4), the temperature of the pre-sintering is 200-400 ℃ and the heat preservation time is 1-5 h.
In carbonization treatment, the high polymer material should be carbonized thoroughly, and the low temperature or short time can cause incomplete carbonization, thereby affecting the conductivity of the material. Preferably, in the step (4), the carbonization temperature is 1200-1500 ℃, and the heat preservation time is 1-6 h.
Based on the technical scheme, the core-shell fiber yarn is formed by adopting two materials of the core shell to carry out electrostatic spinning simultaneously. And adding the core-shell fiber into a solvent for dissolution. Because the shell is insoluble in the solvent and the core is soluble in toluene, the core in the sphere will be dissolved by the solvent leaving a hollow channel.
In a second aspect of the invention, a porous carbon sphere with more sodium storage space and shorter sodium ion deintercalation path is provided, and the porous carbon sphere is prepared by the method of the first aspect of the invention.
In a third aspect of the invention, there is provided the use of the porous carbon spheres of the second aspect of the invention, in particular as a hard carbon material in the preparation of sodium ion batteries.
Based on the technical scheme, the porous carbon sphere prepared by the invention has a porous negative electrode structure, and the sodium ion channel formed by the middle pore passage shortens half of the sodium ion deintercalation path under the same negative electrode particle size, so that the effect of improving the multiplying power performance is achieved. Meanwhile, compared with a small-particle anode material with the same-grade sodium ion deintercalation path, the porous anode structure has smaller specific surface, effectively reduces the active contact surface of the anode and electrolyte, and can play a role in improving the cycle performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a preparation method of a pore canal carbon sphere, which adopts a coaxial electrostatic spinning process in a soft template synthesis mode, and is simple, convenient and quick.
The invention provides a pore canal carbon sphere, which is characterized in that a pore canal which can allow electrolyte to enter is drilled in the center of the carbon sphere, so that more sodium storage space is provided; the pore carbon sphere has a pore type negative electrode structure, and the sodium ion channel formed by the middle pore shortens the sodium ion deintercalation path under the same negative electrode particle size, thereby playing the role of improving the multiplying power performance.
The invention provides application of a pore canal carbon sphere, which is used in a sodium ion battery, and improves the multiplying power performance and the cycle performance of a sodium ion hard carbon negative electrode.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) picture of the porous carbon sphere of example 1.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
A preparation method of a pore canal carbon sphere comprises the following steps:
(1) Polymethyl methacrylate is added into N, N-dimethylformamide, and is heated and stirred at the speed of 500rpm for 60min at the temperature of 60 ℃ to prepare an inner layer solution with the concentration of 10 wt%; adding polyamide into N, N-dimethylformamide, heating and stirring at a speed of 500rpm at 60 ℃ for 60min to prepare an outer layer solution with a concentration of 10wt.% for later use;
(2) Adopting coaxial electrostatic spinning equipment, setting the voltage to be 10kV, the propulsion rate of the inner layer solution to be 50mL/min, and the propulsion rate of the outer layer solution to be 250mL/min, so that the ratio of the propulsion rates of the inner layer solution to the outer layer solution is controlled to be 0.2, and the electrode distance is 30cm; then preparing fiber with a core-shell structure through coaxial electrostatic spinning for standby;
(3) Adding the obtained fiber filaments into excessive toluene, mixing for 1h at 100 ℃ at a rotating speed of 200rpm to dissolve the inner core, filtering by adopting a suction filtration device, collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor for later use;
(4) And (3) pre-sintering the obtained carbon sphere precursor for 5 hours at 200 ℃ under the air atmosphere, then calcining and carbonizing for 6 hours at 1200 ℃ under the protection of nitrogen, and cooling to obtain the pore channel carbon sphere.
The microscopic morphology of the porous carbon spheres was observed by Scanning Electron Microscopy (SEM), and the results are shown in fig. 1. From the figure, it is apparent that the tunnel structure provides a pathway for sodium ion transport.
Example 2
A preparation method of a pore canal carbon sphere comprises the following steps:
(1) Adding polyethylene into dimethylfuran, heating and stirring at a speed of 1000rpm at 80 ℃ for 30min to prepare an inner layer solution with a concentration of 15 wt.%; adding polyacrylonitrile into dimethylfuran, heating and stirring at a speed of 1000rpm at 80 ℃ for 30min to prepare an outer layer solution with a concentration of 20wt.% for later use;
(2) Adopting coaxial electrostatic spinning equipment, setting the voltage to be 20kV, the propulsion rate of the inner layer solution to be 50mL/min, and the propulsion rate of the outer layer solution to be 50mL/min, so that the ratio of the propulsion rates of the inner layer solution to the outer layer solution is controlled to be 1.0, and the electrode distance is 20cm; then preparing fiber with a core-shell structure through coaxial electrostatic spinning for standby;
(3) Adding the obtained fiber filaments into excessive tetrahydrofuran, mixing for 3 hours at the temperature of 80 ℃ and the rotating speed of 600rpm to dissolve the inner core, filtering by adopting a suction filtration device, collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor for later use;
(4) And (3) pre-sintering the obtained carbon sphere precursor for 3 hours at 300 ℃ under the air atmosphere, then calcining and carbonizing for 3 hours at 1300 ℃ under the protection of argon, and cooling to obtain the pore channel carbon sphere.
Example 3
A preparation method of a pore canal carbon sphere comprises the following steps:
(1) Adding polystyrene into N-methyl pyrrolidone, heating and stirring at 1500rpm for 5min at 100 ℃ to prepare an inner layer solution with the concentration of 20 wt.%; adding polyvinyl alcohol into N-methyl pyrrolidone, heating and stirring at 1500rpm for 5min at 100 ℃ to prepare an outer layer solution with the concentration of 30wt.% for later use;
(2) Adopting coaxial electrostatic spinning equipment, setting the voltage to be 30kV, the propulsion rate of the inner layer solution to be 50mL/min, and the propulsion rate of the outer layer solution to be 25mL/min, so that the ratio of the propulsion rates of the inner layer solution to the outer layer solution is controlled to be 2.0, and the electrode distance is 15cm; then preparing fiber with a core-shell structure through coaxial electrostatic spinning for standby;
(3) Adding the obtained fiber filaments into excessive dimethylbenzene, mixing for 5 hours at the temperature of 60 ℃ at the speed of 1000rpm to dissolve the inner core, filtering by adopting a suction filtration device, collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor for later use;
(4) And (3) pre-sintering the obtained carbon sphere precursor for 1h at 400 ℃ under the air atmosphere, then calcining and carbonizing for 1h at 1500 ℃ under the protection of nitrogen, and cooling to obtain the pore channel carbon sphere.
Example 4
The physical parameters of the pore canal carbon sphere prepared by the invention are tested, and the multiplying power performance of the pore canal carbon sphere when the pore canal carbon sphere is applied to sodium ion batteries is researched. Hard carbon commercialized as d50=5.2 μm was used as comparative example 1, and hard carbon commercialized as d50=10.6 μm was used as comparative example 2. The porous carbon spheres of examples 1 to 3 and the hard porous carbon spheres of comparative examples 1 and 2 were preparedCarbon is used as an electrode current collector in a conventional 2016 button cell, in which the positive electrode active material pore carbon sphere or hard carbon is 90.0wt.%, the remainder is 5.0wt.% carbon tube and 5.0wt.% binder, and the negative electrode uses a metallic sodium sheet. The pole pieces prepared in examples 1 to 3 and comparative examples 1 and 2 each had a thickness of 30. Mu.m, and a compacted density of 1.0/cm 3 。
The batteries thus prepared were subjected to respective rate performance tests, and the test results are shown in table 1.
Table 1:
in the table "/" indicates no pore passage.
From the results of the volumetric data, the embodiment provides more sodium storage space through the special pore structure, so that the effect is obviously improved.
From the data of comparative example 1 and example 2, it is clear that the rate performance of the examples is significantly due to the comparative example under the same formulation ratio and the same particle size.
From the capacity and rate data of examples 1 to 3, the capacity and rate performance exhibited a significant increase as the particle size was reduced. While the capacity and rate performance of the comparative example show the opposite trend with decreasing particle size. The magnification and capacity of the illustrated examples are affected by the pore channels more than the particle size.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the pore canal carbon sphere is characterized by adopting a coaxial electrostatic spinning process and comprising the following steps:
(1) Respectively dissolving high molecular polymers in solvents to respectively obtain corresponding inner layer solution and outer layer solution;
(2) The inner layer solution and the outer layer solution are subjected to coaxial electrostatic spinning to prepare fiber filaments with a core-shell structure;
(3) Dissolving the core of the fiber yarn with the core-shell structure by a solvent to form a shell layer with a hollow pore canal, filtering and collecting a filter cake, and drying the filter cake to obtain a carbon sphere precursor;
(4) And presintering the carbon sphere precursor in an air atmosphere, carbonizing under the protection of inert gas, and finishing treatment to obtain the pore channel carbon sphere.
2. The method according to claim 1, characterized in that: in the step (1), the high molecular polymer in the inner layer solution includes at least one of polymethyl methacrylate, polyethylene, polystyrene and polyvinyl acetate; in the outer layer solution, the high molecular polymer comprises at least one of polyamide, polyacrylonitrile, polyvinyl alcohol and polyvinyl chloride.
3. The method according to claim 2, characterized in that: the solvent for dissolving the high molecular polymer comprises at least one of N, N-dimethylformamide, dimethyl furan, dimethyl sulfoxide and N-methylpyrrolidone; the concentration of the inner layer solution is 7wt.% to 20wt.% and the concentration of the outer layer solution is 7wt.% to 30wt.%.
4. The method according to claim 1, characterized in that: in the step (1), the dissolution is promoted by heating and stirring, the temperature of the heating and stirring is 60-100 ℃, the rotating speed is 500-2000 rpm, and the treatment time is 5-60 min.
5. The method according to claim 1, characterized in that: in the step (2), the voltage of the coaxial electrostatic spinning is 10-30 kV, the advancing rate of the inner layer solution is 20-500 mL/min, the advancing rate of the outer layer solution is 25-250 mL/min, the ratio of the advancing rates of the inner layer solution and the outer layer solution is 0.2-2.0, and the electrode distance is 15-30 cm.
6. The method according to claim 1, characterized in that: in the step (3), the solvent comprises at least one of toluene, tetrahydrofuran, xylene and amyl acetate.
7. The method according to claim 1, characterized in that: and (3) mixing by heating and stirring, wherein the temperature of the heating and stirring is 60-100 ℃, the rotating speed is 200-1000 rpm, and the treatment time is 1-5 h.
8. The method according to claim 1, characterized in that: in the step (4), the presintering temperature is 200-400 ℃ and the heat preservation time is 1-5 h; the carbonization temperature is 1200-1500 ℃, and the heat preservation time is 1-6 h.
9. The utility model provides a pore carbon sphere which characterized in that: the method according to any one of claims 1 to 8.
10. Use of the porous carbon sphere of claim 9, wherein: the application of the pore canal carbon sphere as a hard carbon material in the preparation of sodium ion batteries.
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