CN114864928A - Carbon material with enlarged accessible subsurface layer and preparation method thereof - Google Patents
Carbon material with enlarged accessible subsurface layer and preparation method thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002344 surface layer Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 25
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005411 Van der Waals force Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 plates, in particular to a carbon material with an enlarged accessible sub-surface layer and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of electrode plates, and particularly relates to a carbon material with an enlarged accessible sub-surface layer and a preparation method thereof.
Background
Carbon materials have been widely used as negative electrode host materials for potassium ion batteries because of their high conductivity, flexible bulk structure and low cost. The carbon negative electrode material mainly has two ways of realizing potassium ion storage in the charging and discharging processes: namely a high voltage area capacitance controlled adsorption process (capacitance contribution) and a low voltage area diffusion controlled embedding process (diffusion contribution); the capacitance contribution can provide an additional potassium storage site and simultaneously ensure the rapid transfer of potassium ions under high current density, and has important significance for improving the capacity and the power density of the whole battery system.
At present, the main strategy for improving the capacitance contribution rate of the carbon material is to increase the specific surface area of the carbon material, and the effective contact area of electrolyte ions and an electrode active material is enlarged by utilizing the increase of the specific surface area of the carbon material; or the structural defects are increased by increasing the doping concentration of the heteroatoms. However, both of these strategies have certain drawbacks, and the increase of the specific surface area leads to excessive consumption of the electrolyte solution to generate excessive solid electrolyte interface layer (SEI), resulting in low initial coulombic efficiency; the increase of the doping concentration of the heteroatom destroys the conjugated pi system of the carbon structure, is not favorable for rapid electronic conductance and affects the conductivity. How to improve the capacitance contribution rate of the carbon material and ensure that the initial coulombic efficiency and the conductivity of the carbon material are not affected is always a key research direction of researchers.
Disclosure of Invention
Aiming at the technical problem that the improvement strategy of the capacitance contribution rate of the carbon material in the prior art can reduce the initial coulombic efficiency and the electric conductivity of the carbon material, the invention provides the carbon material with the enlarged accessible sub-surface layer and the preparation method thereof.
The preparation method of the carbon material specifically comprises the following steps:
s1: dissolving a carbon source in water to obtain a carbon source solution; dissolving isopropanol in a DMF (N, N-dimethylformamide) solvent, adding a sulfur source, uniformly mixing to obtain a sulfur source solution, and uniformly mixing the carbon source solution and the sulfur source solution to obtain a reaction solution, wherein the mass ratio of the carbon source to the sulfur source is (1-5): 10-30 parts;
s2: preserving the temperature of the reaction solution obtained in the step S1 at 160-180 ℃ for 5-7 h, separating the obtained solid matter, washing and drying to obtain an intermediate product;
s3: and (3) uniformly heating the intermediate product obtained in the step (S2) to 500-1000 ℃ in an inert atmosphere, carrying out pyrolysis reaction at a constant temperature, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Compared with the prior art, the carbon material with the enlarged accessible subsurface layer is prepared by adopting a high-temperature hydrothermal molten salt method, wherein isopropanol is used as a medium to reduce the nucleation driving force of carbon atoms, so that a certain amount of carbon atoms are crystallized and precipitated, the sufficient contact between a sulfur source and the carbon source is ensured, the surface diffusion degree between the carbon source and the carbon source is improved, the contacted carbon source and the sulfur source are pyrolyzed and reacted at 500-1000 ℃ to gradually form a C-S-S-C bond, the generated C-S-S-C bond has a bond angle close to 90 degrees, and the surface layer of the carbon material is expanded outwards by strong tensile stress which can be generated; the decomposition process of the carbon source at high temperature weakens Van der Waals force between carbon atoms of the subsurface layer, and the weakening effect of the Van der Waals force can generate synergistic action with the tensile stress action of a C-S-S-C bond angle to jointly promote the further expansion of the subsurface layer spacing. The whole preparation process is safe and reliable, simple and easy to operate, and can generate C-S-S-C bonds to the maximum extent to obtain the carbon material with an enlarged accessible sub-surface layer structure, and the obtained carbon material can improve the capacitance contribution rate and simultaneously cannot influence the ICE and the conductivity of the carbon material.
Preferably, the carbon source is at least one of polyacrylonitrile, melamine, sucrose, glucose, and dopamine.
Preferably, the sulfur source is at least one of thioacetamide, thiourea and dimethyl sulfoxide.
Preferably, the volume of the isopropanol used for each 0.1-0.5 g of the carbon source is 10-30 ml.
Preferably, the volume ratio of isopropanol to DMF is 1-3: 3 to 6.
Preferably, the sulfur source is added into S1 and then the mixture is stirred for 1 to 3 hours at a speed of 400 to 500r/min and is uniformly mixed; the carbon source solution and the sulfur source solution are uniformly mixed in the following mode: slowly adding the carbon source solution into the sulfur source solution under the stirring state, wherein the stirring speed is 650-750 r/min, and continuously stirring for 10-30 min after the addition is finished.
Preferably, the solid material in S2 is washed with absolute ethanol and then with deionized water.
Preferably, the inert atmosphere in S3 is a rare gas atmosphere or a nitrogen atmosphere.
Preferably, the constant-speed heating rate in S3 is 2-5 ℃/min, and the pyrolysis reaction time is 3-5 h.
Embodiments of the present invention also provide a carbon material having an enlarged accessible subsurface layer, which is prepared by the above method for preparing a carbon material having an enlarged accessible subsurface layer.
The embodiment of the invention also provides the carbon material with the enlarged accessible sub-surface layer prepared by the preparation method and the application of the carbon material in preparing the negative electrode of the ion battery.
Drawings
FIG. 1 is a schematic representation of the principle of the synergy of tensile stress and van der Waals forces in a carbon material having an enlarged accessible subsurface layer to enlarge the subsurface interlayer distance provided by the present invention;
FIG. 2 is a comparison of the interlayer distances of the sub-surface layers in the carbon materials prepared in examples 1 to 3 and comparative examples 1 to 4;
FIG. 3 is a comparison of the capacitance contribution ratios of the carbon materials prepared in examples 1 to 3 and comparative examples 1 to 4 at a scanning speed of 2 mV/s;
FIG. 4 is a comparison of initial coulombic efficiencies of carbon materials prepared in examples 1 to 3 and comparative examples 1 to 4.
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.
In the cathode main body material of the potassium ion battery, the carbon material is more and more popular due to the characteristics of high conductivity, flexible bulk phase structure and low cost. The carbon negative electrode material mainly has two ways of realizing potassium ion storage in the charge and discharge process of the ion battery: namely a high voltage area capacitance controlled adsorption process (capacitance contribution) and a low voltage area diffusion controlled embedding process (diffusion contribution). The capacitance contribution of the high voltage region can provide an additional potassium storage site and simultaneously ensure the rapid transfer of potassium ions under high current density, and is significant for improving the capacity and the power density of a battery system.
In the prior art, two main strategies for improving the capacitance contribution rate of the carbon material are provided, one of the two strategies is to increase the specific surface area of the carbon material, and the increase of the specific surface area is utilized to enlarge the contact area between electrolyte ions and an electrode active material, so that more ions are adsorbed and stored; and secondly, the structural defects of the carbon material are increased by improving the doping degree of the heteroatom. Both strategies have certain drawbacks: the specific surface area is increased, the area of the solid electrolyte interface layer is also increased, the amount of electrolyte used in the process of generating the solid electrolyte interface layer is also increased, more electrolyte is lost, and meanwhile, the low initial coulombic efficiency is caused by the excessive solid electrolyte interface layer; high-concentration heteroatom doping can also damage a conjugated pi system of a carbon structure, reduce the conductance rate of electrons and influence the conductivity of the carbon material. How to improve the capacitance contribution of the carbon material and avoid influencing the initial coulombic efficiency and the electric conductivity of the carbon material is always a technical problem.
In view of the above technical problems, the inventors have found through research that, during high current density discharge, the accessible subsurface layer thickness (L) of the carbon electrode material has a positive linear correlation with the diffusion coefficient (D) of potassium ions, and a higher capacitance contribution capacity can be obtained by expanding the interlayer spacing of the subsurface region, and the initial coulombic efficiency and the electrical conductivity of the carbon material are not affected. Based on this, the inventors further investigated methods for increasing the accessible sub-surface layer spacing of carbon electrode materials, and found that it is an effective way to form a chemical bond with a specific structure on the carbon substrate surface and expand the sub-surface layer spacing of the carbon material by using the chemical bond to generate an outward tensile stress. On the basis of these discoveries, a method for preparing a carbon material with an enlarged accessible subsurface layer is finally obtained, which comprises the following steps:
s1: dissolving a carbon source in water to obtain a carbon source solution; dissolving isopropanol in a DMF (N, N-dimethylformamide) solvent, adding a sulfur source, uniformly mixing to obtain a sulfur source solution, and uniformly mixing a carbon source solution and the sulfur source solution to obtain a reaction solution, wherein the mass ratio of the carbon source to the sulfur source is (1-5): 10-30;
s2: preserving the temperature of the reaction solution obtained in the step S1 at 160-180 ℃ for 5-7 h, separating the obtained solid matter, washing and drying to obtain an intermediate product;
s3: and (3) heating the intermediate product obtained in the step (S2) to 500-1000 ℃ at a constant speed in an inert atmosphere, carrying out pyrolysis reaction at a constant temperature, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
In the preparation method, the sulfur source and the carbon source are continuously pyrolyzed at the high temperature of 500-1000 ℃, and the van der Waals force between carbon atoms in the carbon source is weakened in the process, so that conditions are established for expanding the interlayer distance of the subsurface of the carbon material; and along with the proceeding of the pyrolysis reaction, the pyrolyzed sulfur source and carbon source can also react to form a C-S-S-C bond on the surface of the carbon matrix, and the bond angle of the C-S-S-C bond close to 90 degrees can generate strong outward tensile stress to promote the surface layer of the carbon to continuously expand outward; isopropanol in the reaction solution can be used as a medium to reduce nucleation driving force of carbon atoms in a carbon source, so that a certain amount of carbon atoms in the carbon source are crystallized and separated out, the pyrolysis reaction of the carbon source and a sulfur source is ensured to occur on the surface of the carbon source, the carbon source and the sulfur source are mixed in the solution under a specific condition, the earlier mixing time is favorable for the crystallization and separation of the carbon atoms, the sufficient contact and surface diffusion of the carbon source and the sulfur source can also be ensured, thermodynamic conditions are provided for the formation of C-S-S-C bonds, the generation amount of the C-S-S-C bonds is increased, the whole process is safe and reliable, easy to operate and control, and the accessible sub-surface layer of the carbon material can be enlarged to the greatest extent.
The invention is further illustrated below in the following examples.
Example 1
This example provides a carbon material with an enlarged accessible subsurface layer, and the method for preparing the carbon material specifically includes the following steps:
s1: dissolving 0.1g of polyacrylonitrile in 3ml of deionized water by ultrasonic dispersion to obtain a polyacrylonitrile solution; dissolving 30ml of isopropanol in 50ml of DMF, adding 2.0g of thioacetamide, stirring at 450r/min for 1h to obtain a thioacetamide solution, increasing the rotating speed to 700r/min, adding the polyacrylonitrile solution, and continuously stirring for 20min to obtain a reaction solution;
s2: transferring the reaction solution obtained in the step S1 into a high-pressure reaction kettle, carrying out heat preservation reaction for 6 hours at the temperature of 180 ℃, separating the obtained solid substance, washing with anhydrous alcohol and deionized water in sequence, and drying to obtain an intermediate product;
s3: and heating the intermediate product obtained in the step S2 to 600 ℃ at a heating rate of 3 ℃/min under Ar atmosphere, preserving heat, reacting for 3h, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Example 2
This example provides a carbon material with an enlarged accessible subsurface layer, and the method for preparing the carbon material specifically includes the following steps:
s1: dissolving 0.1g of melamine in 3ml of deionized water by rapid stirring to obtain a melamine solution; dissolving 30ml of isopropanol in 50ml of DMF solvent, adding 2.0g of thiourea, stirring at 450r/min for 1h to obtain a thiourea solution, increasing the rotating speed to 700r/min, adding the melamine solution, and continuously stirring for 20min to obtain a reaction solution;
s2: transferring the reaction solution obtained in the step S1 into a high-pressure reaction kettle, carrying out heat preservation reaction for 6 hours at the temperature of 180 ℃, separating the obtained solid substance, washing with anhydrous alcohol and deionized water in sequence, and drying to obtain an intermediate product;
s3: and heating the intermediate product obtained in the step S2 to 700 ℃ at a heating rate of 3 ℃/min under Ar atmosphere, preserving heat, reacting for 3h, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Example 3
This example provides a carbon material with an enlarged accessible subsurface layer, and the method for preparing the carbon material specifically includes the following steps:
s1: dissolving 0.05g of sucrose and 0.05g of dopamine in 3ml of deionized water to obtain a mixed solution of sucrose and dopamine; dissolving 30ml of isopropanol in 50ml of DMF solvent, adding 2.0g of dimethyl sulfoxide, stirring at 450r/min for 1h to obtain a dimethyl sulfoxide solution, increasing the rotating speed to 700r/min, adding a mixed solution of sucrose and dopamine, and continuously stirring for 20min to obtain a reaction solution;
s2: transferring the reaction solution obtained in the step S1 into a high-pressure reaction kettle, carrying out heat preservation reaction for 6 hours at the temperature of 180 ℃, separating the obtained solid substance, washing with anhydrous alcohol and deionized water in sequence, and drying to obtain an intermediate product;
s3: and heating the intermediate product obtained in the step S2 to 800 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, preserving heat, reacting for 3 hours, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Example 4
The present embodiment provides an electrode plate, and a negative electrode material of the electrode plate is the carbon material prepared in any one of embodiments 1 to 3.
Comparative example 1
The present comparative example provides a carbon material doped with sulfur atoms, the carbon material prepared by the method comprising:
0.1g of polyacrylonitrile was directly attached to H 2 And (3) heating to 700 ℃ at a heating rate of 3 ℃/min in the S atmosphere, and keeping the temperature for 3 hours to obtain the carbon material doped with sulfur atoms.
Comparative example 2
The present comparative example provides a carbon material having an enlarged accessible subsurface layer, the carbon material prepared by a method comprising the steps of:
s1: weighing 0.1g of polyacrylonitrile, and dissolving in 3ml of deionized water to obtain a polyacrylonitrile solution; dissolving 30ml of isopropanol in 50ml of DMF solvent, adding 2.0g of thioacetamide, stirring at 450r/min for 1h to obtain a thioacetamide solution, increasing the rotating speed to 700r/min, adding the polyacrylonitrile solution, and continuously stirring for 20min to obtain a reaction solution;
s2: transferring the reaction solution obtained in the step S1 to a high-pressure reaction kettle, carrying out heat preservation reaction for 3 hours at 180 ℃, separating the obtained solid substance, washing with absolute alcohol and deionized water in sequence, and drying to obtain an intermediate product;
s3: and heating the intermediate product obtained in the step S2 to 700 ℃ at a heating rate of 3 ℃/min under Ar atmosphere, preserving heat, reacting for 3h, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Comparative example 3
The present comparative example provides a carbon material having an enlarged accessible subsurface layer, the carbon material prepared by a method comprising the steps of:
s1: weighing 0.1g of polyacrylonitrile, and dissolving in 3ml of deionized water to obtain a polyacrylonitrile solution; dissolving 30ml of isopropanol in 50ml of DMF solvent, adding 2.0g of thioacetamide, stirring at 450r/min for 1h to obtain a thioacetamide solution, increasing the rotating speed to 700r/min, adding the polyacrylonitrile solution, and continuously stirring for 20min to obtain a reaction solution;
s2: transferring the mixed solution obtained in the step S1 to a high-pressure reaction kettle, reacting for 8 hours at a constant temperature of 180 ℃, separating the obtained solid substance, washing with anhydrous alcohol and deionized water in sequence, and drying to obtain an intermediate product;
s3: and heating the intermediate product obtained in the step S2 to 700 ℃ at a heating rate of 3 ℃/min under Ar atmosphere, preserving heat, reacting for 3h, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
Comparative example 4
The present comparative example provides a carbon material having an enlarged accessible subsurface layer, the carbon material prepared by a method comprising the steps of:
s1: 0.1g of polyacrylonitrile was dissolved in 3ml of N, N-dimethylformamide under a water bath condition of 50 ℃;
s2: dissolving 3ml of glycerol and 30ml of isopropanol in 50ml of polytetrafluoroethylene, stirring for 1h at 450r/min, increasing the rotating speed to 700r/min, adding the substance obtained in S1, and continuously stirring for 20min to obtain a mixed solution;
s3: sealing the mixed solution obtained in the step 2, filling the mixed solution into a reaction kettle, carrying out heat preservation reaction for 6 hours at the constant temperature of 180 ℃, washing the obtained precipitate with absolute ethyl alcohol and deionized water, and drying to obtain a crude product;
s4: and heating the crude product obtained in the step S3 to 700 ℃ at a heating rate of 3 ℃/min in an Ar atmosphere, and preserving heat for 3h to obtain the carbon material with the enlarged accessible subsurface layer.
Example of detection
The principle of tensile stress and van der waals forces in combination to extend the interlayer distance of a subsurface is shown in fig. 1.
The results of testing the sub-surface interlayer distances in the carbon materials prepared in examples 1-3 and comparative examples 1-4 are shown in FIG. 2. As can be seen from FIG. 2, the sub-surface interlayer distances of the carbon materials prepared in examples 1-3 of the present invention are significantly higher than those of the carbon materials prepared in comparative examples 1-4, and the products obtained when the temperature is maintained at 700 ℃ for 3 hours have the largest sub-surface layer distance.
The comparison graph of the capacitance contribution of the carbon materials prepared in the examples 1 to 3 and the comparative examples 1 to 4 of the present invention at the sweep rate of 2mV/s is shown in FIG. 3, and it can be seen from FIG. 3 that the capacitance contribution rate of the carbon materials prepared in the examples 1 to 3 of the present invention under the same condition is significantly higher than that of the carbon materials prepared in the comparative examples 1 to 4.
The ICE performance of the carbon materials prepared in the examples 1-3 and the comparative examples 1-4 of the present invention is shown in Table 3. it can be seen from FIG. 3 that the ICE performance of the carbon materials prepared in the examples 1-3 of the present invention is significantly higher than that of the carbon materials prepared in the comparative examples 1-4.
The carbon materials prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention have C-S-C bond contents shown in Table 1:
TABLE 1C-S-C bond content
As can be seen from the data in Table 1, the carbon materials obtained in examples 1 to 3 of the present invention have higher C-S-C bond contents than those obtained in comparative examples 1 to 4.
The electrical conductivity of the carbon materials prepared in examples 1 to 3 of the present invention and comparative examples 1 to 4 is shown in Table 2:
TABLE 2 conductivity
| Material | Conductivity (s/cm) |
| Example 1 | 1.57815 |
| Example 2 | 1.76834 |
| Example 3 | 1.66625 |
| Comparative example 1 | 1.33824 |
| Comparative example 2 | 1.46874 |
| Comparative example 3 | 1.49826 |
| Comparative example 4 | 1.39924 |
As can be seen from the data in Table 2, the electrical conductivity of the carbon materials prepared in examples 1 to 3 of the present invention is significantly higher than that of the carbon materials prepared in comparative examples 1 to 4.
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 (10)
1. A method for preparing a carbon material having an enlarged accessible subsurface layer, comprising the steps of:
s1: dissolving a carbon source in water to obtain a carbon source solution; dissolving isopropanol in DMF, adding a sulfur source, uniformly mixing to obtain a sulfur source solution, and uniformly mixing the carbon source solution and the sulfur source solution to obtain a reaction solution; wherein the mass ratio of the carbon source to the sulfur source is 1-5: 10-30;
s2: preserving the temperature of the reaction solution at 160-180 ℃ for 5-7 h, separating the obtained solid matter, washing and drying the solid matter to obtain an intermediate product;
s3: and (3) uniformly heating the intermediate product to 500-1000 ℃ in an inert atmosphere, carrying out a pyrolysis reaction at a constant temperature, and naturally cooling to room temperature to obtain the carbon material with the enlarged accessible subsurface layer.
2. The method of producing a carbon material having an enlarged accessible subsurface layer as claimed in claim 1 wherein the carbon source is at least one of polyacrylonitrile, melamine, glucose and dopamine.
3. The method of producing a carbon material having an enlarged accessible subsurface layer according to claim 1, wherein the sulfur source is at least one of thioacetamide, thiourea and dimethyl sulfoxide.
4. The method of claim 1, wherein the volume of isopropyl alcohol is 10-30 ml per 0.1-0.5 g of the carbon source.
5. The method of preparing a carbon material having an enlarged accessible subsurface layer according to claim 1, wherein the volume ratio of isopropanol to DMF is 1 to 3: 3 to 6.
6. The method for producing a carbon material with an enlarged accessible subsurface layer according to claim 1, wherein the sulfur source is added in S1 and then the mixture is stirred at 400 to 500r/min for 1 to 3 hours to mix uniformly; and/or
The carbon source solution and the sulfur source solution are uniformly mixed in the following mode: and adding the carbon source solution into the sulfur source solution under the stirring state, wherein the stirring speed is 650-750 r/min, and continuously stirring for 10-30 min after the addition is finished.
7. The method of claim 1, wherein the solid material in S2 is washed with absolute ethanol followed by deionized water.
8. A method of producing a carbon material having an enlarged accessible sub-surface layer according to claim 1, wherein: in S3, the constant-speed heating rate is 2-5 ℃/min, and the pyrolysis reaction time is 3-5 h.
9. A carbon material having an enlarged accessible subsurface layer, characterized in that it is produced by the method for producing a carbon material having an enlarged accessible subsurface layer according to any one of claims 1 to 8.
10. Use of the carbon material with an enlarged accessible sub-surface layer according to claim 9 for the preparation of an ion battery negative electrode.
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