CN111441107A - Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method - Google Patents
Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method Download PDFInfo
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- 238000009987 spinning Methods 0.000 title claims abstract description 75
- 239000007772 electrode material Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 39
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 34
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 22
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 17
- 239000002086 nanomaterial Substances 0.000 claims description 57
- 239000000835 fiber Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000002070 nanowire Substances 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
- 238000005245 sintering Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- -1 transition metal nitride Chemical class 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002657 fibrous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000002042 Silver nanowire Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 spinning solution for preparing a carbon fiber material, which comprises the following components: polyvinylpyrrolidone, glacial acetic acid, tetraethyl silicate, tetrabutyl titanate and organic solvents. On the basis of the above, the invention also discloses a flexible electrode material and a preparation method of the flexible electrode material. The flexible electrode material prepared by the spinning solution has a hollow structure, and can realize excellent mechanical property and excellent electrochemical property.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a spinning solution for preparing a carbon fiber material, a flexible electrode material and a preparation method.
Background
In the field of electrode material preparation, the existing carbon fiber material preparation process is realized by sintering organic polymer fibers with extremely high carbon content, the prepared carbon fiber material has low surface polarity and few surface functional groups, is mostly of a solid structure and is mostly represented as a superhard material, and more importantly, the carbon fiber material of the solid structure cannot ensure the complete infiltration of electrolyte, so that the application of the carbon fiber material in an energy storage system is hindered.
At present, in order to realize functionalization of carbon fiber materials, modification of functional groups or secondary loading of other functional active substances on the surface of prepared carbon fiber materials is required. This complicates the practical implementation of carbon fiber materials and renders it impractical to develop more and better in energy storage systems.
Disclosure of Invention
The invention aims to provide at least a spinning solution for preparing a carbon fiber material, a flexible electrode material and a preparation method. The flexible electrode material prepared by the spinning solution has a hollow structure, and can realize excellent mechanical property and excellent electrochemical property.
The invention is realized by the following technical scheme:
first aspect of the invention
A first aspect of the present invention provides a spinning dope for preparing a carbon fiber material, the spinning dope comprising: polyvinylpyrrolidone, a catalyst, tetraethyl silicate, tetrabutyl titanate and an organic solvent. Wherein the catalyst is glacial acetic acid.
In some embodiments, the spinning dope comprises: 5-15 parts of polyvinylpyrrolidone; 5-15 parts of catalyst; tetraethyl silicate, 15-25 parts by weight; 2-8 parts of tetrabutyl titanate; 40-60 parts of organic solvent.
In some embodiments, the spinning dope comprises: 9-11 parts of polyvinylpyrrolidone; 9-11 parts of catalyst; tetraethyl silicate, 18-22 parts by weight; 4-6 parts of tetrabutyl titanate; 50-60 parts of organic solvent.
In some embodiments, the spinning dope further comprises nanomaterials comprising at least one of one-dimensional nanomaterials and two-dimensional nanomaterials; the addition amount of the nano material is 0.1-1 part by weight based on 100 parts by weight of the spinning solution.
In some embodiments, the one-dimensional nanomaterial includes at least one of a carbon nanotube and a metal nanowire; the metal nanowires are VIII, IB and IIIA group metal nanowires. Preferably, the metal nanowires may be gold, silver, copper, nickel, platinum, palladium, aluminum nanowires.
In some embodiments, the two-dimensional nanomaterial includes at least one of graphene oxide, a two-dimensional transition metal carbide, and a two-dimensional transition metal nitride.
In some embodiments, the organic solvent includes at least one of absolute ethanol, N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.
Second aspect of the invention
In a second aspect of the invention there is provided a flexible electrode material prepared from a spinning dope according to the first aspect of the invention.
Since the fiber material prepared by the spinning solution of the first aspect can generate a pore channel structure after spinning, the flexible electrode material of the second aspect is a lithium-philic three-dimensional flexible electrode material with a hollow structure.
Third aspect of the invention
On the basis of the first aspect and the second aspect, the third aspect of the present invention provides a method for preparing a flexible electrode material, including:
adding polyvinylpyrrolidone and glacial acetic acid into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material.
Fourth aspect of the invention
On the basis of the third aspect, the fourth aspect of the present invention provides a preferred preparation method of a flexible electrode material, comprising:
adding polyvinylpyrrolidone, glacial acetic acid and nano materials into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material.
The embodiment of the invention has at least the following beneficial effects:
1. the flexible electrode material prepared in some embodiments of the invention has a hollow structure, can ensure complete infiltration of electrolyte, and has excellent electrochemical performance.
2. According to the flexible electrode material prepared by some embodiments of the invention, the nanometer material is added, and the flexibility of the nanometer material is designed by changing the content of the one-dimensional or two-dimensional nanometer material in the nanometer material, so that the mechanical property of the fiber in the flexible electrode material is improved.
3. The prior art needs to further perform functional group modification or secondary loading of other functional active substances on the surface of the prepared carbon fiber material, but some embodiments of the invention do not have the step, so that the process flow for preparing the flexible electrode material is reduced.
Drawings
FIG. 1 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material with carbon nanotubes added in example 1;
FIG. 2 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material of example 8 with graphene oxide added;
FIG. 3 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material of example 9 with titanium carbide added;
FIG. 4 is a schematic cross-sectional view of the carbon fiber material in the electrode material of comparative example 1 in the prior art;
FIG. 5 is a graph showing the results of electrochemical measurements on the flexible electrode material prepared in example 1;
FIG. 6 is a graph showing the results of electrochemical measurements on the flexible electrode material prepared in example 8;
FIG. 7 is a graph showing the results of electrochemical measurements on the flexible electrode material prepared in example 9;
fig. 8 is a graph showing the results of comparison of electrochemical performance tests of the electrodes prepared in examples 1 and 11.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
First aspect of the invention
A first aspect of the present invention provides a spinning dope for preparing a carbon fiber material, comprising:
polyvinylpyrrolidone, glacial acetic acid, tetraethyl silicate, tetrabutyl titanate and organic solvents.
Wherein the polyvinylpyrrolidone is used for providing a carbon source for the fiber material;
the organic solvent is used to uniformly disperse the component substances, and preferably includes at least one of absolute ethanol, N-methylpyrrolidone, dimethylformamide, and dimethylacetamide. The organic solvent can also be halogenated hydrocarbon solvent, alcohols, amines, nitroalkane, low molecular fatty acid and the like;
the catalyst plays a catalytic role, provides an acidic environment for hydrolysis of tetraethyl silicate and tetrabutyl titanate, and accelerates hydrolysis of tetraethyl silicate and tetrabutyl titanate; the catalyst is preferably glacial acetic acid, and has proper acidity and convenient use amount regulation. Glacial acetic acid can be replaced by acidic substances such as hydrochloric acid, sulfuric acid and the like, but the use amount of the latter two acids needs to be adjusted because the acidity is stronger.
Tetraethyl silicate as SiO2With tetrabutyl titanate as the TiO source2The source of (1).
The working principle of the spinning solution is as follows: the raw materials of hydrolyzable tetraethyl silicate and tetrabutyl titanate are added into the spinning solution, and the fiber material produced by spinning the spinning solution can generate a pore channel structure in the fiber through the hydrolysis process of the two substances. Wherein, the generation principle of the pore channel structure is as follows: tetraethyl silicate and tetrabutyl titanate are easy to hydrolyze in water under acidic conditions, and the hydrolysis of the tetraethyl silicate and the tetrabutyl titanate can diffuse from the center of the fiber to the periphery, so that the fiber generates a porous structure. And due to the introduction of the nano flexible material, the overall flexibility of the fiber is further improved.
Therefore, the carbon fiber material prepared by using the spinning solution and the flexible motor prepared by using the carbon fiber material have a hollow structure, and can realize excellent electrochemical performance.
Further, the spinning solution comprises: 5-15 parts of polyvinylpyrrolidone; 5-15 parts of catalyst; tetraethyl silicate, 15-25 parts by weight; 2-8 parts of tetrabutyl titanate; 40-60 parts of organic solvent.
More preferably, the spinning solution comprises: 9-11 parts of polyvinylpyrrolidone; 9-11 parts of catalyst; tetraethyl silicate, 18-22 parts by weight; 4-6 parts of tetrabutyl titanate; 50-60 parts of organic solvent.
The optimal content of each substance of the spinning solution is as follows: 10 parts by weight of polyvinylpyrrolidone; 10 parts by weight of a catalyst; 20 parts by weight of tetraethyl silicate; 5 parts by weight of tetrabutyl titanate; when the organic solvent is 55 parts by weight, the spinning solution fiber has relatively better effect.
Further, the spinning solution further includes a nanomaterial including at least one of a one-dimensional nanomaterial and a two-dimensional nanomaterial.
The nano material has excellent mechanical property, so that the fiber material prepared by the spinning solution has good flexibility, and further preparation of the flexible electrode material is realized. When the spinning solution is prepared, the flexibility of the nano material can be changed by adding different contents of one-dimensional or two-dimensional nano materials or the combination of the one-dimensional or two-dimensional nano materials, so that the mechanical property of the fiber can be improved. Preferably, the spinning solution further comprises a nanomaterial comprising at least one of a one-dimensional nanomaterial and a two-dimensional nanomaterial; the addition amount of the nano material is 0.1-1 part by weight based on 100 parts by weight of the spinning solution. Preferably, the nano material is added in an amount of 0.1-0.5 parts by weight based on 100 parts by weight of the spinning solution, specifically, 0.1-0.5 parts by weight of the nano material is additionally added to 100 parts by weight of the spinning solution.
Preferably, in the spinning solution, the one-dimensional nanomaterial includes at least one of carbon nanotubes and metal nanowires.
The metal nanowires are VIII, IB and IIIA group metal nanowires. Preferably, the metal nanowire is a metal nanowire containing gold, silver, copper, nickel, platinum, palladium and aluminum, so that the prepared carbon fiber material has good mechanical properties.
Preferably, in the spinning solution, the two-dimensional nanomaterial includes at least one of graphene oxide, a two-dimensional transition metal carbide, and a two-dimensional transition metal nitride.
The preferable one-dimensional nano material, two-dimensional nano material and mixture thereof are added, and the mechanical property of the whole prepared spinning fiber can be improved through the flexibility of the one-dimensional or two-dimensional nano material.
Second aspect of the invention
In a second aspect of the invention there is provided a flexible electrode material prepared from a spinning dope according to the first aspect of the invention.
Since the fiber material prepared by the spinning solution of the first aspect can generate a pore channel structure after spinning, the flexible electrode material of the second aspect is a lithium-philic three-dimensional flexible electrode material with a hollow structure.
Third aspect of the invention
On the basis of the first aspect and the second aspect, the third aspect of the present invention provides a method for preparing a flexible electrode material, including:
adding polyvinylpyrrolidone and glacial acetic acid into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material.
In the preparation method, the tetraethyl silicate and the tetrabutyl titanate are easy to hydrolyze in water under an acidic condition, and the hydrolysis of the tetraethyl silicate and the tetrabutyl titanate can diffuse from the center of the fiber to the periphery, so that the fiber has a porous structure. In addition, the protection of the inert gas during sintering can protect the carbon content in the fiber and endow the fiber with electric conductivity.
Fourth aspect of the invention
On the basis of the third aspect, the fourth aspect of the present invention provides a preferred preparation method of a flexible electrode material, comprising: adding polyvinylpyrrolidone, glacial acetic acid and nano materials into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
the nano material is added into an organic solvent before tetraethyl silicate and tetrabutyl titanate, and if the nano material, the tetraethyl silicate and the tetrabutyl titanate are simultaneously added into the organic solvent, the nano material cannot be uniformly dispersed in the spinning solution, because the tetraethyl silicate and the tetrabutyl titanate are two viscous organic matters, the solvent is viscous after the nano material is added, and the powdery nano material cannot be uniformly dispersed;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers; electrostatic spinning is a prior art;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material. The textile fiber is placed in the air for more than 24 hours, and the activation hydrolysis can be carried out by water vapor in the air without a catalyst. Adding inert gas such as high-purity argon (with purity of 99.999%) during sintering, mainly protecting the carbon in the fiber from being stable during sintering, and changing the carbon in the air into CO2 gas; the carbon content of the fibers in the prepared flexible electrode material can be protected, and the fibers are endowed with conductivity. The temperature is controlled at 400-800 ℃, which is beneficial to controlling the graphitization degree of carbon and avoiding the graphitization degree of carbon from being too high.
In the preparation method, the tetraethyl silicate and the tetrabutyl titanate are easy to hydrolyze when meeting water under the acidic condition, and the hydrolysis of the tetraethyl silicate and the tetrabutyl titanate can diffuse from the center of the fiber to the periphery, so that the fiber generates a porous structure; and the nano material is added, so that the fiber has better mechanical property. In addition, the protection of the inert gas during sintering can protect the carbon content in the fiber and endow the fiber with electric conductivity.
Example 1
A preparation method of a flexible electrode material comprises the following steps:
adding polyvinylpyrrolidone, glacial acetic acid and nano materials into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
activating and hydrolyzing the spinning fiber, introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material;
wherein, the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate and the organic solvent are respectively added by 10 parts by weight, 20 parts by weight, 5 parts by weight and 55 parts by weight;
the organic solvent is absolute ethyl alcohol;
0.5 part by weight of nano material is added into the textile solution, and the nano material is a one-dimensional nano material, in particular a carbon nano tube.
Example 2
The implementation steps are the same as the embodiment steps, except that:
the addition amounts of the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate and the organic solvent are as follows: 5 parts by weight, 15 parts by weight, 8 parts by weight, 57 parts by weight; the addition amount of the nano material is 1 part by weight.
Example 3
The procedure was the same as in example 1, except that:
the addition amounts of the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate, the nano material and the organic solvent are as follows: 15 parts by weight, 5 parts by weight, 25 parts by weight, 2 parts by weight, 53 parts by weight; the addition amount of the nano material is 0.1 part by weight.
Example 4
The procedure was the same as in example 1, except that:
the organic solvent is dimethylformamide.
Example 5
The procedure was the same as in example 1, except that:
the organic solvent is N-methyl pyrrolidone.
Example 6
The procedure was the same as in example 1, except that:
the catalyst adopts hydrochloric acid instead of glacial acetic acid.
Example 7
The procedure was the same as in example 1, except that:
the nano material is a one-dimensional nano material, in particular to a metal silver nanowire.
Example 8
The procedure was the same as in example 1, except that:
the nano material is a two-dimensional nano material, and specifically is graphene oxide.
Example 9
The procedure was the same as in example 1, except that:
the nano material is a two-dimensional nano material, specifically a two-dimensional transition metal carbide, more specifically titanium carbide.
Example 10
The procedure was the same as in example 1, except that:
the nano material is a two-dimensional nano material, in particular to a two-dimensional transition metal nitride.
Example 11
The procedure was the same as in example 1, except that:
the nanomaterial was not added.
Comparative example 1
Mixing dimethylacetamide and Polyacrylonitrile (PAN) to prepare spinning solution, and performing electrostatic spinning on the spinning solution to prepare the electrode material, wherein the mass ratio of dimethylacetamide to Polyacrylonitrile (PAN) is 88: 12.
experiment one: flexible electrode material hollow structure test experiment
The flexible electrode materials prepared in examples 1 to 11 of the present invention and the electrode material prepared in comparative example 1 were scanned by a Hitachi SU8010 scanning electron microscope, and the cross-sectional morphology of the carbon fiber material in all the electrode materials was recorded, with the following results:
TABLE 1 hollowness of carbon fiber materials
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Hollow core | Hollow core | Hollow core | Hollow core | Hollow core | Hollow core |
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Comparative example 1 |
| Hollow core | Hollow core | Hollow core | Hollow core | Hollow core | Is solid |
From the results in table 1 above, it can be seen that the cross-section of the carbon fiber material in all of the flexible electrode materials of examples 1 to 11 of the present invention is a hollow structure, while the cross-section of the carbon fiber material of comparative example 1 of the prior art is a solid structure. It is demonstrated that the flexible electrode material prepared by the foregoing embodiments of the present invention has good electrochemical performance compared to the prior art.
In addition, fig. 1 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material to which Carbon Nanotubes (CNTs) are added in example 1, and fig. 2 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material to which graphene oxide is added in example 8; FIG. 3 is a schematic cross-sectional view of a carbon fiber material in a flexible electrode material of example 9 with titanium carbide added; FIG. 4 is a schematic cross-sectional view of the carbon fiber material in the electrode material of comparative example 1 in the prior art. As can be seen from the results shown in fig. 1 to 4, the cross section of the carbon fiber material in all the flexible electrode materials of examples 1, 8 and 9 of the present invention has a hollow structure, while the cross section of the carbon fiber material in comparative example 1 of the prior art has a solid structure.
Experiment two: electrochemical performance experiment of flexible electrode material
The assembled battery is subjected to electrochemical performance test by adopting L AND test equipment, AND the specific experimental process comprises the following steps of cutting the flexible electrode material into a wafer with the diameter of 10mm, depositing quantitative metal lithium at constant current, AND matching with the NCM523 to assemble the whole battery for constant current charge AND discharge test.
In fig. 5, fig. 6, and fig. 7, the lower black lines respectively represent the discharge capacities of the assembled battery after graphene oxide (rGO), MXene titanium carbide, carbon nanotube CNT fiber and lithium are added and composited, and gray is blank comparison. The upper black line is the coulombic efficiency, and the gray is the coulombic efficiency for the blank comparison.
As can be seen from the results shown in fig. 5 to fig. 7, the flexible electrode materials prepared by the embodiments 1, 8, and 9 of the present invention have higher coulombic efficiency and better electrochemical performance.
The lower black lines in fig. 8 represent the discharge capacity of the assembled battery after the carbon nanotube CNT fiber and the lithium are compounded in example 1, and gray represents the discharge capacity of the flexible battery prepared in example 11 without the added nanomaterial. As can be seen from the results shown in fig. 8, the electrochemical performance of the flexible electrode material prepared in example 11 without adding the nanomaterial is slightly inferior to that of example 1.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited thereto. The protection scope of the present invention is not limited to the above embodiments, but equivalent modifications or changes made by those skilled in the art according to the disclosure of the present invention should be included in the protection scope of the claims.
Claims (10)
1. A dope for preparing a carbon fiber material, comprising:
polyvinylpyrrolidone, a catalyst, tetraethyl silicate, tetrabutyl titanate and an organic solvent.
2. The dope of claim 1, wherein the catalyst is glacial acetic acid.
3. The spinning dope of claim 1, comprising:
5-15 parts of polyvinylpyrrolidone;
5-15 parts of catalyst;
tetraethyl silicate, 15-25 parts by weight;
2-8 parts of tetrabutyl titanate;
40-60 parts of organic solvent.
4. The spinning dope of claim 3, comprising:
9-11 parts of polyvinylpyrrolidone;
9-11 parts of catalyst;
tetraethyl silicate, 18-22 parts by weight;
4-6 parts of tetrabutyl titanate;
50-60 parts of organic solvent.
5. The dope of claim 1, further comprising a nanomaterial comprising at least one of a one-dimensional nanomaterial and a two-dimensional nanomaterial; the addition amount of the nano material is 0.1-1 part by weight based on 100 parts by weight of the spinning solution.
6. The spinning dope of claim 5, wherein the one-dimensional nanomaterial comprises at least one of carbon nanotubes and metal nanowires; the metal nanowires are VIII, IB and IIIA group metal nanowires;
the two-dimensional nano material at least comprises one of graphene oxide, two-dimensional transition metal carbide and two-dimensional transition metal nitride.
7. The dope according to any one of claims 1 to 6, wherein the organic solvent comprises at least one of absolute ethanol, N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
8. A flexible electrode material prepared from the spinning dope of any one of claims 1 to 7.
9. A preparation method of a flexible electrode material is characterized by comprising the following steps:
adding polyvinylpyrrolidone and glacial acetic acid into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material.
10. A preparation method of a flexible electrode material is characterized by comprising the following steps:
adding polyvinylpyrrolidone, glacial acetic acid and nano materials into an organic solvent, uniformly stirring, and then adding tetraethyl silicate and tetrabutyl titanate to prepare a spinning solution;
carrying out electrostatic spinning on the spinning solution to prepare spinning fibers;
and (3) carrying out activation hydrolysis on the spinning fiber, then introducing inert gas and sintering at the temperature of 400-800 ℃ to prepare the flexible electrode material.
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