CN113072058A - Preparation method and application of nano carbon material with porous structure - Google Patents
Preparation method and application of nano carbon material with porous structure Download PDFInfo
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- CN113072058A CN113072058A CN202110320497.5A CN202110320497A CN113072058A CN 113072058 A CN113072058 A CN 113072058A CN 202110320497 A CN202110320497 A CN 202110320497A CN 113072058 A CN113072058 A CN 113072058A
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003990 capacitor Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000007833 carbon precursor Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims abstract description 7
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000011056 performance test Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 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
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a nano carbon material with a porous structure, belonging to the technical field of lithium ion capacitors. According to the preparation method of the nano carbon material with the porous structure, butane tetracarboxylic acid and zinc acetylacetonate are used as precursors, ethylene glycol is used as a solvent, the carbon precursor is synthesized through a coprecipitation method, and the carbon precursor is carbonized at high temperature, washed by hydrochloric acid and subjected to subsequent drying treatment to obtain the nano carbon with a high pore volume and a large specific surface. The nano carbon material has a special layered structure, and the reasonable pore size distribution of the nano carbon material is beneficial to the diffusion and storage of electrolyte ions, so that the material has high conductivity. The preparation method is simple in preparation process, simple and convenient to operate and convenient to characterize. The carbon with the porous structure can be prepared into an electrode slice, and the electrode slice is assembled into a CR2032 lithium ion button capacitor for electrochemical performance test, and the carbon has good cycling stability and higher specific capacity when used as a lithium ion capacitor anode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion capacitors, and particularly relates to a preparation method and application of a nano carbon material with a porous structure.
Background
Lithium ion capacitors are an emerging energy storage device that combines the features of high power type capacitors and high energy density batteries. They have excellent energy storage capacity, as compared to conventional electrochemical devices, and thus can be considered as a strong competitor to alternative energy storage systems. In addition, the lithium ion capacitor has extremely high stable cycle life, low maintenance cost and safe use. However, the commercial activated carbon as the positive electrode of the lithium ion capacitor has an extremely low specific capacity, represented only by 30-40mAh/g, due to the irrational distribution of its internal pores, which greatly limits the capacity of the lithium ion capacitor. Therefore, developing a high specific capacity and good cycle stability lithium ion capacitor cathode carbon material has become a key technical difficulty in this field.
According to the mechanism of energy storage of the capacitor, the pore volume and pore size distribution are the key factors determining the specific capacity. According to the related research, when the pore diameter of the micropores is matched with the ionic radius of the electrolyte, the capacitor can obtain larger capacitance value. In addition, the mesoporous structure can provide a small resistance channel for the transfer of ions, which is beneficial to the mobility of the ions, and the macropores reduce the transfer distance of the ions. Therefore, it is very important to prepare and synthesize a carbon material having a large pore volume and a reasonable pore size distribution.
Disclosure of Invention
The invention aims to solve the technical problems of low specific capacity and poor cycle stability of the existing lithium ion capacitor anode material in the prior art, and provides a preparation method of a nano carbon material with a porous structure, the nano carbon material is used as the lithium ion capacitor anode material to be applied to a lithium ion capacitor, the nano carbon material with the porous structure has reasonable pore size distribution, micropores can increase the specific capacity by improving the specific surface area of the material, a mesoporous structure can provide a small resistance channel for the transfer of ions, and macropores can reduce the transfer distance of the ions, so that high specific capacity and cycle performance are realized.
In order to solve the above technical problems, an embodiment of the present invention provides a method for preparing a nanocarbon material having a porous structure, including the following steps:
(1) weighing 1.5g of butanetetracarboxylic acid and 3.6g of zinc acetylacetonate, dissolving in 200ml of ethylene glycol, and stirring to obtain a mixed solution;
(2) stirring the mixed solution at 80 ℃ in an oil bath for 24 hours, and then sequentially carrying out immersion cleaning treatment and filtration treatment to obtain a carbon precursor;
(3) placing the carbon precursor in a horizontal tube furnace, carrying out carbonization treatment under the condition of continuously introducing inert gas, and then naturally cooling to room temperature to obtain a carbonized product;
(4) sequentially carrying out immersion cleaning treatment, cleaning treatment and filtering treatment on the carbonized product to obtain an acid-cleaned product;
(5) and drying the acid washing product to obtain the nano carbon material with the porous structure.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the immersion cleaning treatment in the step (2) is specifically immersion cleaning by sequentially using deionized water and absolute ethyl alcohol.
Further, the inert gas is argon.
Further, the carbonization treatment is specifically carried out by heating from room temperature to 800 ℃, and keeping the temperature for 4 hours.
Further, in the carbonization treatment, the temperature rise rate is 5 degrees centigrade per minute.
Further, the immersion cleaning in the step (4) is specifically performed by using a hydrochloric acid solution with a concentration of 20%, and the cleaning is specifically performed by using deionized water for 5 times.
Further, the drying treatment specifically comprises the step of drying the acid-washed product in a vacuum drying oven at 75 ℃ for 24 hours.
Further, the pore volume of the nanocarbon material having a porous structure is 1.836cm3/g。
In order to solve the above technical problems, embodiments of the present invention provide an application of the nanocarbon material with a porous structure as a positive electrode material in the preparation of a lithium ion capacitor.
The invention has the beneficial effects that: according to the preparation method of the nano carbon material with the porous structure, which is suitable for the anode material of the lithium ion capacitor, is prepared through simple carbon precursor preparation and reasonable carbonization temperature. The carbon material has a large pore volume and a reasonable pore size distribution, which will favor PF6-The absorption of ions further improves the specific capacity of the capacitor and relieves the structural damage in the circulating process. When the charge-discharge current density is 0.1A/g, the capacitor has high specific capacity of 83.9mAh/g and good rate performance. In addition, under the condition of 5A/g of super-large current density, the specific capacity of about 30mAh/g is still kept after 10000 cycles of circulation.
Drawings
FIG. 1 is an SEM image of a nanocarbon material having a porous structure according to example 1 of the present invention;
FIG. 2 is a pore size distribution curve of a nanocarbon material having a porous structure according to example 1 of the present invention;
FIG. 3 is a Raman diagram of a nanocarbon material having a porous structure according to example 1 of the present invention;
FIG. 4 is a cycle performance curve of a nanocarbon material having a porous structure at a current density of 5A/g according to example 1 of the present invention;
FIG. 5 is a graph showing the rate performance of a nanocarbon material having a porous structure at different current densities according to an embodiment of the present invention;
fig. 6 is a CV curve of a nanocarbon material having a porous structure according to an embodiment of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
1.5g of butanetetracarboxylic acid and 3.6g of zinc acetylacetonate were added to 200mL of ethylene glycol and stirred to form a pale yellow-green mixed solution. And then transferring the mixed solution to an oil bath at 80 ℃ and stirring for 24 hours, sequentially using deionized water and absolute ethyl alcohol for immersion cleaning, and filtering to obtain the carbon precursor. And putting the carbon precursor into a tube furnace, carbonizing for 4 hours at 800 ℃ under the argon atmosphere, cooling to room temperature, and taking out the sample. And taking out the sample, washing the sample for 24 hours by using 20% hydrochloric acid, washing the sample for 5 times by using deionized water, filtering the sample, and finally drying the sample in a vacuum drying oven at the temperature of 75 ℃ to obtain the nano carbon material with the porous structure.
In order to test the specific capacity, rate capability and cycle performance of the nano carbon material with the porous structure, the nano carbon material with the porous structure is used as a positive electrode in a lithium ion capacitor to assemble a button capacitor, and the process is as follows: drying the nano carbon material with the porous structure in a vacuum oven at 75 ℃ for 12 hours; then weighing the nano carbon material with the porous structure, the conductive carbon black and the polyvinylidene fluoride according to the mass ratio of 8:1:1, mixing with a proper amount of N-methyl pyrrolidone, grinding into electrode slurry, coating the electrode slurry on an aluminum foil, drying for 24 hours in a vacuum oven at 75 ℃, and cutting into electrode plates with the diameter of 14 mm by using a slicing machine; celgard2400 is used as a diaphragm, metal lithium is used as another electrode, a dimethyl carbonate/diethyl carbonate/ethylene carbonate solution containing 1mol/L lithium hexafluorophosphate is used as an electrolyte, a mixed solution of dimethyl carbonate, diethyl carbonate and ethylene carbonate in a ratio of 1:1:1 is used as a solution, 1mol/L lithium hexafluorophosphate is used as a solute, and the electrolyte and an electrode plate are assembled together to form the lithium ion button semi-capacitor.
The lithium ion button semi-capacitor is subjected to electrochemical performance test on a battery test system of a CT2001A model and an electrochemical workstation of a CH604E model, and the voltage range of the lithium ion button semi-capacitor is 2-4.5V.
Fig. 1 is an SEM image of the nanocarbon material having a porous structure obtained by the method of this example, and it can be seen that the carbon material exhibits a layered sheet-like structure.
FIG. 2 is a pore size distribution curve of a nanocarbon material having a porous structure obtained by the method of this example, the nanocarbon material having a pore size of 1.836cm3Pore volume in g, with micropores concentrated around 1nm, with PF6-The anion has excellent compatibility and also has a large mesopore distribution.
Fig. 3 is a Raman chart of the nanocarbon material with a porous structure obtained by the method of the present embodiment, and it can be seen that the material has a high degree of defects, which is advantageous for improving electrochemical performance.
Fig. 4 shows that the nanocarbon material with a porous structure obtained by the method of the present embodiment is used as the positive electrode active material of the lithium ion capacitor, and has a cycle performance curve with a current density of 5A/g, and after 10000 cycles of cycle, the specific capacity is stabilized around 30mAh/g, and the nanocarbon material has good cycle stability.
Fig. 5 shows the rate performance curves of the nanocarbon material with a porous structure as the positive electrode active material of the lithium ion capacitor obtained by the method of the embodiment under different current densities, and when the current densities are 0.1, 0.2, 0.5, 1, 2, 5 and 10A/g, the capacitor has specific capacities of 83.9, 78, 69.3, 62.3, 54.7, 42.1 and 30.3mAh/g, and has excellent rate performance.
Fig. 6 is a CV curve measured on an electrochemical workstation of a model CH604E, in which the nanocarbon material with a porous structure obtained by the method of the present embodiment is used as a positive electrode active material of a lithium ion capacitor, and the curve has good symmetry, which indicates high stability.
Example 2
1.5g of butanetetracarboxylic acid and 3.6g of zinc acetylacetonate were added to 200mL of ethylene glycol and stirred to form a pale yellow-green mixed solution. And then transferring the mixed solution to an oil bath at 80 ℃ and stirring for 24 hours, sequentially using deionized water and absolute ethyl alcohol for immersion cleaning, and filtering to obtain the carbon precursor. And putting the carbon precursor into a tubular furnace, and carbonizing at 800 ℃ for 4 hours under the argon atmosphere to obtain the nano carbon material.
The process of example 2 is essentially the same as that of example 1, except that example 2 does not pass hydrochloric acidWashing. The porous nanocarbon obtained by the method has the thickness of 0.995cm3Pore volume per gram, it can be seen that the pore volume of the nanocarbon having a porous structure is greatly reduced without being washed with hydrochloric acid.
Example 3
1.5g of butanetetracarboxylic acid and 3.6g of zinc acetylacetonate were added to 200mL of ethylene glycol and stirred to form a pale yellow-green mixed solution. And then transferring the mixed solution to an oil bath at 80 ℃ and stirring for 24 hours, sequentially using deionized water and absolute ethyl alcohol for immersion cleaning, and filtering to obtain the carbon precursor. And putting the carbon precursor into a tube furnace, carbonizing for 4 hours at 700 ℃ or 900 ℃ under the argon atmosphere, cooling to room temperature, and taking out the sample. And taking out, washing the sample for 24 hours by using 20% hydrochloric acid, washing for 5 times by using deionized water, filtering, and finally drying in a vacuum drying oven at 75 ℃ to obtain the nano carbon material.
The assembly process of the capacitor is as follows: weighing a nano carbon material with a porous structure, conductive carbon black and polyvinylidene fluoride according to a mass ratio of 8:1:1, mixing with a proper amount of N-methyl pyrrolidone, grinding into electrode slurry, coating the electrode slurry on an aluminum foil, drying for 24 hours in a vacuum oven at 75 ℃, and cutting into electrode plates with the diameter of 14 mm by using a slicing machine; celgard2400 is used as a diaphragm, metal lithium is used as another electrode, 1mol/L dimethyl carbonate/diethyl carbonate/ethylene carbonate solution of lithium hexafluorophosphate is used as electrolyte, wherein the volume ratio of dimethyl carbonate, diethyl carbonate and ethylene carbonate is 1:1:1, and the electrolyte and an electrode plate are jointly assembled into the lithium ion button semi-capacitor.
The process of example 3 is substantially the same as that of example 1, except that example 3 uses a carbonization temperature of 700 degrees celsius or 900 degrees celsius. Compared with the nanocarbon prepared in example 1, the two nanocarbon materials synthesized at 700 ℃ and 900 ℃ have lower specific capacity and cycling stability.
According to the preparation method of the nano carbon material with the porous structure, butane tetracarboxylic acid and zinc acetylacetonate are used as precursors, ethylene glycol is used as a solvent, the carbon precursor is synthesized through a coprecipitation method, and the carbon precursor is carbonized at high temperature, washed by hydrochloric acid and subjected to subsequent drying treatment to obtain the nano carbon with a high pore volume and a large specific surface. The nano carbon material has a special layered structure, and the reasonable pore size distribution of the nano carbon material is beneficial to the diffusion and storage of electrolyte ions, so that the material has high conductivity. The preparation method is simple in preparation process, simple and convenient to operate and convenient to characterize. The carbon with the porous structure can be prepared into an electrode slice, and the electrode slice is assembled into a CR2032 lithium ion button capacitor for electrochemical performance test, and the carbon has good cycling stability and higher specific capacity when used as a lithium ion capacitor anode material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a nano carbon material with a porous structure is characterized by comprising the following steps:
(1) weighing 1.5g of butanetetracarboxylic acid and 3.6g of zinc acetylacetonate, dissolving in 200ml of ethylene glycol, and stirring to obtain a mixed solution;
(2) stirring the mixed solution at 80 ℃ in an oil bath for 24 hours, and then sequentially performing immersion cleaning treatment and filtration treatment to obtain the carbon precursor;
(3) placing the carbon precursor in a horizontal tube furnace, carrying out carbonization treatment under the condition of continuously introducing inert gas, and then naturally cooling to room temperature to obtain a carbonized product;
(4) sequentially carrying out immersion cleaning treatment, cleaning treatment and filtering treatment on the carbonized product to obtain an acid-cleaned product;
(5) and drying the acid washing product to obtain the nano carbon material with the porous structure.
2. The method for preparing a nanocarbon material having a porous structure according to claim 1, wherein the step (2) comprises a step of sequentially performing an immersion cleaning with deionized water and absolute ethyl alcohol.
3. The method for preparing a nanocarbon material having a porous structure according to claim 1, wherein the inert gas is argon gas.
4. The method for preparing a nanocarbon material having a porous structure according to claim 1, wherein the carbonization treatment is carried out at room temperature to 800 ℃ for 4 hours.
5. The method according to claim 1, wherein the temperature increase rate in the carbonization treatment is 5 degrees celsius/minute.
6. The method for preparing a nanocarbon material having a porous structure according to claim 1, wherein the rinsing treatment in the step (4) is rinsing with 20% hydrochloric acid solution, and the rinsing treatment is rinsing with deionized water for 5 times.
7. The method for preparing a nano carbon material with a porous structure according to claim 1, wherein the drying treatment is specifically to dry the acid-washed product in a vacuum drying oven at 75 ℃ for 24 hours.
8. The method for preparing a nanocarbon material having a porous structure according to claim 1, wherein the pore volume of the nanocarbon material having a porous structure is 1.836cm3/g。
9. Use of the nanocarbon material having a porous structure according to any one of claims 1 to 8 as a positive electrode material for producing a lithium ion capacitor.
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