CN115172073A - 3D printed oxide/carbon composite aerogel electrode and preparation method thereof - Google Patents
3D printed oxide/carbon composite aerogel electrode and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000004964 aerogel Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 230000008021 deposition Effects 0.000 claims abstract description 46
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 34
- 238000010146 3D printing Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
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- 229910021641 deionized water Inorganic materials 0.000 description 7
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- 238000013329 compounding Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
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- 239000012071 phase Substances 0.000 description 5
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- 239000007772 electrode material Substances 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention relates to a 3D printing oxide/carbon composite aerogel electrode and a preparation method thereof. The preparation method of the electrode comprises the following steps: soaking the carbon aerogel obtained by 3D printing in a cobalt-containing deposition solution, standing, and fully drying to realize liquid phase deposition; and (3) placing the carbon aerogel subjected to liquid phase deposition in an inert atmosphere for heat treatment to obtain the 3D printing oxide/carbon composite aerogel electrode. Compared with the prior art, the invention avoids starting from a complicated ink preparation process, realizes the preparation of the 3D printing oxide/carbon composite aerogel electrode from a new angle, and has high commercial and industrial practicability for the used raw materials, methods and performances. In addition, the simple preparation method can also stimulate other potential applications, such as solar steam power generation, electromagnetic shielding, catalysis and the like.
Description
Technical Field
The invention relates to the field of 3D printing composite aerogel and energy storage, in particular to a 3D printing oxide/carbon composite aerogel electrode and a preparation method thereof.
Background
The 3D printed carbon aerogel has abundant porosity, ultra-high specific surface area, good electrical conductivity, excellent permeability, abundant active sites, and good substance/electron/ion diffusion and transport channels, and is considered as the most promising electrode material for supercapacitor electrodes.
In the preparation of 3D printed carbon composite aerogels, most of the prior art prepares printable composite inks from the required precursor components in a one-pot process, for example, chinese patent CN109534320A, entitled: ' a preparation method of 3D printing graphene composite aerogel and the composite aerogel. In order to realize good dispersion of precursor components, the method usually needs to chemically modify the introduced functional materials, add other organic components additionally, and strictly limit the addition amount of the functional materials, so that the prepared composite ink is very easy to cause poor printing effect (easy to block, short in service life and the like); in addition, the specific formulation of a composite ink almost directly determines the electrochemical performance of the final supercapacitor electrode, which requires readjustment of various parameters (ink rheology, extrusion pressure, printing speed, needle size, etc.) printable with ink from the ink formulation for the material design of the electrode with optimal electrochemical performance, thus increasing the workload of technicians and consuming a large amount of resource cost.
Therefore, for the directly obtained 3D printing electrode material, the ink raw material formula directly determines and limits the capacitance performance of the final printing electrode, and the strict conditions of ink rheology and printability need to be satisfied, so there are few types of ink raw materials that can be used for preparing 3D printing carbon aerogel, and it is challenging to further maximize the capacitance performance.
Disclosure of Invention
The present invention is directed to overcoming at least one of the above-mentioned disadvantages of the prior art and providing a 3D printed oxide/carbon composite aerogel electrode and a method for preparing the same.
The purpose of the invention can be realized by the following technical scheme:
the basic idea is as follows: the electrode of the oxide/carbon composite aerogel is further prepared by combining the pure carbon aerogel electrode obtained by 3D printing with a liquid phase deposition and heat treatment method. Mainly through soaking the pure carbon aerogel that obtains 3D printing in the deposition solution that contains the customization composition, carry out spontaneous liquid phase deposition under the normal atmospheric temperature, then redundant moisture in the carbon aerogel is got rid of in vacuum drying, carries out thermal treatment at last and accomplishes the preparation that 3D printed oxide/carbon composite aerogel electrode promptly, and the concrete scheme is as follows:
a preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following steps:
soaking the carbon aerogel obtained by 3D printing in a cobalt-containing deposition solution, standing, and fully drying to realize liquid phase deposition;
in the scheme, the carbon aerogel obtained by 3D printing is obtained by 3D direct writing molding of resorcinol-formaldehyde sol-gel ink which is widely researched, then the organic aerogel is obtained by freeze drying, and finally the carbon aerogel material for 3D printing is obtained by carbonization. The 3D network skeleton structure of the graphene aerogel is composed of carbon nanoparticles, and a skeleton with a hierarchical porous structure is obtained by combining a freeze drying technology and a 3D printing technology, and is different from carbon aerogel (the pore structure mainly comprises micropores) and graphene aerogel (the skeleton structure is composed of a lamellar structure) obtained by conventional supercritical drying. Specific surface area, pore size distribution, etc. are shown as CA in FIG. 2.
And (3) placing the carbon aerogel subjected to liquid phase deposition in an inert atmosphere for heat treatment to obtain the 3D printing oxide/carbon composite aerogel electrode.
Further, the concentration of the cobalt-containing deposition solution is 0.2-1.0M.
Further, the cobalt-containing deposition solution is prepared by the following method: adding cobalt salt into water, and stirring to obtain a cobalt-containing deposition solution.
Further, the cobalt salt comprises cobalt nitrate hexahydrate.
Furthermore, the temperature of the heat treatment is 400-600 ℃, and the time is 1.5-2.5h.
Further, the standing time is 1-3 days.
Further, the stirring time is 1-3h.
Further, the drying temperature is 90-100 ℃.
Further, the gas flow rate in the inert atmosphere is 250-350mL min -1 。
A 3D printed oxide/carbon composite aerogel electrode prepared as described above. The electrode thus prepared showed 3949mF cm -2 (at a scan rate of 5mV s -1 Lower), which is 33.4% higher than the performance before compounding, and is much higher than the capacitance performance of other carbonaceous material electrodes. High capacitance performance may result from two aspects:
(1) 3D printing the self layered porosity, good conductivity and abundant active sites of the carbon aerogel;
(2) The pseudocapacitance characteristics of cobalt oxide and its good dispersion.
In conclusion, the invention makes up the defects of completing the preparation of the 3D printing carbon aerogel electrode by directly preparing the ink, and solves the problem of limited ink types which can be used for 3D printing carbon aerogel from a new angle. Meanwhile, the simple preparation method can also stimulate other potential applications, such as solar steam power generation, electromagnetic shielding, catalysis and the like.
Compared with the prior art, the invention has the characteristics of simple preparation method, lower cost, easier control of composite components or concentration, strong universality and the like. On one hand, by reasonably regulating and controlling the deposition concentration, the layered porosity, good conductivity and rich active sites of the 3D printing carbon aerogel are reserved, and the negative influence on the capacitance performance of the carbon aerogel is avoided; on the other hand, the pseudo-capacitance characteristic of cobalt oxide is effectively and uniformly introduced into the 3D printed carbon aerogel through a simple preparation method, and the capacitance performance of the electrode is further improved remarkably. The invention avoids starting from a complicated ink preparation process, realizes simple preparation of the 3D printing oxide/carbon composite aerogel electrode from a new and different angle, and has high commercial and industrial practicability for the raw materials, methods and performances used by the electrode. In addition, the simple preparation method can also stimulate other potential applications, such as solar steam power generation, electromagnetic shielding, catalysis and the like.
Drawings
FIG. 1 is an XRD spectrum of a pure carbon aerogel and electrode materials at different processing temperatures;
FIG. 2 is a graph showing the adsorption-desorption curve (a) and the pore size distribution (b) of electrode materials of different deposition concentrations;
FIG. 3 is a photograph showing a real object of a 0.2M CA @ Co electrode (a), SEM images of the front (b, c) and cross section (d), and Mapping images of the front (e) and cross section (f);
FIG. 4 is a front SEM image of electrodes from 0.5M (a) and 1M (b) deposition concentrations;
FIG. 5 is TEM images of CA (a) and CA @ Co (b);
FIG. 6 is a comparison of electrode area capacitance obtained for different deposition concentrations;
FIG. 7 is a cyclic voltammogram of the CA electrode (a) and the CA @ Co electrode (b);
FIG. 8 is a comparison of the area capacitance of an electrode evaluated in terms of current density (a) and scan rate (b) with the capacitance performance of other carbonaceous material electrodes;
fig. 9 is a schematic diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
In the following examples, the raw materials were all commercially available materials, and the purity was chemically pure or analytically pure.
Example 1
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 2.33g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring at normal temperature for 2h, and preparing a deposition solution with the molar concentration of 0.2M;
(2) The 3D-printed pure carbon aerogel structure was immersed in the above deposition solution, left to stand at room temperature and stored for 2 days, and then taken out and sufficiently dried overnight in a vacuum drier (at 100 c), whereby the resulting electrode was named "ca @ co-100".
Example 2
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 2.33g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring at normal temperature for 2h, and preparing a deposition solution with the molar concentration of 0.2M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) Placing the deposited structure obtained in step (2) in a nitrogen stream (300 mL min) -1 ) The preparation of the 3D printed oxide/carbon composite aerogel electrode can be realized by carrying out heat treatment (keeping the temperature at 400 ℃ for 2 h) in a quartz tube furnace under protection, and the obtained electrode is named as 'CA @ Co-400' or '0.2MCA @ Co' or 'CA @ Co'.
Example 3
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 2.33g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring for 2h at normal temperature, and preparing a deposition solution with the molar concentration of 0.2M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) The deposited structure obtained in step (2) was placed under a stream of nitrogen (300 mL min) -1 ) The preparation of the 3D printed oxide/carbon composite aerogel electrode can be realized by carrying out heat treatment (keeping the temperature at 600 ℃ for 2 h) in a quartz tube furnace under protection, and the obtained electrode is named as 'CA @ Co-600'.
Example 4
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 1.16g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring at normal temperature for 2h, and preparing a deposition solution with the molar concentration of 0.1M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) Placing the deposited structure obtained in step (2) in a nitrogen stream (300 mL min) -1 ) The preparation of the 3D printed oxide/carbon composite aerogel electrode can be realized by carrying out heat treatment (keeping the temperature at 400 ℃ for 2 h) in a quartz tube furnace under protection, and the obtained electrode is named as '0.1M CA @ Co'.
Example 5
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 3.49g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring for 2h at normal temperature, and preparing a deposition solution with the molar concentration of 0.3M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) Placing the deposited structure obtained in step (2) in a nitrogen stream (300 mL min) -1 ) The preparation of the 3D printed oxide/carbon composite aerogel electrode can be realized by carrying out heat treatment (keeping the temperature at 400 ℃ for 2 h) in a quartz tube furnace under protection, and the obtained electrode is named as '0.3M CA @ Co'.
Example 6
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 5.82g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring for 2h at normal temperature, and preparing a deposition solution with the molar concentration of 0.5M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) Placing the deposited structure obtained in step (2) in a nitrogen stream (300 mL min) -1 ) The preparation of the 3D printed oxide/carbon composite aerogel electrode can be realized by carrying out heat treatment (keeping at 400 ℃ for 2 h) in a quartz tube furnace under protection, and the obtained electrode is named as '0.5M CA @ Co'.
Example 7
A simple preparation method of a 3D printed oxide/carbon composite aerogel electrode comprises the following specific steps:
(1) Adding 11.64g of cobalt nitrate hexahydrate into 40mL of deionized water, stirring at normal temperature for 2h, and preparing a deposition solution with the molar concentration of 1M;
(2) Soaking a pure carbon aerogel structure obtained by 3D printing in the deposition solution, standing at room temperature, storing for 2 days, taking out, and fully drying in a vacuum drier (at 100 ℃) overnight to realize liquid phase deposition;
(3) Placing the deposited structure obtained in step (2) in a nitrogen stream (300 mL min) -1 ) The composite aerogel electrode is subjected to heat treatment in a quartz tube furnace under protection (the temperature is kept at 400 ℃ for 2 hours), so that the preparation of the 3D printing oxide/carbon composite aerogel electrode can be realized, and the obtained electrode is named as '1M CA @ Co'.
As shown in FIG. 1, the electrode obtained in example 1 exhibited diffraction peaks at 2. Theta. Values of 10.9, 13.6, 16.6, 20.6, 21.8 and 25.1 in the XRD spectrum, which were labeled as cobalt nitrate hydrate phases (PDF NO. 48-0091), indicating that the introduction temperature was insufficient to decompose the introduced cobalt nitrate phase, and thus was also insufficient to decompose the introduced cobalt nitrate phaseSubsequent heat treatment is required; the electrode obtained in example 2 exhibited typical diffraction peaks (Co) of (3 1), (5 1) and (4 0) 3 O 4 Phase, PDF Nos. 42-1467) and (1 1), (2 0), (2 2 0), (3 1) and (2) diffraction peaks (CoO phase, PDF No. 75-0418), indicating successful preparation of cobalt oxide upon heat treatment at 400 deg.C; the electrode obtained in example 3 exhibited typical diffraction peaks (Co phase, PDF No. 15-0806) of (1 1), (2 0) and (22), indicating that cobalt in an oxidized state was completely reduced by carbon at a temperature of 600 ℃. Therefore, in the subsequent simple preparation of 3D printed oxide/carbon composite aerogel electrodes, the heat treatment conditions were preferentially selected from those in example 2 (400 ℃ for 2 h).
As shown in fig. 2, the electrodes obtained in examples 2, 4 and 5 all showed well-defined mesoporous materials, the well-defined mesoporous materials: mainly seen from the absorption and desorption curves, the curve type is represented as an isotherm IV type, which is the absorption and desorption curve type of a typical mesoporous material.
And exhibit a more distributed hierarchical porous structure (1-100 nm). The specific surface area of the electrode decreased slightly with increasing concentration of the deposition solution (0.1-0.3M) (CA: 767.7M) 2 g -1 ，0.1MCA@Co：630.3m 2 g -1 ，0.2M CA@Co：611.7m 2 g -1 ，0.3M CA@Co：590.8m 2 g -1 )。
As shown in fig. 3, the electrode obtained in example 2 has an intact overall shape, and this simple preparation method not only retains the hierarchical porosity of 3D printed carbon aerogel, but also effectively and uniformly distributes cobalt oxide in the carbon aerogel micro-framework, thereby ensuring that the high-capacitance electrode is finally successfully obtained.
As shown in fig. 4, the electrodes obtained in examples 6 and 7 had cobalt-containing oxide particles aggregated to form larger clusters as the deposition concentration was further increased.
As shown in fig. 5, the electrode obtained in example 2 had a relatively uniform distribution of the cobalt oxide component in the microporous structure of the electrode after the compounding, compared to the microstructure before the Compounding (CA).
As shown in fig. 6, the electrode obtained in example 2 exhibited higher capacitance performance than the electrode obtained in other examples, and thus the 0.2M deposition concentration was prioritized.
As shown in fig. 7, the electrode obtained in example 2 exhibited a distinct redox peak after the recombination (CA @ co) as compared to that before the recombination (CA).
As shown in fig. 8, when the capacitance of the electrode obtained in example 2 was evaluated by using a potential window common to pure carbon aerogels (-1-0V), the area capacitance was almost equal to that of the electrode before Compounding (CA) under the same current density condition, but was significantly better than that of the electrode made of other carbonaceous materials; when a potential window (-1-0.6V) including the redox peak was selected, the area capacitance of the electrode after compounding (CA @ co) showed a significant improvement compared to the electrode before Compounding (CA) and other carbonaceous materials.
In conclusion, the invention realizes simple preparation of the 3D printing oxide/carbon composite aerogel electrode from a novel angle, avoids starting from a complicated ink preparation process, and has the characteristics of simple preparation method, lower cost, easier control of composite components or concentration, strong universality and the like. By reasonably regulating and controlling the deposition concentration, the layered porosity, good conductivity and rich active sites of the 3D printing carbon aerogel are reserved, and the negative influence on the capacitance performance of the carbon aerogel is avoided. The pseudo-capacitance characteristic of cobalt oxide is effectively and uniformly introduced into the 3D printing carbon aerogel through a simple preparation method, and the capacitance performance of the electrode is further improved remarkably. The simple preparation method can also stimulate other potential applications, such as solar steam power generation, electromagnetic shielding, catalysis and the like. The unique method of preparation has high commercial and industrial applicability, both in view of the raw materials used, the process, and the properties of the final electrode structure.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a 3D printed oxide/carbon composite aerogel electrode is characterized by comprising the following steps:
soaking the carbon aerogel obtained by 3D printing in a cobalt-containing deposition solution, standing, and fully drying to realize liquid phase deposition;
and (3) placing the carbon aerogel subjected to liquid phase deposition in an inert atmosphere for heat treatment to obtain the 3D printing oxide/carbon composite aerogel electrode.
2. The method of claim 1, wherein the cobalt-containing deposition solution is present in a concentration of 0.2 to 1.0M.
3. The method of claim 1, wherein the cobalt-containing deposition solution is prepared by the following steps: adding cobalt salt into water, and stirring to obtain a cobalt-containing deposition solution.
4. The method of claim 3, wherein the cobalt salt comprises cobalt nitrate hexahydrate.
5. The method for preparing a 3D printed oxide/carbon composite aerogel electrode according to claim 1, wherein the temperature of the heat treatment is 400-600 ℃ and the time is 1.5-2.5h.
6. The method of claim 1, wherein the resting time is 1-3 days.
7. The method of claim 3, wherein the stirring time is 1-3 hours.
8. The method of claim 1, wherein the drying temperature is 90-100 ℃.
9. The method of claim 1, wherein the gas flow rate in the inert atmosphere is 250-350mL _ min -1 。
10. A 3D printed oxide/carbon composite aerogel electrode prepared according to the method of any of claims 1-9.
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