CN113871214A - High-flexibility integrated super capacitor and preparation method thereof - Google Patents
High-flexibility integrated super capacitor and preparation method thereof Download PDFInfo
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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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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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Abstract
The invention discloses a high-flexibility integrated supercapacitor which comprises a hydrogel electrolyte layer and conducting polymer/GO composite electrodes which are polymerized and deposited in situ on two sides of the hydrogel electrolyte layer, wherein the hydrogel electrolyte layer is ammonium alginate-polyacrylic acid-polyacrylamide hydrogel electrolyte. The preparation method comprises the following steps: s1, soaking the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel membrane in an aqueous solution containing transition metal ions and halogen ions to obtain a hydrogel electrolyte; s2, fully dissolving the GO aqueous solution and the conductive polymer monomer in H2SO4A solution; s3, dissolving persulfate in H2SO4Dissolving in the solution and cooling; s4, rapidly mixing the solutions obtained in the steps S2 and S3, adding a hydrogel electrolyte, enabling the conductive polymer/GO composite electrode to be deposited in situ on two sides of the hydrogel electrolyte, cleaning residues, and cutting for four weeks to obtain the conductive polymer/GO composite electrode. The invention has excellent high flexibilityDeformation capability, good electrochemical performance and simple preparation method.
Description
Technical Field
The invention relates to a capacitor and a preparation method thereof, in particular to a high-flexibility integrated super capacitor and a preparation method thereof.
Background
Flexible stretchable electrodes and electrolyte materials are key to assembling flexible devices. The most widely used electrode material in the field of flexible supercapacitors is a conductive polymer which is compatible with various flexible substrates and has high conductivity, for example, DOI:10.1039/C9NR00427K reports that a flexible electrode made of porous PANI composite material has excellent electrochemical performance but has great performance loss under external force stimulation. The hydrogel is a porous, stretchable and high-water-content hydrophilic polymer network, can be used for an electrode-electrolyte-electrode layered structure, and has a good application prospect in a stretchable flexible supercapacitor. Sandwich structure devices still have some problems in long term applications. Firstly, a certain pressure needs to be continuously applied to the device in the charging and discharging process so as to realize the close contact between the electrode and the electrolyte. Secondly, the laminated structure is easy to delaminate and displace under large deformation, which leads to the obvious reduction of energy storage performance. Therefore, in stretchable flexible supercapacitors, seamless connection and conformal deformation of the electrodes to the electrolyte are imperative.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention provides a high-flexibility integrated supercapacitor, and a method for manufacturing the high-flexibility integrated supercapacitor, which solves the problem of performance degradation of a flexible capacitor with a laminated structure under mechanical deformation.
The technical scheme of the invention is as follows: the utility model provides a high flexible integration ultracapacitor system, includes hydrogel electrolyte layer and at the conducting polymer of hydrogel electrolyte layer both sides in situ polymerization deposit/graphite oxide composite electrode, hydrogel electrolyte layer is ammonium alginate-polyacrylic acid-polyacrylamide hydrogel electrolyte.
Further, the conductive polymer in the conductive polymer/graphene oxide composite electrode is one or more of polyacetylene, polypyrrole, polythiophene and polyaniline.
A preparation method of a high-flexibility integrated supercapacitor comprises the following steps: s1, soaking the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel membrane in an aqueous solution containing transition metal ions and halogen ions to obtain a hydrogel electrolyte; s2, stirring continuously in an ice-water bath,fully dissolving graphene oxide aqueous solution and conductive polymer monomer in H2SO4A solution; s3, dissolving persulfate in H2SO4Dissolving in the solution and cooling; s4, rapidly mixing the solutions obtained in the steps S2 and S3, adding the hydrogel electrolyte, enabling the conductive polymer/graphene oxide composite electrode to be deposited in situ on two sides of the hydrogel electrolyte, cleaning and removing residues, and cutting for four weeks to obtain the high-flexibility integrated supercapacitor.
Further, the hydrogel soaking time in the step S1 is 12-48 h, and the concentration of each transition metal ion is 0.05-0.50M.
Further, the transition metal ion is Cu2+、Fe2+、Fe3+、Mn2+One or more of (a).
Further, the halogen ion is Cl-、Br-One or both of them.
Further, the conductive polymer in the conductive polymer/graphene oxide composite electrode is one or more of polyacetylene, polypyrrole, polythiophene and polyaniline.
Further, said H2SO4The concentration of the solution is 0.5-2.0M, the concentration of the graphene oxide aqueous solution is 1.0-10.0 mg/mL, the persulfate is ammonium persulfate, and the ammonium persulfate and the H are2SO4The mass-to-volume ratio of the solution is 0.2-1.0 g/mL.
Further, in the step S4, the solutions obtained in the steps S2 and S3 are rapidly mixed, and the hydrogel electrolyte is added to the mixture, and then the reaction temperature is maintained at-10 to-5 ℃.
Further, the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel film is prepared by the following steps: fully dissolving acrylamide in deionized water to obtain an acrylamide solution, adding a sodium alginate aqueous solution and acrylic acid into the acrylamide solution, mixing to form a uniform solution, sequentially adding an initiator and a cross-linking agent, uniformly mixing, transferring into a mold, sealing the mold, and heating in a drying oven to obtain the acrylic acid acrylamide.
Compared with the prior art, the invention has the advantages that:
in the conductive polymer/graphene oxide-hydrogel electrolyte integrated supercapacitor constructed by the invention, the hydrogel electrolyte layer contains various physical and chemical crosslinking networks, has excellent toughness and mechanical strength, and provides a template for the deposition of a composite electrode active material; multiple ions are introduced into a hydrogel system to form a multi-crosslinking network, and the conductive polymer/graphene oxide composite active electrode material is polymerized in situ and deposited on two sides of a hydrogel electrolyte to form a strong conformal with the hydrogel electrolyte based on a hydrogen bond effect. Therefore, the conductive polymer/graphene oxide-hydrogel electrolyte integrated supercapacitor has good flexibility, can inhibit the generation of active layer microcracks in the stretching process, keeps the stability of a conductive network and an ion path, and has excellent electrochemical performance even under large stretching deformation. The integrated supercapacitor prepared by the method disclosed by the invention can keep better electrochemical performance under the deformation of bending, compression, stretching and the like, and can meet the energy supply requirement of a flexible wearable electronic device. The preparation method has simple preparation process, does not need special preparation conditions, and adopts halogen ions and SO4 2-The plasma is introduced into a hydrogel system as a cross-linking agent to form a multi-cross-linked network, so that the mechanical property is improved, and the electrical property of the integrated flexible device is further improved. The integrated super capacitor prepared by the invention is suitable for the traditional field of super capacitors and the high-end application fields of wearable electronic equipment, electronic skin, flexible sensors and the like.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a high-flexibility integrated supercapacitor.
Fig. 2 shows the capacity retention of the high-flexibility integrated supercapacitor prepared in example 1 under bending conditions.
Fig. 3 shows the capacity retention of the high-flexibility integrated supercapacitor prepared in example 1 under pressure.
Fig. 4 shows the capacity retention of the high-flexibility integrated supercapacitor prepared in example 1 under tensile deformation conditions.
FIG. 5 is a graph of the flexibility performance of the hydrogel, hydrogel electrolyte and integrated supercapacitor made from example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
Referring to fig. 1, a method for manufacturing a high-flexibility integrated supercapacitor includes the following steps:
preparation of a precursor of the gel electrolyte: 0.1g acrylamide was dissolved in 4.0mL deionized water, added to 4.5g sodium alginate aqueous solution (4.0%), stirred well, then 2.0mL acrylic acid was added, followed by 30min sonication to ensure complete dissolution of the monomer. 0.2g of ammonium persulfate as an initiator and 5.0mg of N, N-methylenebisacrylamide as a crosslinking agent were dissolved in the above solution by sonication to form a mixed solution. Pouring the mixed solution into a mould, and placing the mould in an oven at 55 ℃ for 2h to polymerize the mixed solution to form the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel film. The hydrogel film was removed from the mold and rinsed several times with deionized water to remove unreacted monomer.
Preparation of gel electrolyte: weighing a certain amount of CuSO4And CuBr dissolved in 20mL deionized water to form 0.1M CuSO4And 0.1M CuBr, and soaking the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel film in the solution for 24 hours to form the hydrogel electrolyte.
Preparing a high-flexibility integrated supercapacitor: 1.0mL of aniline and 2.0mL of graphene oxide solution (3.0mg/mL) were mixed in 2.0mL of H in an ice-water bath with constant stirring2SO4(1M) solution A was formed. 0.6g ammonium persulfate dissolved in 2.0mL H2SO4(1M) to form a solution B.
And (3) rapidly mixing the solution A and the solution B, adding the hydrogel electrolyte prepared in the earlier stage, performing cross-linking polymerization at-7 ℃, washing away residues by using ethanol and deionized water after 30min, cutting the periphery of the edge by using a blade to expose the electrode-electrolyte-electrode layered structure, and finally obtaining the integrated anti-deformation supercapacitor taking the PANI/GO composite material as the electrode.
Referring to FIGS. 2 to 4, the elongation at break of the integrated supercapacitor made in this example was determined to be 2500% and the stress at break was determined to be 115 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 150 percent; the specific capacity retention at 50% tensile deformation was 59.3%.
Example 2
Preparing a high-flexibility integrated supercapacitor: 1.0mL of aniline and 2.0mL of graphene oxide solution (1.0mg/mL) were mixed in 2.0mL of H in an ice-water bath with constant stirring2SO4(0.5M) solution A was formed. 0.4g ammonium persulfate dissolved in 2.0mL H2SO4(0.5M) to form solution B. And (2) rapidly mixing the solution A and the solution B, adding the hydrogel electrolyte prepared in the embodiment 1, performing cross-linking polymerization at the temperature of-10 ℃, washing away residues by using ethanol and deionized water after 30min, and cutting the periphery of the edge by using a blade to expose the electrode-electrolyte-electrode layered structure, thereby finally obtaining the integrated anti-deformation supercapacitor taking the PANI/GO composite material as the electrode.
As shown in FIG. 5, the elongation at break of the integrated super capacitor made in this example was 2532% and the stress at break was 200 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention ratio was 56.2% at a tensile deformation of 50%.
Example 3
Preparing a high-flexibility integrated supercapacitor: 1.0mL of aniline and 2.0mL of graphene oxide solution (5.0mg/mL) were mixed in 2.0mL of H in an ice-water bath with constant stirring2SO4(1.5M) to form solution A. 1.0g ammonium persulfate dissolved in 2.0mL H2SO4(1.5M) to form solution B. Rapidly mixing the solutions A and B, adding the hydrogel electrolyte prepared in example 1, performing crosslinking polymerization at-7 deg.C, washing with ethanol and deionized water to remove residues after 30min, and cutting edge with a bladeAnd finally obtaining the integrated anti-deformation supercapacitor taking the PANI/GO composite material as the electrode by exposing the layered structure of the electrode-electrolyte-electrode.
The elongation at break of the integrated supercapacitor prepared in the example is 2516%, and the stress at break is 196 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention ratio was 57.6% at a tensile deformation of 50%.
Example 4
The preparation method of the high-flexibility integrated supercapacitor comprises the following steps:
preparation of a precursor of the gel electrolyte: 0.32g acrylamide was dissolved in 8.0mL deionized water, added to 9.0g sodium alginate aqueous solution (7.0%), stirred well, then 16.0mL acrylic acid was added, followed by sonication for 30min to ensure complete dissolution of the monomer. 0.4g of ammonium persulfate and 10.0mg of N, N-methylenebisacrylamide were dissolved in the above solution by sonication to form a mixed solution. Pouring the mixed solution into a mould, and placing the mould in an oven at 55 ℃ for 2h to polymerize the mixed solution to form the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel film. The hydrogel film was removed from the mold and rinsed several times with deionized water to remove unreacted monomer.
Preparation of gel electrolyte: weighing a certain amount of MnCl2And FeBr in 40mL deionized water to form 0.5M MnCl2And 0.5M FeBr, and soaking the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel membrane in the solution for 48 hours to form the hydrogel electrolyte.
Preparing a high-flexibility integrated supercapacitor: in an ice-water bath, 2.0mL polypyrrole (PPy) and 4.0mL GO solution (10.0mg mL) were added with constant stirring-1) Mixing in 4.0mL H2SO4(2M) solution A was formed. 1.0g ammonium persulfate dissolved in 2.0mL H2SO4(2M) solution B was formed. Rapidly mixing solution A and B, adding the hydrogel electrolyte prepared at the previous stage, performing crosslinking polymerization at-10 deg.C, washing with ethanol and deionized water after 45min to remove residues, and cutting edge with bladeAnd exposing the electrode-electrolyte-electrode layered structure at the periphery to finally obtain the integrated anti-deformation supercapacitor taking the PPy/GO composite material as the electrode.
The super capacitor prepared in the example is detected to have the elongation at break of 2300% and the stress at break of 108 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention at 50% tensile deformation was 68.2%.
Example 5
Preparing a high-flexibility integrated supercapacitor: in an ice-water bath, 2.0mL polypyrrole (PPy) and 4.0mL GO solution (8.0mg mL) were added with constant stirring-1) Mixing in 4.0mL H2SO4(2M) solution A was formed. 1.0g ammonium persulfate dissolved in 2.0mL H2SO4(2M) solution B was formed. And (3) rapidly mixing the solution A and the solution B, adding the hydrogel electrolyte prepared in the embodiment 4, performing cross-linking polymerization at the temperature of-10 ℃, washing away residues by using ethanol and deionized water after 45min, and cutting the periphery of the edge by using a blade to expose the layered structure of the electrode-electrolyte-electrode, thereby finally obtaining the integrated anti-deformation supercapacitor taking the PPy/GO composite material as the electrode.
The supercapacitor made in this example was tested for elongation at break 2382% and stress at break 186 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention at 50% tensile deformation was 58.2%.
Example 6
Preparing a high-flexibility integrated supercapacitor: in an ice-water bath, 2.0mL polypyrrole (PPy) and 4.0mL GO solution (5.0mg mL) were added with constant stirring-1) Mixing in 4.0mL H2SO4(1M) solution A was formed. 2.0g ammonium persulfate dissolved in 2.0mL H2SO4(1M) to form a solution B. Rapidly mixing solution A and B, adding the hydrogel electrolyte prepared in example 4, performing crosslinking polymerization at-10 deg.C, washing with ethanol and deionized water after 45min to remove residue, and cutting with a bladeAnd cutting the periphery of the edge to expose the layered structure of the electrode, the electrolyte and the electrode, and finally obtaining the integrated deformation-resistant supercapacitor taking the PPy/GO composite material as the electrode.
The super capacitor prepared in the example was tested to have elongation at break of 2455% and stress at break of 198 kPa. The specific capacitance of the device is basically lossless under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention at 50% tensile deformation was 59.7%.
Comparative example
Preparing a composite electrode: 1.0mL of aniline and 2.0mL of graphene oxide solution (3.0mg/mL) were mixed in 2.0mL of H in an ice-water bath with constant stirring2SO4(1M) solution A was formed. 0.6g ammonium persulfate dissolved in 2.0mL H2SO4(1M) to form a solution B. And (3) rapidly mixing the solution A and the solution B, performing cross-linking polymerization at the temperature of-7 ℃, and flushing with ethanol and deionized water to remove residues after 30min to obtain the conductive polymer/graphene oxide composite electrode.
Two conducting polymer/graphene oxide composite electrodes with the same size and mass are used as electrode materials, a piece of hydrogel electrolyte with the same size in the embodiment 1 is taken, and PDMS is adopted to stick positive and negative electrodes to two sides of the electrolyte membrane, so that the supercapacitor with the sandwich structure can be obtained.
The comparative supercapacitor was tested to have low stretchability (elongation at break: 155%), poor mechanical strength (stress at break: 23 kPa). The specific capacitance loss of the device is 55% under the bending condition of 0-180 degrees; under the pressure of 5kPa, the specific capacity retention rate exceeds 140 percent; the specific capacity retention at 50% tensile deformation was 33.8%.
Claims (10)
1. The high-flexibility integrated supercapacitor is characterized by comprising a hydrogel electrolyte layer and conducting polymer/graphene oxide composite electrodes which are polymerized and deposited in situ on two sides of the hydrogel electrolyte layer, wherein the hydrogel electrolyte layer is ammonium alginate-polyacrylic acid-polyacrylamide hydrogel electrolyte.
2. The high-flexibility integrated supercapacitor according to claim 1, wherein the conductive polymer in the conductive polymer/graphene oxide composite electrode is one or more of polyacetylene, polypyrrole, polythiophene and polyaniline.
3. A preparation method of a high-flexibility integrated supercapacitor is characterized by comprising the following steps: s1, soaking the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel membrane in an aqueous solution containing transition metal ions and halogen ions to obtain a hydrogel electrolyte; s2, fully dissolving the graphene oxide aqueous solution and the conductive polymer monomer in H by continuously stirring in an ice-water bath2SO4A solution; s3, dissolving persulfate in H2SO4Dissolving in the solution and cooling; s4, rapidly mixing the solutions obtained in the steps S2 and S3, adding the hydrogel electrolyte, enabling the conductive polymer/graphene oxide composite electrode to be deposited in situ on two sides of the hydrogel electrolyte, cleaning and removing residues, and cutting for four weeks to obtain the high-flexibility integrated supercapacitor.
4. The preparation method of the high-flexibility integrated supercapacitor according to claim 3, wherein the hydrogel soaking time in the step S1 is 12-48 h, and the concentration of the transition metal ions is 0.05-0.50M.
5. The method for preparing the high-flexibility integrated supercapacitor according to claim 3, wherein the transition metal ions are Cu2+、Fe2+、Fe3+、Mn2+One or more of (a).
6. The method for preparing the high-flexibility integrated supercapacitor according to claim 3, wherein the halogen ions are Cl-、Br-One or both of them.
7. The preparation method of the high-flexibility integrated supercapacitor according to claim 3, wherein the conductive polymer in the conductive polymer/graphene oxide composite electrode is one or more of polyacetylene, polypyrrole, polythiophene and polyaniline.
8. The method for preparing the high-flexibility integrated supercapacitor according to claim 3, wherein the H is2SO4The concentration of the solution is 0.5-2.0M, the concentration of the graphene oxide aqueous solution is 1.0-10.0 mg/mL, the persulfate is ammonium persulfate, and the ammonium persulfate and the H in the step S3 are mixed2SO4The mass-to-volume ratio of the solution is 0.2-1.0 g/mL.
9. The method for preparing the high-flexibility integrated supercapacitor according to claim 3, wherein in the step S4, the solution obtained in the steps S2 and S3 is rapidly mixed, and then the hydrogel electrolyte is added to the mixture, and then the reaction temperature is maintained at-10 ℃ to-5 ℃.
10. The method for preparing the high-flexibility integrated supercapacitor according to claim 3, wherein the ammonium alginate-polyacrylic acid-polyacrylamide hydrogel film is prepared by the following steps: fully dissolving acrylamide in deionized water to obtain an acrylamide solution, adding a sodium alginate aqueous solution and acrylic acid into the acrylamide solution, mixing to form a uniform solution, sequentially adding an initiator and a cross-linking agent, uniformly mixing, transferring into a mold, sealing the mold, and heating in a drying oven to obtain the acrylic acid acrylamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114429867A (en) * | 2022-03-21 | 2022-05-03 | 南京邮电大学 | Preparation method of full-gel flexible supercapacitor |
| CN115394571A (en) * | 2022-08-03 | 2022-11-25 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
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2021
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114429867A (en) * | 2022-03-21 | 2022-05-03 | 南京邮电大学 | Preparation method of full-gel flexible supercapacitor |
| CN114429867B (en) * | 2022-03-21 | 2023-06-23 | 南京邮电大学 | Preparation method of full-gel flexible supercapacitor |
| CN115394571A (en) * | 2022-08-03 | 2022-11-25 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
| CN115394571B (en) * | 2022-08-03 | 2023-08-18 | 西北工业大学宁波研究院 | Integrated 3D printing flexible supercapacitor prepared through ionic crosslinking and preparation method thereof |
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