CN114464468A - 3D printing flexible supercapacitor based on nitrogen, oxygen, sulfur and chlorine multiple heteroatom doped porous carbon material as electrode - Google Patents
3D printing flexible supercapacitor based on nitrogen, oxygen, sulfur and chlorine multiple heteroatom doped porous carbon material as electrode 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a 3D printing flexible supercapacitor based on a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material as an electrode, which comprises the electrode and an electrolyte, and is prepared according to the following steps: s1: dissolving a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material in a proper solvent, adding an additive in a certain mass ratio into the solvent, and obtaining printing ink by a ball milling method; s2: printing the printing ink serving as a raw material by a 3D printing technology to obtain an interdigital electrode; s3: and (3) adding acid into polyvinyl alcohol serving as a raw material to adjust the pH value, heating and stirring at high temperature to prepare an acidic electrolyte, and coating the acidic electrolyte in the interdigital electrode gap to obtain the flexible micro supercapacitor. The 3D printing technology is simple and convenient to operate, the process is accurate, the obtained flexible super capacitor has excellent electrical performance, high energy density and power density can be kept in stable work, and good conductivity and cycling stability are achieved.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a 3D printing flexible supercapacitor taking a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material as an electrode.
Background
Today, electronic products are facing a transition from rigid devices to flexible, foldable, wherein flexible, wearable electronic products are attracting much attention due to their attractive properties, such as light weight, portability, durability, bendability, and wear resistance. The traditional power supply mode needs to charge or replace the substrate regularly, and is extremely environmentally-friendly; the power output of emerging storage devices that harvest and store energy from natural light, temperature, or motion is mostly irregular and non-uniform; the presence of toxic chemicals in subsequently developed batteries sometimes causes safety problems, while the cycle life of the batteries is often inadequate and instability of the battery assembly can occur. As a substitute for battery, super capacitor has advantages of excellent power density, good stability and long cycle life, and with the rapid development of portable and wearable electronic devices, it is required to develop devices with flexibility and high energy and power performance to meet the demand of miniaturized energy storage devices. Among them, the printed electronics technology provides a series of simple, low-cost, multifunctional and environment-friendly manufacturing technologies for flexible micro supercapacitors. But the processability and stability of the material used for printing is crucial for the successful printing of flexible supercapacitors, where the electrodes, current collectors and electrolyte are the main components of the supercapacitor, with specific requirements in the context of 3D printed supercapacitors.
CN112509820A discloses a 3D printing self-repairing flexible supercapacitor taking an ionic gel electrolyte as a substrate, wherein a carbon nano tube is taken as printing ink, a 1-butyl-3-methylimidazole trifluoromethanesulfonyl imide film (BMIMTFSI-P) is taken as the ionic gel electrolyte and the substrate at the same time, the carbon nano tube is taken as a positive electrode material and a negative electrode material at the same time, and the self-repairing flexible supercapacitor is obtained through an ink direct writing technology.
As described above, the prior art discloses a method for 3D printing a flexible supercapacitor, but the electrode material used in the prior art and the flexible supercapacitor obtained by 3D printing with the adaptive ink have poor electrochemical performance. Based on the defects and improvement direction of the flexible supercapacitor prepared at present, how to select proper electrode materials and printing ink has great significance in obtaining the flexible supercapacitor with good mechanical and electrical properties through a 3D printing technology, wherein the 3D printing of the flexible supercapacitor based on the heteroatom-doped carbon material for the electrode becomes a research hotspot and a focus in the technical field of electrochemical energy storage at present, and the focus and the power of the invention are the aspects of the invention.
Disclosure of Invention
The invention aims to select a proper electrode material and printing ink, and a 3D printing technology is used for obtaining a flexible super capacitor with good mechanical and electrical properties, so that a novel high-performance flexible super capacitor is developed, and particularly a 3D printing flexible super capacitor taking a multi-heteroatom-doped porous carbon material as an electrode is obtained.
Specifically, the technical scheme and content of the invention relate to a 3D printing flexible supercapacitor taking a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material as an electrode.
More specifically, the invention relates to a preparation method of a 3D printing flexible supercapacitor taking a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material as an electrode, which comprises the following steps:
s1: dissolving a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material in a proper solvent, adding an additive in a certain mass proportion into the solvent, and obtaining printing ink by a ball milling method;
s2: printing the printing ink serving as a raw material by a 3D printing technology to obtain an interdigital electrode;
s3: and (3) adding acid into polyvinyl alcohol serving as a raw material to adjust the pH value, heating and stirring at high temperature to prepare an acidic electrolyte, and coating the acidic electrolyte in the interdigital electrode gap to obtain the flexible micro supercapacitor.
In the method for manufacturing a flexible supercapacitor according to the present invention, in step S1, the solvent is required to have a surface tension of 26 to 40mN/m and to have a stable dispersion of the material, and may be, for example, a single system solution, preferably containing ethylene glycol and glycerol as components; the preferred components and proportion of the two-system solution are that the ethylene glycol is acetone, the ethylene glycol is cyclohexanone and the glycerol is cyclohexanone which is 1: 2; the preferred components and the proportion of the three-system solution are acetone, glycol and glycerol 20:9: 1; the most preferred is a three-system solution, i.e. the most preferred components and ratio are acetone, ethylene glycol and glycerol, 20:9: 1.
In the preparation method of the flexible supercapacitor, in step S1, the additives are a binder and a conductive agent, and most preferably, the binder is PVDF and the conductive agent is acetylene black; nitrogen oxygen sulfur chlorine multiple heteroatom doped porous carbon material: adhesive: the molar ratio of the conductive agent is 7-8:1-1.5:1-2, for example, the molar ratio of the nitrogen, oxygen, sulfur and chlorine multiple hetero atom doped porous carbon material to the conductive agent can be 8:1:1, 7:1.5:1.5, 7:2:1, 7:1:2, and most preferably, the molar ratio of the nitrogen, oxygen, sulfur and chlorine multiple hetero atom doped porous carbon material to the conductive agent is 8:1: 1.
In the preparation method of the flexible supercapacitor, in step S1, an instrument used in the ball milling method is a planetary ball mill; the rotation speed of the ball mill is 400-600rpm, for example, 400rpm, 500rpm or 600rpm, and most preferably 500 rpm; the ball milling time is 10-12h, for example 10, 11 or 12h, most preferably 12 h.
In the preparation method of the flexible supercapacitor, in step S2, the 3D printing technology is inkjet printing or dispensing printing, the inkjet printing technology can directly print out an electrode, the printing process is accurate, the pattern uniformity is high, and the printing cost is high; the cost can be reduced and the printing precision can be achieved by dispensing and printing, the problem of high impedance is solved by adding a current collector in a device at the later stage, and the current collector is preferably conductive silver paste; in general, the most preferable 3D printing technique is dispensing printing.
In the method for manufacturing a flexible supercapacitor, in step S3, the electrolyte raw material is polyvinyl alcohol; the acid is concentrated sulfuric acid or concentrated phosphoric acid, and most preferably concentrated sulfuric acid; in the pH adjustment, the amount of polyvinyl alcohol is 1 to 3g, for example 1g, 2g or 3 g; the water amount is 30-40ml, such as 30ml, 35ml or 40 ml; an acid amount of 0.5-2.5g, which may be, for example, 0.5g, 1.5g or 2.5 g; most preferably 3g of polyvinyl alcohol, 40ml of water and 2.5g of concentrated sulfuric acid.
The inventor finds that when the preparation method disclosed by the invention is adopted, particularly certain preferred process parameters are adopted, a flexible supercapacitor with excellent mechanical property and electrochemical property can be obtained, and the beneficial effects are as follows:
1. the nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material is selected as an electrode, the material is a complex two-dimensional structure represented by an interdigital plane structure, the porous structure of the material is favorable for charge storage and electrolyte ion transfer, and the power density and the conductivity of the printed super capacitor can be improved; meanwhile, the material has higher density, and lays a certain foundation for the good mechanical properties of the obtained super capacitor.
2. And (3) selecting a proper additive and a proper solvent in the step S1, selecting a proper electrolyte formula in the step S3, wherein the viscosity of a finally obtained system is 1.55cp, the surface tension is 29.9mN/m, and the ink with high viscosity and thin thinning behavior is obtained, meets the printing requirements of ink-jet printing ink, and can realize the ideal rheological property of 3D printing.
3. The printing method is prepared by a 3D printing technology, so that the printing process is accurate, the pattern integrity is high, the operation is simple and convenient, the forming is rapid, the cost is low, and the printing method is multifunctional and environment-friendly.
4. The 3D printing flexible supercapacitor taking the nitrogen-oxygen-sulfur-chlorine multi-heteroatom doped porous carbon material as the electrode has a plurality of excellent electrochemical functions, and the surface capacitance reaches 11mF/cm at 1mV/s2Current densityThe degree is 0.2mA/cm2When the capacitance is 6mF/cm2Meanwhile, the impedance of the device is only 6 omega, so that high energy density and power density, and good conductivity and cycling stability can be kept in stable work, and the device is applied to the field of electrochemical energy storage and has huge application potential and industrial value.
Drawings
FIG. 1 is a plot of Cyclic Voltammetry (CV) at different scan rates for a flexible supercapacitor of example 1 of the present invention;
FIG. 2 is a graph of constant current charge and discharge curves (GCD) for a flexible supercapacitor according to example 1 of the present invention at different current densities;
FIG. 3 is an electrochemical impedance test chart of the electrodes of the flexible supercapacitor according to example 1 of the present invention;
FIG. 4 is a graph of different electrolyte impedances for comparative examples 4-7;
FIG. 5 is a diagram showing the mixing and dispersion conditions of the nano carbon powders and different solvent ratios in comparative examples 8 to 22.
Detailed Description
The present invention is described in detail below with reference to specific drawings and examples, but the use and purpose of these exemplary drawings and embodiments are only to exemplify the present invention, not to limit the actual scope of the present invention in any way, and not to limit the scope of the present invention.
Example 1: 3D dispensing printing flexible super capacitor M1
S1: weighing 50mg of nitrogen, oxygen, sulfur and chlorine multiple heteroatom doped porous carbon material, 6.25mg of acetylene black and 6.25mg of PVDFF (carbon material: binder: conductive agent: 8:1:1), and performing ball milling for 12 hours by using a planetary ball mill at the rotating speed of 500rpm to uniformly disperse and dissolve the material in 4ml of absolute ethyl alcohol to finally obtain printing ink;
s2: taking the printing ink as a raw material, adding 1.5ml of pH1000 for enhancing conductivity, and carrying out ultrasonic printing for 72 hours to obtain an interdigital electrode; printing conductive silver paste by using dispensing again, heating the conductive silver paste to 150 ℃ in an oven for 30min, and curing the silver paste to obtain a current collector;
s3: weighing 3g of polyvinyl alcohol, adding 30mL of ultrapure water and 2.5mL of concentrated sulfuric acid to adjust the pH, heating at high temperature and stirring to prepare an acidic electrolyte; and printing 1 layer of conductive silver paste (namely a current collector) and 10 layers of carbon material layers by using dispensing printing, and manually coating an acidic electrolyte in the gaps of the interdigital electrodes to assemble a device, namely the flexible micro supercapacitor, wherein the flexible micro supercapacitor is named as M1.
Example 2: 3D ink-jet printing flexible super capacitor M2
Example 1 was repeated by repeating the procedure of example 1 except that 4mL of the anhydrous ethanol solvent was replaced with 30mL of a three-solution system (i.e., 20mL of acetone, 9mL of ethylene glycol and 1mL of glycerol) in the above step S1, the dot-gel printing technique was replaced with the inkjet printing technique in the above step S2, and the procedure of step S3 was not changed except for the addition of a current collector, thereby sequentially performing example 2 and designating the resulting composite material as M2.
And (3) electrochemical performance testing:
the flexible supercapacitor M1 obtained in example 1 was subjected to electrochemical performance tests in a number of different ways, with the following results:
1. FIG. 1 is a plot of Cyclic Voltammetry (CV) for a flexible supercapacitor M1 at different scan rates, showing a near rectangular shape, calculated as 1mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s and 200mV/s with scan rate increasing, and having opposite capacitance values of 11mF/cm, respectively2、9.7mF/cm2、3.68mF/cm2、2.15mF/cm2、1.6mF/cm2、1.2mF/cm2And 0.98mF/cm2The capacitance also has good performance at large scan rates with a constant amount of electrode adhesion.
2. FIG. 2 is a graph of the constant current charge and discharge curve (GCD) of the flexible supercapacitor M1 at different current densities of 0.2mA/cm2、0.3mA/cm2、0.4mA/cm2、0.6mA/cm2、0.8mA/cm2And 1mA/cm2The corresponding surface capacitance is 6mF/cm2、4.8mF/cm2、3.8mF/cm2、3.375mF/cm2、3mF/cm2And 2.6mF/cm2。
3. Fig. 3 is an electrochemical impedance test chart of the flexible supercapacitor M1, and the impedance obtained from the chart is about 6 Ω, because the porous carbon material doped with multiple heteroatoms such as nitrogen, oxygen, sulfur and chlorine has micro mesopores, which is helpful for charge storage and transfer, and finally the device has good conductivity and low impedance.
In conclusion, the 3D printing flexible supercapacitor based on the electrode made of the nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material has a plurality of excellent electrochemical functions, and the surface capacitance reaches 11mF/cm at 1mV/s2The current density is 0.2mA/cm2When the capacitance is 6mF/cm2Meanwhile, the impedance of the device is only 6 omega, so that high energy density and power density, and good conductivity and cycling stability can be kept in stable work, and the device is applied to the field of electrochemical energy storage and has huge application potential and industrial value.
All the characteristics of the electrode M2 of the flexible supercapacitor obtained in example 2 are highly identical to those of the electrode M1 (only the experimental error of measurement exists), and therefore, under the premise of high similarity, the test chart of each electrical property is not listed.
Comparative examples 1 to 3: examination of additives in step S1
Operation S1 was repeated except that the additive ratio in step S1 was changed from the carbon material, binder, and conductive agent to 8:1:1 instead of 7:1.5:1.5, 7:2:1, and 7:1:2, respectively, to obtain comparative examples 1 to 3, and the resulting printed ink was therefore designated as L1 to L3.
The characterization data for each of the printed inks of comparative examples 1-3 is shown in table 1 below:
TABLE 1
Comparative examples 4 to 7: examination of electrolyte in step S3
The operation S3 was repeated except that the electrolyte formulation in step S3 was changed from 3g of polyvinyl alcohol, 30mL of ultrapure water and 2.5mL of concentrated sulfuric acid to that shown in Table 2, to thereby obtain comparative examples 4 to 7, and the resulting electrolytes were thus designated as D1 to D4.
The characterization data for each of the composites of comparative examples 4-7 is shown in Table 2 below:
TABLE 2
Comparative examples 8 to 22: examination of solvent in step S1
Except that the solvent ratio in the step S1 is replaced by (a) butyl acetate from absolute ethyl alcohol; (b) acetone; (c) cyclohexanone; (d) ethylene glycol; (e) glycerol; (f) 1:2 of ethylene glycol and acetone; (g) ethylene glycol, cyclohexanone, 1: 2; (h) ethylene glycol, butyl acetate 1: 2; (i) glycerol acetone is 1: 2; (j) glycerol cyclohexanone is 1: 2; (k) is glycerol butyl acetate 1: 2; (l) Acetone, glycol, glycerol 20:9: 1; (m) Cyclohexanone ethylene glycol Glycerol 20:9:1, the other operations were not changed, so that operation S1 was repeated to obtain comparative examples 8 to 22 in order, and the resulting printed inks were thus designated as a-m.
Conditional screening Performance test
The comparative examples 4 to 22 were tested for performance in different ways, and the results are as follows:
1. FIG. 4 is a graph of the impedance of the various electrolytes of comparative examples 4-7, and it can be seen that the impedance of the D1 acid electrolyte and D3 acid electrolyte is relatively high and not suitable for use in flexible micro supercapacitors, with the minimum impedance being the M1 acid electrolyte formulation, which is optimal.
2. FIG. 5 is a diagram showing the mixing and dispersion of the nano carbon powder in different solvent ratios of comparative examples 8-22, the nano carbon powder cannot be dispersed in the solvents of (a) butyl acetate, (b) acetone and (c) cyclohexanone, and the carbon powder is best dispersed in the separate solvents of (d) ethylene glycol and (e) glycerol; in the two system solutions, (f) the ethylene glycol is acetone, (g) the ethylene glycol is cyclohexanone and the glycerol is cyclohexanone in a ratio of 1:2, the carbon powder is well dispersed in the solvent system, and the delamination and coagulation phenomena occur in the rest of the solutions. Therefore, butyl acetate cannot be used as a dispersant for the carbon material. Meanwhile, in the three-system solution, under the condition that the main solvents of acetone and cyclohexanone and the auxiliary solvents of ethylene glycol and glycerol are 2:1, when the main solvents of cyclohexanone, ethylene glycol and glycerol are 20:7:3, acetone, ethylene glycol and glycerol are 20:7:3, and (m) cyclohexanone, ethylene glycol and glycerol are 20:9:1, carbon powder cannot be dispersed in the system, and in the solvent system of (l), ethylene glycol and glycerol are 20:9:1, the carbon powder can be stably dispersed, and the precipitation phenomenon does not occur. At this time, the viscosity of the (l) acetone-ethylene glycol-glycerol system was measured to be 1.55cp, and the surface tension thereof was measured to be 29.9mN/m, which was in accordance with the printing requirements of the ink-jet printing ink.
Most preferred conditions are:
a: the additive in S1 comprises carbon material, binder and conductive agent in a ratio of 8:1
B: the ratio of the solvent in S1 is acetone, glycol and glycerol is 20:9:1
C: electrolyte formula of S3 ═ 3g polyvinyl alcohol, 30mL ultrapure water and 2.5mL concentrated sulfuric acid
Therefore, when the additive ratio in step S1 is carbon material, binder and conductive agent is 8:1:1, and the viscosity and surface tension of the ink are not greatly affected, the same number of layers are printed, the resistance of a single electrode is the minimum, and the additive ratio is the optimal additive ratio; when the electrolyte formula in the step S3 is 3g of polyvinyl alcohol, 30mL of ultrapure water and 2.5mL of concentrated sulfuric acid, the impedance is the minimum, and the formula is the optimal electrolyte formula; when the solvent ratio in step S1 is acetone, ethylene glycol, and glycerol 20:9:1, the viscosity of the system is 1.55cp, and the surface tension is 29.9mN/m, which meets the printing requirements of the inkjet printing ink, and is the optimal solvent ratio.
As described above, it can be seen from all the above embodiments that the preparation method of the present invention obtains the flexible supercapacitor with excellent electrical properties through the synergistic combination and coordination of specific process steps, process parameters, material selection, etc., so that the flexible supercapacitor can be applied to the field of electrochemical energy storage, and has good application prospects and industrialization potentials.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (8)
1. A3D printing flexible supercapacitor based on a nitrogen oxygen sulfur chlorine multiple heteroatom doped porous carbon material as an electrode comprises the electrode and electrolyte, and is characterized in that: the flexible supercapacitor is prepared according to the following steps:
s1: dissolving a nitrogen-oxygen-sulfur-chlorine multiple heteroatom doped porous carbon material in a proper solvent, adding an additive in a certain mass ratio into the solvent, and obtaining printing ink by a ball milling method;
s2: printing the printing ink serving as a raw material by a 3D printing technology to obtain an interdigital electrode;
s3: and (3) adding acid into polyvinyl alcohol serving as a raw material to adjust the pH value, heating and stirring at high temperature to prepare an acidic electrolyte, and coating the acidic electrolyte in the interdigital electrode gap to obtain the flexible micro supercapacitor.
2. The method of claim 1, wherein: in step S1, the solvent is a single system solution, and preferably contains ethylene glycol and glycerol as components; the preferred components and proportion of the two-system solution are that the ethylene glycol is acetone, the ethylene glycol is cyclohexanone and the glycerol is cyclohexanone which is 1: 2; the preferred components and the proportion of the three-system solution are acetone, glycol and glycerol 20:9: 1; the most preferred is a three-system solution, i.e. the most preferred components and ratio are acetone, ethylene glycol and glycerol, 20:9: 1.
3. The method of claim 1, wherein: in step S1, the additives are a binder and a conductive agent, and the molar ratio of the additives is nitrogen, oxygen, sulfur and chlorine multiple heteroatom doped porous carbon material: adhesive: the conductive agent is 7-8:1-1.5:1-2, and the optimal component selection molar ratio is that the nitrogen, oxygen, sulfur and chlorine multiple heteroatom is doped with the porous carbon material: adhesive: the conductive agent is 8:1: 1.
4. The method of claim 1, wherein: in step S2, the 3D printing technique is inkjet printing or dot printing, and most preferably dot printing.
5. The method of claim 1, wherein: in step S3, the acid is concentrated sulfuric acid, concentrated phosphoric acid, and most preferably concentrated sulfuric acid.
6. A3D printing flexible supercapacitor taking the nitrogen oxygen sulfur chlorine multiple heteroatom doped porous carbon material as an electrode as claimed in any one of claims 1 to 5, wherein: under the condition that the electrode attachment amount is certain, along with the increase of the sweeping speed, the cyclic voltammetry curve stability is good, namely the flexible supercapacitor has good ion conduction capability and shows excellent capacitance performance.
7. A3D printing flexible supercapacitor taking the nitrogen oxygen sulfur chlorine multiple heteroatom doped porous carbon material as an electrode as claimed in any one of claims 1 to 5, wherein: the specific capacitance of the flexible super capacitor reaches 11mF/cm at a scanning rate of 1mV/s2The impedance of the whole device is only 6 omega, and the good conductivity is shown.
8. A3D printing flexible supercapacitor taking the nitrogen oxygen sulfur chlorine multiple heteroatom doped porous carbon material as an electrode as claimed in any one of claims 1 to 5, wherein: when the current density is 0.2-1mA/cm2The specific capacity of the flexible super capacitor is 2.6-6mF/cm2The capacity retention rate is 40-50%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520829A (en) * | 2018-04-11 | 2018-09-11 | 北京理工大学 | A kind of nitrogen oxygen codope activated carbon gas gel electrode material, solid-state super capacitor and preparation method thereof |
| CN110431410A (en) * | 2017-03-31 | 2019-11-08 | 英诺斯森提亚公司 | Sensing material, the method and its application for manufacturing function device |
| CN110895998A (en) * | 2019-11-22 | 2020-03-20 | 西安交通大学 | Electrode material ink, preparation method and method for preparing miniature super capacitor by using electrode material ink |
| CN112357900A (en) * | 2020-09-08 | 2021-02-12 | 温州大学新材料与产业技术研究院 | High-density nitrogen, oxygen and chlorine co-doped carbon particle material, and preparation method and application thereof |
| CN112357901A (en) * | 2020-09-09 | 2021-02-12 | 温州大学新材料与产业技术研究院 | Preparation method of nitrogen-sulfur co-doped micro-mesoporous carbon sphere/sheet material, product and application thereof |
| CN112908727A (en) * | 2021-02-05 | 2021-06-04 | 华南理工大学 | High-performance flexible micro super capacitor and preparation method and application thereof |
-
2022
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110431410A (en) * | 2017-03-31 | 2019-11-08 | 英诺斯森提亚公司 | Sensing material, the method and its application for manufacturing function device |
| CN108520829A (en) * | 2018-04-11 | 2018-09-11 | 北京理工大学 | A kind of nitrogen oxygen codope activated carbon gas gel electrode material, solid-state super capacitor and preparation method thereof |
| CN110895998A (en) * | 2019-11-22 | 2020-03-20 | 西安交通大学 | Electrode material ink, preparation method and method for preparing miniature super capacitor by using electrode material ink |
| CN112357900A (en) * | 2020-09-08 | 2021-02-12 | 温州大学新材料与产业技术研究院 | High-density nitrogen, oxygen and chlorine co-doped carbon particle material, and preparation method and application thereof |
| CN112357901A (en) * | 2020-09-09 | 2021-02-12 | 温州大学新材料与产业技术研究院 | Preparation method of nitrogen-sulfur co-doped micro-mesoporous carbon sphere/sheet material, product and application thereof |
| CN112908727A (en) * | 2021-02-05 | 2021-06-04 | 华南理工大学 | High-performance flexible micro super capacitor and preparation method and application thereof |
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