CN113327775B - Preparation method of potassium ion micro hybrid capacitor and electrode material - Google Patents
Preparation method of potassium ion micro hybrid capacitor and electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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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Abstract
The invention relates to a preparation method of a potassium ion micro hybrid capacitor and an electrode material. The method uses an air spray gun to spray an active material on polyethylene terephthalate (PET) with the assistance of a mould, and a miniature flexible interdigital electrode with a multidirectional ion transmission channel is constructed on a PET transparent flexible substrate. And after the electrodes are dried in vacuum, coating the microporous polymer electrolyte on the surfaces of the electrodes, finally putting the electrodes into a vacuum bag, dropwise adding the electrolyte and packaging to obtain the flexible potassium ion micro-hybrid capacitor. The electrode material is a multidimensional topological structure material with part of potassium titanate growing between graphite layers; in the preparation method, potassium hydroxide is taken as a potassium source, nano titanium dioxide is taken as a titanium source, and the potassium hydroxide and the nano titanium dioxide are hydrothermally compounded with flake graphite at the temperature of 100-250 ℃. The material obtained by the invention effectively solves the problems of low conductivity, low capacity and poor rate capability of the potassium titanate material.
Description
Technical Field
The invention belongs to the field of high specific energy supercapacitors, and particularly relates to an electrode material of a potassium ion micro hybrid capacitor, and a preparation method and application thereof.
Background
With the continuous development of society, the functional requirements of people on electronic products are also continuously improved, and the electronic products also meet the high-speed development period. For example, smart phones, tablet computers, smart robots, electronic watches, and various wearable devices are continuously developing towards miniaturization and flexibility. These self-powered electronic products, which are gradually becoming smaller and more flexible, also face power supply problems. Therefore, electrochemical energy storage devices of various dimensions become key power sources for miniaturized and flexible intelligent and integrated electronic products, such as self-powered microsystems of human body sensors, micro-robots and the like. At present, various advanced energy storage devices mainly comprise lithium ion batteries and capacitors, but limited lithium resources of the advanced energy storage devices also arouse the enthusiasm of people for developing other energy storage devices. Potassium ions are a hotspot of research because of abundant resources and oxidation-reduction potential close to that of lithium ions.
However, potassium ion energy storage devices also face some challenges, such as potassium ion (0.138 nm) being larger in size than lithium ion (0.076 nm), so that the kinetics of insertion/extraction of potassium ions in the electrode material is slow, resulting in low capacity and poor cycling stability and rate capability of the electrode material. The Ti-based compound can be used as an ideal candidate material for safe and stable operation of a negative electrode of a lithium ion battery, such as lithium titanate (Li)4Ti5O12LTO), is currently used on a large scale in the field of commercial lithium ion batteries and lithium ion hybrid capacitors. Thus, potassium titanate (K)2TinO2n+1KTO) is also expected to be well applied in the field of potassium ion batteries or hybrid capacitors. The KTO ternary cathode can provide high-efficiency K+The intercalation channel and the insertion/de-intercalation process have little influence on the basic structure and the performance, thereby having good cycle stability. However, the electronic conductivity of the material is low, so that the performance of potassium storage performance is inhibited, and the development of potassium ion energy storage devices is limited. Recently two titanium-based compounds K have been reported2Ti4O9And K2Ti8O17And applied to potassium ion energy storage devices, however, they have very limited cycling and rate capability. In order to improve the potassium storage performance of KTO, the effective technical route is to regulate and control the component composition, the microstructure and the composition with the high-conductivity carbon material.
Disclosure of Invention
The invention aims to provide a potassium ion micro hybrid capacitor, a preparation method thereof and an electrode material, aiming at the problem that the raw material resource of a lithium ion energy storage device in the prior art is limited. The electrode material is a multidimensional topological structure material with part of potassium titanate growing between graphite layers; in the preparation method, potassium hydroxide is used as a potassium source, nano titanium dioxide is used as a titanium source, and the potassium hydroxide and the flake graphite are subjected to hydrothermal compounding at the temperature of 100-250 ℃, so that the obtained material effectively solves the problems of low conductivity, low capacity and poor rate capability of the potassium titanate material. In application, the invention abandons the traditional sandwich type flexible capacitor, uses an air spray gun to spray the active material on polyethylene terephthalate (PET) with the assistance of a mould, and constructs the miniature flexible interdigital electrode with a multidirectional ion transmission channel on a PET transparent flexible substrate. And after the electrodes are dried in vacuum, coating the microporous polymer electrolyte on the surfaces of the electrodes, drying an organic solvent in the electrolyte, putting the electrodes into a vacuum bag in an argon glove box, dropwise adding electrolyte, and packaging to obtain the flexible potassium ion micro-hybrid capacitor. By controlling the spraying amount of the active material, the capacitor can obtain different area specific capacities.
In order to achieve the above purpose, the invention adopts the following technical scheme.
A preparation method of a potassium ion micro hybrid capacitor comprises the following steps:
(1) adding polyoxyethylene and PVDF-HFP into an organic solvent, and stirring for 18-24h at 40-80 ℃ to obtain a microporous polymer electrolyte;
wherein, 20-50mg of polyoxyethylene and 800-1000mg of PVDF-HFP are added into each 6-19ml of organic solvent;
(2) adding a potassium titanate @ graphite compound serving as a capacitor negative electrode active substance into deionized water to prepare a mixed solution with the concentration of 0.5-1mg/ml, adding a certain amount of alkalized MXene solution, conductive Carbon Black (CB) serving as a conductive agent and carboxymethyl cellulose (CMC) serving as a binder into the mixed solution, and preparing a negative electrode material mixed solution;
wherein the mass ratio of the potassium titanate @ graphite compound to the alkalized MXene, CB and CMC is (14: 2-5: 0.5-2.5: 0.5-3), and the concentration of the alkalized MXene solution is 4-6 mg/ml;
in addition, adding Activated Carbon (AC) into deionized water to prepare a mixed solution with the concentration of 0.5-1mg/ml as a capacitor positive electrode active substance, and adding an alkalized MXene solution, conductive Carbon Black (CB) and carboxymethyl cellulose (CMC) into the mixed solution to prepare a positive electrode material mixed solution; wherein the mass ratio of AC, alkalized MXene, CB and CMC is (14: 2-5: 0.5-2.5: 0.5-3), and the concentration of the alkalized MXene solution is 4-6 mg/ml;
(3) fixing an interdigital electrode metal mold on PET, shielding the anode of the metal mold by using a baffle, spraying 0.05-0.1ml of silver nanowire solution on the PET by using a spray gun to serve as a current collector, and spraying the prepared cathode mixed solution on the silver nanowires to construct the cathode part of the interdigital electrode; the density of the active material (potassium titanate @ graphite compound) dressing of the negative electrode is 4-480 mu g cm-2；
Then taking down the baffle fixed on the positive electrode of the mold, fixing the negative part of the metal mold, spraying 0.05-0.1ml silver nanowire solution on PET as a current collector by using a spray gun, and spraying the prepared positive electrode mixed solution on the silver nanowires to construct the positive electrode part of the interdigital electrode, wherein the active substance (AC) dressing density of the positive electrode is 6-500 mu g cm-2；
(4) Respectively adhering an aluminum lug and a nickel lug to the positive electrode part and the negative electrode part of the interdigital electrode prepared in the previous step by using copper paste, drying at 50-100 ℃, coating the prepared microporous polymer electrolyte on the electrode, drying at 50-110 ℃, and finally putting the dried electrode into a vacuum bag in an argon glove box, dropwise adding electrolyte and packaging.
The organic solvent in the step (1) is acetone and alcohol with the volume ratio of (4-5): 1 in a liquid mixture.
And (4) drying in vacuum.
A potassium titanate @ graphite composite serving as an electrode material of a potassium ion battery is composed of one-dimensional nanowire-shaped potassium titanate and quasi-two-dimensional graphite nano-sheets, wherein the mass ratio of the potassium titanate to the graphite nano-sheets is (4-5): 1; the interconnected nanowire-shaped potassium titanate with the diameter of 7.5-8.0nm is uniformly distributed among the two-dimensional graphite nanoplatelets to form a multi-dimensional hierarchical structure; meanwhile, the specific surface area of the material is as high as 168.9m2 g-1The corresponding pore size is mainly distributed in the range of 5-30nm, and one existsAnd the micropores and the macropores show the stacking structure of the one-dimensional and two-dimensional composite materials.
A preparation method of an electrode material potassium titanate @ graphite compound of a potassium ion battery comprises the following steps:
adding a titanium source into the potassium source solution, adding graphite, and carrying out hydrothermal reaction at the temperature of 100 ℃ and 250 ℃ for 20-50h to obtain the nano linear potassium titanate @ graphite composite material;
wherein, the potassium source is potassium hydroxide, and the titanium source is nano titanium dioxide; the mass ratio of the potassium hydroxide to the titanium dioxide to the graphite is (200-): (2-3): 1, the concentration of the potassium hydroxide aqueous solution is (9-11) mol/L;
the preparation method of the two-dimensional alkalized MXene comprises the following steps:
adding lithium fluoride into hydrochloric acid, mixing to obtain etching solution, adding Ti3ALC2Etching at 30-40 ℃ for 20-35h, centrifuging with deionized water at 3000-8000r/min for 7-9 times to remove the acidic etching solution, dissolving the centrifuged precipitate in water, dissolving the precipitate obtained per 10mL hydrochloric acid in 50-80mL of water, and performing ice domain ultrasound for 30-60 min; centrifuging the solution after ultrasonic treatment at the rotating speed of 2000-4000r/min for 5-10min, and taking out the upper layer liquid, namely the single-layer MXene solution;
then alkalizing the monolayer MXene for 20-40h at room temperature according to the proportion of adding 10-30g of potassium hydroxide into each 60ml of MXene solution, centrifuging at the rotating speed of 4000-;
the concentration of the hydrochloric acid is (10-15) M, and 800-2000mg of lithium fluoride is added into each 10ml of hydrochloric acid; adding 500-1200mg Ti into 10mL etching solution3ALC2；
The invention has the beneficial effects that:
(1) the invention provides a potassium titanate @ graphite electrode material, which not only eliminates the problem of extremely poor electrochemical performance caused by a two-dimensional stacking effect after pure graphite spraying, but also effectively solves the problems of low conductivity, low capacity and poor rate capability of a potassium titanate material by carrying out hydrothermal compounding on nano linear potassium titanate and flake graphite.
(2) The two-dimensional MXene material with excellent conductivity is used as a conductive agent, and is respectively added into the negative electrode and the positive electrode according to a certain proportion to prepare the interdigital electrode, so that the interdigital electrode can play a role of a bridge, and the negative electrode potassium titanate @ graphite electrode material and the positive electrode active material active carbon are respectively connected, so that a good channel is provided for electron transmission, and the conductivity of the interdigital electrode is greatly improved.
(3) The two-dimensional MXene material is alkalized for a certain time in a potassium hydroxide solution with a certain concentration, so that a certain amount of nano holes are generated on the two-dimensional surface of the two-dimensional MXene material, and the two-dimensional MXene material can play a role in transmitting electrons and cannot block the diffusion of ions in an electrode when being used as a conductive agent, so that the blocking effect of the two-dimensional MXene material on the electrochemical performance of an electrode active substance is greatly reduced.
(4) The invention abandons the traditional capacitor with a sandwich structure and adopts the interdigital electrode with a multidirectional rapid ion transmission channel, and the distance between each anode and cathode interdigital of the interdigital structure is 500 mu m, so that the micro capacitor electrode has 12.5mF cm-2Very high area specific capacity.
(5) Compared with the traditional water system capacitor with the maximum voltage of 1.5V, the capacitor provided by the invention can be charged to 3V due to the use of the interdigital electrode, the potassium titanate @ graphite electrode material and the semi-solid organic electrolyte. And has good integration performance, and the maximum voltage of 6V can be obtained if two capacitors are connected in series.
Drawings
FIG. 1 is an XRD pattern of the potassium titanate graphite composite in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the potassium titanate graphite composite in example 1;
FIG. 3 is a photograph of the assembled micro-capacitor;
FIG. 4 is a time-voltage diagram for different current densities for example 1;
Detailed Description
The invention will be further described with reference to the accompanying drawings in connection with preferred embodiments.
The object of the present invention is to produce a flexible micro-capacitor with a high area specific capacity and a high energy power density. The potassium titanate and the graphite are compounded by a hydrothermal method, so that the agglomeration of the potassium titanate and the tiling effect of the graphite are reduced, the specific capacity of the material is improved, and the rate capability and the cycling stability of the potassium titanate material are improved. And after the active carbon serving as the cathode is mixed with a certain proportion of alkalized porous MXene, CMC and CB, the asymmetric miniature capacitor is assembled on a PET flexible substrate. The specific method comprises the following steps: (1) preparation of an alkalised MXene solution: adding 800-2000mg lithium fluoride into 10ml (10-15) M hydrochloric acid, stirring for 5-10min, and adding 500-1200mg Ti3ALC2Stirring the powder at 30-40 deg.C for 20-35h, centrifuging with deionized water to pH of about 7, dissolving the centrifuged precipitate in 60-100mL deionized water, and subjecting to ice field ultrasound for 30-60 min. Centrifuging the solution after ultrasonic treatment for 5-10min at the rotation speed of 2000-4000r/min, and taking out the upper layer liquid to obtain the MXene solution. Adding 10-30g of potassium hydroxide into the dispersed MXene solution, stirring for 20-40h, and removing the potassium hydroxide in the solution by centrifugation to obtain the alkalized MXene. (2) Preparation of potassium titanate @ graphite composite material: adding 10-20mg of graphite, 30-60mg of nano titanium dioxide and 5-8g of potassium hydroxide into deionized water to obtain a mixed solution, stirring for 300min, transferring the mixed solution into a high-pressure reaction kettle, reacting for 20-50h at the temperature of 100-250 ℃ to obtain a potassium titanate @ graphite compound, washing the potassium titanate @ graphite compound with deionized water until the pH value is neutral, and drying in an oven at the temperature of 70-100 ℃ for 12-24h to obtain potassium titanate @ graphite compound powder. (3) Preparation of microporous polymer electrolyte material: taking 20-50mg of polyoxyethylene and 800-1000mg of PVDF-HFP, adding 5-15ml of acetone and 1-4ml of absolute ethyl alcohol, and stirring at 40-80 ℃ for 18-24h to obtain the microporous polymer electrolyte. (4) Preparation of negative electrode material solution: deionized water is used as a solvent, a certain amount of potassium titanate @ graphite compound is added to serve as a capacitor negative electrode active substance, and a certain amount of alkalized MXene solution, conductive carbon Black (BC) and CMC are added to prepare a negative electrode material solution. (5) Preparing a positive electrode material solution: deionized water is used as solvent, and a certain amount of activity is added into the deionized waterCarbon is used as a negative electrode active substance of the capacitor, and a certain amount of alkalized MXene, conductive carbon Black (BC) and CMC are added into the carbon to prepare a positive electrode material solution. (6) Preparing an interdigital electrode: fixing the interdigital electrode metal mold on PET, fixing a baffle plate of the interdigital electrode mold at the position of the anode of the metal mold, spraying silver nanowires with a certain thickness by using a spray gun, and spraying the prepared cathode mixed solution on the silver nanowires to construct the cathode part of the interdigital electrode. And then the baffle fixed on the positive electrode of the metal mold is taken down from the negative electrode part fixed on the metal mold, and the positive electrode part of the interdigital electrode is constructed in the same step similar to the negative electrode. (7) And assembling the micro capacitor, namely respectively adhering an aluminum lug and a nickel lug to the positive electrode part and the negative electrode part of the interdigital electrode prepared in the previous step by using copper paste, drying the interdigital electrode in vacuum at 50-100 ℃, coating the prepared microporous polymer electrolyte on the interdigital electrode, drying the interdigital electrode in vacuum at 50-110 ℃, putting the interdigital electrode into a vacuum bag in an argon glove box, dropwise adding the electrolyte, and packaging.
For a better understanding of the invention, it will be described in detail below with reference to 4 examples. It should be understood that these examples are illustrative only and are not limiting. The compounds or reagents used in the following examples are commercially available or can be prepared by conventional methods known to those skilled in the art; the laboratory instruments used are commercially available.
Example 1:
the method comprises the following steps: 1600mg of lithium fluoride is added into 10ml (12M) of dilute hydrochloric acid, stirred for 5min and then 1000mg of Ti with the particle size of 300 molybdenum is added3ALC2Powder, stirring at 35 deg.C for 24 hr to remove Ti3ALC2The AL layer in the powder was etched away, then washed centrifugally with deionized water at 3500r/min to a pH of about 7, and the centrifuged precipitate was dissolved in 60mL of deionized water and subjected to ice bath sonication for 60 min. Centrifuging the solution after ultrasonic treatment at 3500r/min for 5min, and taking out the upper layer liquid to obtain the monolayer MXene solution.
20.16g of potassium hydroxide is added to the dispersed MXene solution, after stirring at room temperature for 36h (room temperature basification of the monolayer MXene), the solution is centrifuged at 4500r/min to pH 7 to remove the potassium hydroxide, and a certain amount of deionized water is added to the centrifuged precipitate to obtain an alkalized MXene solution with a porous structure having a concentration of 5 mg/ml.
Adding 20mg of graphite and 50mg of nano titanium dioxide into 10ml (10M) of potassium hydroxide aqueous solution to obtain a mixed solution, stirring for 250min, transferring the mixed solution into a high-pressure reaction kettle, reacting for 48h at 200 ℃ to obtain a potassium titanate @ graphite compound, centrifugally washing the potassium titanate @ graphite compound with deionized water at a rotating speed of 8000r/min until the pH value is neutral, and drying in an oven at 80 ℃ for 12h to obtain potassium titanate @ graphite compound powder.
40mg of polyethylene oxide and 800mg of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) were taken, 10ml of acetone, 2ml of anhydrous ethanol was further added thereto, and stirring was carried out at 70 ℃ for 20 hours to obtain a microporous polymer electrolyte.
Step two: taking 1.8mg of potassium titanate @ graphite compound, dispersing the potassium titanate @ graphite compound in 4ml of deionized water, adding 0.103ml of alkalized MXene dispersion liquid with the concentration of 5mg/ml, 0.129mg of CB and 0.129mg of CMC, and mechanically stirring for 5 hours to obtain a negative electrode material mixed liquid.
Step three: 2.7mg of activated carbon was dispersed in 6ml of deionized water, and 0.155ml of an alkalized MXene dispersion having a concentration of 5mg/ml, 0.194mg of CB and 0.194mg of CMC were added thereto, followed by mechanical stirring for 5 hours to obtain a positive electrode material mixture.
Step four: after the PET was washed clean with water, it was placed in an ultraviolet washer for 2 min.
Step five: the cleaned PET was removed and glued to the metal interdigitated mold with a small amount of solid.
Step six: and shielding the anode part of the metal interdigital mould by using an interdigital electrode baffle.
Step seven: 20 μ L of silver nanowires were placed in a spray gun and sprayed at a rate of 1ml/h onto the negative portion of the interdigitated electrodes. (area of 4.16cm2)
Step eight: and (4) putting the mixed solution prepared in the first step into a spray gun, and completely spraying the mixed solution on the silver nanowires at the speed of 2 ml/h.
Step nine: and after spraying, removing the interdigital baffle of the cathode, and shielding the anode part of the interdigital metal template by using the baffle in the same way.
Step ten: mu.L of silver nanowires were placed in a spray gun and sprayed at a rate of 1ml/h onto the positive part of the interdigitated electrodes (same area as the negative electrode).
Step eleven: and (4) putting the mixed solution prepared in the second step into a spray gun, and completely spraying the mixed solution on the silver nanowires at the speed of 2 ml/h.
Step twelve: and removing the interdigital baffle of the anode after spraying, and then taking down the interdigital template to obtain the interdigital electrode.
Step thirteen: and adhering the aluminum lug and the nickel lug to the positive electrode and the negative electrode of the electrode by using copper paste.
Fourteen steps: and (3) placing the prepared interdigital electrode in a vacuum oven, and drying for 15h at the temperature of 80 ℃ to completely remove the residual moisture in the electrode.
Step fifteen: dropping two drops of the prepared microporous polymer electrolyte on the electrode by using a dropper, uniformly coating the microporous polymer electrolyte, placing the interdigital electrode coated with the microporous polymer in a vacuum oven, and drying at the temperature of 80 ℃ for 12 hours to completely remove the residual organic solvent in the electrode.
Sixthly, the steps are as follows: in an argon glove box, the dried electrodes were sealed with a small vacuum sealer.
Seventeen steps: and opening a small opening on the side, which does not contain the tab, of the vacuum bag of the sealed electrode, and injecting the potassium ion electrolyte into the electrode.
Eighteen steps: electrolyte injection (0.8M KPF)6DEC ═ 1:1 Vol%) for 6h, and then the excess electrolyte was extracted with a vacuum sealer and sealed to obtain a flexible potassium titanate micro capacitor.
Example 2:
the difference between example 2 and example 1 is only that the usage amounts of the positive and negative electrode active material solutions of the interdigital electrode are different, and the usage amounts are 60 μ L of the prepared positive electrode mixed solution and 90 μ L of the prepared negative electrode mixed solution.
Example 3:
example 3 differs from example 1 only in the amount of the positive and negative electrode active material solutions used in the interdigital electrode, and the amount of the positive electrode mixed solution prepared was 40 μ L and the amount of the negative electrode mixed solution prepared was 60 μ L.
Example 4:
example 4 differs from example 1 only in the amount of the positive and negative electrode active material solutions used in the interdigital electrode, and the amount of the positive electrode mixed solution prepared was 20 μ L and the amount of the negative electrode mixed solution prepared was 30 μ L.
The capacitors of the examples were tested for electrochemical performance (using a Princeton electrochemical workstation, with a voltage range selected from 0.01 to 3V and a current density of 0.005mA cm-2-0.2mA cm-2The results are shown in Table 1.
TABLE 1 capacitor Capacity test results for the examples
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The invention is not the best known technology.
Claims (4)
1. A preparation method of a potassium ion micro-hybrid capacitor is characterized by comprising the following steps:
(1) adding polyoxyethylene and PVDF-HFP into an organic solvent, and stirring for 18-24h at 40-80 ℃ to obtain a microporous polymer electrolyte;
wherein, 20-50mg of polyoxyethylene and 800-1000mg of PVDF-HFP are added into each 5-15ml of organic solvent;
(2) adding the potassium titanate @ graphite compound into deionized water as a negative electrode active substance of the capacitor to prepare the additive with the concentration of 0.4-
1mg/ml of mixed solution, and then adding a certain amount of alkalized MXene solution, conductive carbon black serving as a conductive agent and carboxymethyl cellulose serving as a binder to prepare mixed solution of a negative electrode material;
wherein the mass ratio of the potassium titanate @ graphite compound to the alkalized MXene to the conductive carbon black to the carboxymethyl cellulose is (14: 2-5: 0.5-2.5: 0.5-3), and the concentration of the alkalized MXene solution is 4-6 mg/ml;
in addition, adding activated carbon into deionized water to prepare a mixed solution with the concentration of 0.4-1 mg/ml as a capacitor positive electrode active substance, adding an alkalized MXene solution, conductive carbon black and carboxymethyl cellulose into the mixed solution, and mixing to obtain a positive electrode material mixed solution; wherein the mass ratio of the activated carbon to the alkalized MXene to the conductive carbon black to the carboxymethyl cellulose is (14: 2-5: 0.5-2.5: 0.5-3), and the concentration of the alkalized MXene solution is 4-6 mg/ml;
(3) fixing the interdigital electrode metal mold on PET, shielding the anode of the metal mold by a baffle plate, and spraying 4-15 mu L cm by a spray gun-2The silver nanowire solution is used as a current collector on PET, and the prepared negative electrode mixed solution is sprayed on the silver nanowires to construct a negative electrode part of the interdigital electrode; the density of the active material dressing of the negative electrode is 4-480 mu g cm-2；
Then the baffle fixed on the positive electrode of the mold is taken down and fixed on the negative electrode part of the metal mold, and a spray gun is used for spraying 4-15 mu L cm-2The silver nanowire solution is used as a current collector on PET, and the prepared anode mixed solution is sprayed on the silver nanowires to construct an anode part of the interdigital electrode, wherein the active substance dressing density of the anode is 6-500 mu g cm-2；
(4) Respectively adhering an aluminum lug and a nickel lug to the positive electrode part and the negative electrode part of the interdigital electrode prepared in the previous step by using copper paste, drying at 50-100 ℃, coating the prepared microporous polymer electrolyte on the electrode, drying at 50-110 ℃, and finally putting the dried electrode into a vacuum bag in an argon glove box, dropwise adding electrolyte and packaging.
2. The method for preparing a potassium ion micro-hybrid capacitor as claimed in claim 1, wherein the organic solvent in step (1) is acetone and alcohol in a volume ratio of (4-5): 1 in a liquid mixture.
3. The method of claim 1, wherein the drying in step (4) is vacuum drying.
4. The method of claim 1, wherein the method of preparing alkalized MXene comprises the steps of:
adding lithium fluoride into hydrochloric acid, mixing to obtain etching solution, adding Ti3AlC2Etching at 30-40 ℃ for 20-35h, centrifugally washing with deionized water at a rotating speed of 3000-8000r/min to neutrality, dissolving the centrifuged precipitate in water, dissolving the precipitate obtained per 10mL of hydrochloric acid in 50-80mL of water, and performing ice bath ultrasound for 30-60 min; centrifuging the solution after ultrasonic treatment at the rotating speed of 2000-4000r/min for 5-10min, and taking out the upper layer liquid, namely the single-layer MXene solution;
then 10-30g of potassium hydroxide is added into each 60ml of MXene solution, the mixture is stirred for 20-40h, the mixture is centrifuged at the rotating speed of 4000-;
the concentration of the hydrochloric acid is (10-15) M, and 800-2000mg of lithium fluoride is added into each 10ml of hydrochloric acid; adding 500-1200mg Ti into 10mL etching solution3AlC2。
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