CN114614112A - Preparation method of solid-state energy storage device taking MXene as electrode and PVA-based hydrogel as electrolyte - Google Patents
Preparation method of solid-state energy storage device taking MXene as electrode and PVA-based hydrogel as electrolyte Download PDFInfo
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- 239000010936 titanium Substances 0.000 claims description 28
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910019762 Nb4C3 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- PPVRVNPHTDGECD-UHFFFAOYSA-M F.[Cl-].[Li+] Chemical compound F.[Cl-].[Li+] PPVRVNPHTDGECD-UHFFFAOYSA-M 0.000 claims description 2
- 229910003178 Mo2C Inorganic materials 0.000 claims description 2
- 229910004472 Ta4C3 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
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- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
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- 239000011248 coating agent Substances 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 241000282414 Homo sapiens Species 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0056—Preparation of gels containing inorganic material and water
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Abstract
The invention belongs to the technical field of electrolyte of a solid energy storage device and preparation of the whole device, and particularly relates to a preparation method of the solid energy storage device by taking MXene as an electrode and PVA-based hydrogel as the electrolyte, which comprises the following steps of 1: weighing PVA with the mass fraction of 15%, adding water with the mass fraction of 85%, and heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding 4M protonic acid relative to water under stirring, and standing until defoaming; step 2: injecting the solution obtained in the step into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing the electrolyte mould for 20 hours, taking the electrolyte mould out, and standing the electrolyte mould for 3 hours at room temperature; and step 3: and (3) repeating the step 2 of freezing and standing in the step 2, taking out and demoulding to obtain the PVA-based hydrogel electrolyte, wherein the structure is reasonable, and the prepared MXene solid energy storage device has excellent rate performance which exceeds that of a corresponding water system MXene energy storage device. And meanwhile, the composite material has excellent cycle performance, high area capacitance, high energy density and high power density.
Description
Technical Field
The invention relates to the technical field of electrolyte of a solid-state energy storage device and preparation of the whole device, in particular to a preparation method of the solid-state energy storage device by taking MXene as an electrode and PVA-based hydrogel as the electrolyte.
Background
In the 21 st century, the living standard of human beings is greatly improved, and the movable and wearable electronic equipment is rapidly developed, so that great convenience is brought to the human beings. With the rapid rise of the demand of the modern society for rapid and portable movable charging and discharging equipment, more demands are put on the further upgrade of the flexible solid-state energy storage device by human beings. The solid-state energy storage device has the characteristics of high portability, no pollution liquid electrolyte leakage problem, strong environmental protection, multiple application scenes, high stability, simple operation, good low-temperature resistance and the like. Among them, the solid electrolyte is one of the most important components. Industrial solid electrolytes generally need to meet the requirements of low toxicity, simple preparation, high ionic conductivity, and good mechanical stability. The currently prepared solid electrolyte is generally relatively complex to prepare and relatively low in ionic conductivity. MXene is a novel material which develops rapidly, and is very suitable to be used as an electrode material of a solid-state energy storage device due to the advantages of high conductivity, rich surface functional groups and the like. At present, researches on solid-state energy storage of MXene materials are focused on MXene electrode materials, including MXene material modification, composite electrode preparation, asymmetric full-cell assembly and the like. Solid electrolyte and solid energy storage device preparation thereof are also less studied.
Therefore, a novel and simple preparation method of a solid-state energy storage device which takes self-supporting acid/PVA-based hydrogel prepared by a freeze-thaw method as an electrolyte and is coated with a pasty MXene material as an electrode is provided. Firstly, preparing a high-conductivity and low-temperature-resistant acid/PVA hydrogel electrolyte by a freeze-thaw method, and then preparing an energy storage device by simply coating pasty MXene on the surface of a solid electrolyte. The method is simple in process, the obtained MXene electrode is of a porous structure, the MXene stacking effect is inhibited by the structure, the dynamic performance of the device is greatly improved, and the prepared energy storage device has excellent rate performance. In addition, the high-power solar cell has excellent low-temperature resistance, long cycle performance, area capacitance, energy density and power density.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and title of the application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above problems occurring in the prior art.
Therefore, the invention aims to provide a preparation method of a solid-state energy storage device taking MXene as an electrode and PVA-based hydrogel as an electrolyte, and the prepared MXene solid-state energy storage device has excellent rate performance which exceeds that of a corresponding water system MXene energy storage device. And has excellent cycle performance, high area capacitance, and high energy density and power density.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions:
the preparation method of the solid-state energy storage device taking MXene as electrode acid/PVA-based hydrogel as electrolyte is characterized by comprising the following steps of: the method comprises the following steps:
step 1: weighing PVA with the mass fraction of 15%, adding water with the mass fraction of 85%, and heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding 4M protonic acid relative to water under stirring, and standing until defoaming;
step 2: injecting the solution obtained in the step into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing the electrolyte mould for 20 hours, taking the electrolyte mould out, and standing the electrolyte mould for 3 hours at room temperature;
and step 3: repeating the step 2 of freezing and standing in the step 2 for 2 times, taking out and demoulding to obtain the PVA-based hydrogel electrolyte;
and 4, step 4: balancing the anode and cathode quality of the muddy MXene material and the counter electrode material according to the theoretical capacitance, and smearing the muddy MXene material with corresponding quality on the surface of the PVA-based hydrogel electrolyte obtained in the step 3; attaching a cut clean titanium foil with a corresponding size and shape on the outer side of the MXene electrode;
and 5: placing the device obtained in the step 4 in the lower layer of a refrigerator for 20 hours and then at the normal temperature for 3 hours; repeating twice to obtain the target solid MXene/PVA hydrogel solid energy storage device.
The preferable scheme of the preparation method of the solid-state energy storage device taking MXene as the electrode and PVA-based hydrogel as the electrolyte is as follows: the protonic acid in the step 1 is one or more of hydrochloric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, sulfuric acid and phosphoric acid.
The preferable scheme of the preparation method of the solid-state energy storage device taking MXene as the electrode and PVA-based hydrogel as the electrolyte is as follows: the MXene material in the step 4 is Ti3C2Tx、V2CTx、Ti2CTx、Nb4C3Tx、Nb2CTx、Ti3(C,N)2、(Ti,Nb)4C3、(Ti,Zr)4C3、(Nb,Zr)4C3、Ti4N3、Ta4C3、Mo2C、(Ti,V)2C、(Ti,Nb)2C、(Ti,V)3C2、(Cr,V)3C2、(Cr2Ti)C2、(Mo2Ti)C2、(Mo2Ti2)C3、Ti4N3One or more of the positive electrode and the negative electrode are made of the same MXene material or different MXene materials, or one electrode is made of the MXene material, and the other electrode is made of other materials.
The preferable scheme of the preparation method of the solid-state energy storage device taking MXene as the electrode and PVA-based hydrogel as the electrolyte is as follows: the muddy MXene material used in the step 4 can be obtained by an etching method, wherein the etching method is one or more of a hydrofluoric acid etching method, a lithium salt etching method, a hydrochloric acid lithium fluoride etching method and an alkali etching method.
Compared with the prior art, the invention has the beneficial effects that: the acid/PVA hydrogel prepared by a freeze-thaw method is used as a solid electrolyte, and then a mud-like MXene structure is coated on the surface of the electrolyte, so that the porous MXene structure can be obtained, the stacking degree of the layered MXene is greatly reduced, the electrolyte contact is greatly improved, and the dynamic performance of the energy storage device is greatly improved. Therefore, the prepared MXene solid energy storage device has excellent rate performance, and the rate performance of the MXene solid energy storage device exceeds that of a corresponding water system MXene energy storage device. Meanwhile, the composite material has excellent cycle performance, high area capacitance, excellent low temperature resistance, high energy density and power density.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail with reference to the accompanying drawings and detailed embodiments, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise. Wherein:
FIG. 1MSA/PVA hydrogel impedance plot;
FIG. 2Ti3C2TxElectrode scanning electron microscope and element distribution diagram;
FIG. 3Ti3C2TxElectrode and comparative example 2X-ray photoelectron spectroscopy;
FIG. 4Ti3C2TxX-ray diffraction patterns of the electrode and comparative example 2;
FIG. 5 cyclic voltammogram of the device of example 1;
FIG. 6 is a magnification view of example 1 and comparative example 1;
FIG. 7 impedance plot of example 1 device;
FIG. 8 is a graph of constant current charge and discharge for the device of example 1 at different ionization densities;
FIG. 9 is a schematic view of the embodimentEXAMPLE 1 device 100mA cm-1Long cycle plot under current density;
FIG. 10 characterization of low temperature resistance of example 1;
fig. 11 graph comparing energy density/power density of example 1 with other solid state capacitors containing MXene.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described herein, and it will be apparent to those of ordinary skill in the art that the present invention may be practiced without departing from the spirit and scope of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Next, the present invention is described in detail with reference to the drawings, and in the detailed description of the embodiments of the present invention, the cross-sectional view illustrating the structure of the device is not enlarged partially in general scale for the convenience of illustration, and the drawings are only exemplary, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The invention provides the following technical scheme: the solid energy storage device prepared by the method taking MXene as electrode acid/PVA-based hydrogel as electrolyte has excellent rate performance, and the rate performance of the prepared solid energy storage device exceeds that of a corresponding water system MXene energy storage device. Meanwhile, the composite material has excellent cycle performance, low temperature resistance, high area capacitance, high energy density and power density;
example 1
1. 5 g of PVA were weighed into 28.3 g of water and heated to 90 ℃ and stirred for about 20 minutes until the PVA was completely dissolved. A colorless and transparent homogeneous aqueous PVA solution was obtained.
2. After the aqueous PVA solution was cooled to room temperature, 7.38 ml of methanesulfonic acid (MSA) solution was slowly added with stirring, and left to stand after stirring for another ten minutes to give a colorless uniform aqueous acid/PVA solution.
3. And after standing and defoaming, injecting the MSA/PVA aqueous solution into a mold with the thickness of 1 cm × 1 mm, putting the mold into a refrigerator freezing layer, freezing for 20 hours, taking out the mold, and standing for 3 hours at room temperature. Then put into a freezing layer of a refrigerator for freezing for 20 hours, and taken out and kept stand for 3 hours at room temperature. And then placing the mixture into a freezing layer of a refrigerator for freezing for 20 hours, taking the mixture out, standing the mixture for 3 hours at room temperature, and demolding the mixture to obtain the self-supporting acid/PVA hydrogel film.
4. Taking out the mud-shaped single-layer/few-layer Ti3C2TxThe titanium foil is divided into two parts with the mass ratio of 1:3.5, the two parts are respectively and uniformly coated on the two sides of an acid/PVA hydrogel film, and then the titanium foil which is cleaned by alcohol cotton is pasted on the two sides to be used as current collectors.
5. The device was then frozen in a refrigerator for 20 hours and then removed and allowed to stand at room temperature for 3 hours. Repeating the steps twice
6. The mud Ti in the step 43C2TxThe preparation process is as follows
7. 5 ml of water were added to a plastic beaker, and 15 ml of concentrated hydrochloric acid was added with stirring, followed by addition of 1.6 g of lithium fluoride and stirring for 5 minutes.
8. The mixed solution was stirred at 35 degrees Celsius, and 1 gram of Ti was slowly added3AlC2This process lasts approximately 5 minutes.
9. The plastic beaker was sealed with a preservative film and stirred continuously at 35 ℃ for 24 hours.
10. The mixed solution was transferred to a centrifuge tube and washed repeatedly with deionized water until pH ≈ 6.
11. And introducing argon into the mixed solution, sealing, and performing ultrasonic treatment at 25 ℃ for 30 minutes.
12. The mixed solution was centrifuged at 3500 rpm for 30 minutes to obtain an upper layer liquid.
13. Centrifuging the upper layer liquid for 30 minutes at 10000 revolutions to obtain the muddy few-layer/single-layer Ti3C2TxA material.
Example 2
1. 5 g of PVA were weighed into 28.3 g of water and heated to 90 ℃ and stirred for about 20 minutes until the PVA was completely dissolved. A colorless and transparent homogeneous aqueous PVA solution was obtained.
2. When the aqueous PVA solution was cooled to room temperature, 9 ml of trifluoromethanesulfonic acid was slowly added with stirring, and stirring was continued until complete dissolution, resulting in a colorless uniform aqueous p-toluenesulfonic acid/PVA solution.
3. After standing and defoaming, injecting the trifluoromethanesulfonic acid/PVA aqueous solution into a mold with the thickness of 1 cm × 1 mm, putting the mold into a refrigerator freezing layer, freezing for 20 hours, taking out the mold, and standing for 3 hours at room temperature. Then put into a freezing layer of a refrigerator for freezing for 20 hours, and taken out and kept stand for 3 hours at room temperature. And then placing the film into a freezing layer of a refrigerator for freezing for 20 hours, taking the film out, standing the film for 3 hours at room temperature, and demolding the film to obtain the self-supporting p-trifluoromethanesulfonic acid/PVA hydrogel film.
4. Taking out the mud-like single layer/few layer Nb4C3TxThe titanium foil is divided into two parts with the mass ratio of 1: 1, the two parts are respectively and uniformly coated on the two sides of a trifluoromethanesulfonic acid/PVA hydrogel film, and then the titanium foil cleaned by alcohol cotton is pasted on the two sides to be used as current collectors.
5. The device was then frozen in a refrigerator for 20 hours and then removed and allowed to stand at room temperature for 3 hours. Repeating twice
6. The mud Nb in the step 44C3TxThe preparation process comprises the following steps:
7. mixing Nb with4AlC3The material was stirred in 49% mass fraction HF solution at room temperature for 140 hours. Then washed with deionized water to a pH of 7.
8. 1 ml of tetramethylammonium hydroxide and 9 ml of deionized water were added to the beaker and mixed. The solid material obtained in the above step was then added thereto, and shaken at room temperature for 15 minutes.
9. And repeatedly centrifuging and cleaning the solid-liquid mixed solution obtained in the step by using deionized water until the pH value is 7. Obtaining clay-like Nb4C3TxA material.
Example 3
1. 5 g of PVA were weighed into 28.3 g of water and heated to 90 ℃ and stirred for about 20 minutes until the PVA was completely dissolved. A colorless and transparent homogeneous aqueous PVA solution was obtained.
2. After the aqueous PVA solution was cooled to room temperature, 19.4933 g of p-toluenesulfonic acid was slowly added with stirring, and after stirring for ten minutes, the mixture was left to stand to give a colorless uniform aqueous acid/PVA solution.
3. After standing and defoaming, injecting a p-toluenesulfonic acid/PVA aqueous solution into a mold with the thickness of 1 cm × 1 mm, putting the mold into a refrigerator freezing layer, freezing for 20 hours, taking out the mold, and standing for 3 hours at room temperature. Then put into a freezing layer of a refrigerator for freezing for 20 hours, and taken out and kept stand for 3 hours at room temperature. And then placing the film into a freezing layer of a refrigerator for freezing for 20 hours, taking the film out, standing the film for 3 hours at room temperature, and demolding the film to obtain the self-supporting p-toluenesulfonic acid/PVA hydrogel film.
4. Taking out the mud-shaped single-layer/few-layer Ti3C2TxIn which Ti is3C2TxThe preparation of (1) was carried out as described in example 1, uniformly coated on one side of the acid/PVA hydrogel film, the activated carbon film was placed on the other side and then a titanium foil wiped clean with alcohol cotton was applied as a current collector on both sides.
5. The device was then frozen in a refrigerator for 20 hours and then removed and allowed to stand at room temperature for 3 hours. This was repeated twice.
Comparative example 1
Comparative example 1 was prepared using a conventional MXene coating process and a conventional liquid electrolyte coating evaporation process as follows:
step 1: ti prepared as described in example 1 was taken3C2TxTi is applied by conventional coating method3C2TxThe coating was coated on a clean dry carbon cloth with an area of 1 cm to 1 cm and a mass of 1:3.5 mg, respectively.
Step 2: 1 g of PVA and 10 ml of water were added to a beaker and stirred with heating at 85 ℃ until completely dissolved. After the solution was cooled, 1 g of a 4M aqueous solution of methanesulfonic acid was added under stirring, stirred for ten minutes, and allowed to stand for deaeration.
And step 3: and (3) respectively coating the solution obtained in the step (2) on two electrodes, drying at room temperature, dripping a small amount of solution on one side after the PVA solution is formed into a film, and assembling into the all-solid-state energy storage device.
Comparative example 2
The slurry Ti obtained in example 1 was added3C2TxDispersing the deionized water into uniform dispersion, taking a proper amount of the dispersion, carrying out vacuum filtration, and drying to obtain the membrane material, namely the comparative example 2.
While the invention has been described above with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the various features of the disclosed embodiments of the invention may be used in any combination, provided that no structural conflict exists, and the combinations are not exhaustively described in this specification merely for the sake of brevity and resource conservation. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (4)
1. The preparation method of the solid-state energy storage device taking the PVA-based hydrogel as the electrolyte with MXene as the electrode is characterized by comprising the following steps of: the method comprises the following steps:
step 1: weighing PVA with the mass fraction of 15%, adding water with the mass fraction of 85%, and heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding 4M protonic acid relative to water under stirring, and standing until defoaming;
step 2: injecting the solution obtained in the step into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing the electrolyte mould for 20 hours, taking the electrolyte mould out, and standing the electrolyte mould for 3 hours at room temperature;
and step 3: repeating the step 2 of freezing and standing in the step 2 for 2 times, taking out and demoulding to obtain the PVA-based hydrogel electrolyte;
and 4, step 4: balancing the anode and cathode quality of the muddy MXene material and the counter electrode material according to the theoretical capacitance, and smearing the muddy MXene material with corresponding quality on the surface of the PVA-based hydrogel electrolyte obtained in the step 3; attaching a cut clean titanium foil with a corresponding size and shape on the outer side of the MXene electrode;
and 5: placing the device obtained in the step 4 in the lower layer of a refrigerator for 20 hours and then at the normal temperature for 3 hours; repeating twice to obtain the target solid MXene/PVA hydrogel solid energy storage device.
2. The method for preparing the solid-state energy storage device by taking MXene as the electrode and taking the PVA-based hydrogel as the electrolyte according to claim 1 is characterized in that: the protonic acid in the step 1 is one or more of hydrochloric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, sulfuric acid and phosphoric acid.
3. The method for preparing the solid-state energy storage device by taking MXene as the electrode and taking the PVA-based hydrogel as the electrolyte according to claim 1 is characterized in that: the MXene material in the step 4 is Ti3C2Tx、V2CTx、Ti2CTx、Nb4C3Tx、Nb2CTx、Ti3(C,N)2、(Ti,Nb)4C3、(Ti,Zr)4C3、(Nb,Zr)4C3、Ti4N3、Ta4C3、Mo2C、(Ti,V)2C、(Ti,Nb)2C、(Ti,V)3C2、(Cr,V)3C2、(Cr2Ti)C2、(Mo2Ti)C2、(Mo2Ti2)C3、Ti4N3One or more of the positive electrode and the negative electrode are made of the same MXene material or different MXene materials, or one electrode is made of the MXene material, and the other electrode is made of other materials.
4. The method for preparing the solid-state energy storage device by taking MXene as the electrode and taking the PVA-based hydrogel as the electrolyte according to claim 1 is characterized in that: the muddy MXene material used in the step 4 can be obtained by an etching method, wherein the etching method is one or more of a hydrofluoric acid etching method, a lithium salt etching method, a hydrochloric acid lithium fluoride etching method and an alkali etching method.
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