CN114614112B - Preparation method of solid-state energy storage device with MXene as electrode PVA-based hydrogel as electrolyte - Google Patents
Preparation method of solid-state energy storage device with MXene as electrode PVA-based hydrogel as electrolyte Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- 238000004146 energy storage Methods 0.000 title claims abstract description 35
- 239000000017 hydrogel Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000007710 freezing Methods 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- 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 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- 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
- 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
- 239000003513 alkali Substances 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
- 239000010410 layer Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J13/0065—Preparation of gels containing an organic phase
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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
- H01G11/22—Electrodes
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- H01G9/15—Solid electrolytic capacitors
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention belongs to the technical field of electrolyte of solid-state energy storage devices and preparation of all devices, and particularly relates to a preparation method of a solid-state energy storage device with MXene as an electrode PVA-based hydrogel as an electrolyte, which comprises the following steps of: weighing PVA with the mass fraction of 15%, adding water with the mass fraction of 85%, heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding protonic acid with the relative water of 4M under stirring, and standing until defoaming; step 2: injecting the solution obtained in the steps into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing for 20 hours, taking out the electrolyte mould, and standing the electrolyte mould for 3 hours at room temperature; step 3: and (3) repeating the step (2) of cooling and standing for 2 times, taking out and demolding to obtain the PVA-based hydrogel electrolyte, wherein the PVA-based hydrogel electrolyte is reasonable in structure, and the prepared MXene solid-state energy storage device has excellent multiplying power performance, and the multiplying power performance exceeds that of a corresponding water system MXene energy storage device. And simultaneously has excellent cycle performance, high area capacitance, high energy density and power density.
Description
Technical Field
The invention relates to the technical field of electrolyte of solid-state energy storage devices and preparation of all devices, in particular to a preparation method of a solid-state energy storage device by taking MXene as an electrode PVA-based hydrogel as an electrolyte.
Background
In the 21 st century, the human living standard is greatly improved, and the rapid development of mobile and wearable electronic equipment brings great convenience to human beings. With the rapid rise in the demand of modern society for rapidly portable, mobile charge-discharge devices, further upgrades of flexible solid state energy storage devices are put more demands on humans. 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 constituent components. Industrial solid electrolytes are generally required to meet the requirements of low toxicity, simple preparation, high ionic conductivity, and good mechanical stability. Whereas currently prepared solid state electrolytes are generally relatively complex to prepare and have relatively low ionic conductivity. MXene is used as a novel material which is developed rapidly, and is very suitable for being used as an electrode material of a solid-state energy storage device due to the advantages of high conductivity, abundant surface functional groups and the like. Currently, research on solid state energy storage of an MXene material is focused on an MXene electrode material, including modification of the MXene material, preparation of a composite electrode, assembly of an asymmetric full cell and the like. Solid state electrolytes and solid state energy storage device fabrication are also less studied.
Therefore, a novel and simple method for preparing a solid energy storage device by using self-supporting acid/PVA-based hydrogel prepared by a freeze thawing method as an electrolyte and a claying MXene material as an electrode is provided. The method comprises the steps of preparing an acid/PVA hydrogel electrolyte with high conductivity and low temperature resistance by a freeze thawing method, and then preparing the energy storage device by simply coating the pasty MXene on the surface of the solid electrolyte. The method is simple in process, the obtained MXene electrode is of a porous structure, the MXene stacking effect is restrained by the structure, the dynamic performance of the device is greatly improved, and the prepared energy storage device has excellent multiplying power performance. In addition, the alloy also has excellent low temperature resistance, long cycle performance, area capacitance, energy density and power density.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the problems occurring in the prior art.
Therefore, the invention aims to provide a preparation method of a solid-state energy storage device with MXene as an electrode PVA-based hydrogel as an electrolyte, and the prepared MXene solid-state energy storage device has excellent rate capability, and the rate capability exceeds that of a corresponding water system MXene energy storage device. And simultaneously has excellent cycle performance, high area capacitance, high energy density and power density.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
the preparation method of the solid-state energy storage device with 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%, heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding protonic acid with the relative water of 4M under stirring, and standing until defoaming;
step 2: injecting the solution obtained in the steps into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing for 20 hours, taking out the electrolyte mould, and standing the electrolyte mould for 3 hours at room temperature;
step 3: repeating the step 2 for 2 times by cooling and standing, taking out and demolding to obtain PVA-based hydrogel electrolyte;
step 4: matching the quality of the anode and the cathode with the mud-like MXene material and the counter electrode material according to the theoretical capacitance, and smearing the mud-like MXene material with the corresponding quality on the surface of the PVA-based hydrogel electrolyte obtained in the step 3; attaching a clean titanium foil with a cut corresponding size and shape to the outer side of the MXene electrode;
step 5: placing the device obtained in the step 4 in the lower layer of the refrigerator for 20 hours and then in the normal temperature for 3 hours; repeating the steps twice to obtain the target solid-state MXene/PVA hydrogel solid-state energy storage device.
As a preferable scheme of the preparation method of the solid-state energy storage device taking the MXene as the electrode PVA-based hydrogel as the electrolyte, the preparation method comprises the following steps: 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.
As a preferable scheme of the preparation method of the solid-state energy storage device taking the MXene as the electrode PVA-based hydrogel as the electrolyte, the preparation method comprises the following steps: the MXene material in the step 4 is Ti 3 C 2 T x 、V 2 CT x 、Ti 2 CT x 、Nb 4 C 3 T x 、Nb 2 CT x 、Ti 3 (C,N) 2 、(Ti,Nb) 4 C 3 、(Ti,Zr) 4 C 3 、(Nb,Zr) 4 C 3 、Ti 4 N 3 、Ta 4 C 3 、Mo 2 C、(Ti,V) 2 C、(Ti,Nb) 2 C、(Ti,V) 3 C 2 、(Cr,V) 3 C 2 、(Cr 2 Ti)C 2 、(Mo 2 Ti)C 2 、(Mo 2 Ti 2 )C 3 、Ti 4 N 3 One or more of the electrodes and the anode are made of the same type of MXene material or different types of MXene materials, or one electrode is made of the MXene material, and the other electrode is made of other materials.
As a preferable scheme of the preparation method of the solid-state energy storage device taking the MXene as the electrode PVA-based hydrogel as the electrolyte, the preparation method comprises the following steps: the mud-like 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 lithium fluoride hydrochloride 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 the freeze thawing method is used as a solid electrolyte, and then the porous MXene structure can be obtained by coating mud MXene on the surface of the electrolyte, so that the stacking degree of the layered MXene is greatly reduced, the contact property of the electrolyte is greatly improved, and the dynamic performance of the energy storage device is greatly improved. Therefore, the prepared MXene solid-state energy storage device has excellent multiplying power performance, and the multiplying power performance exceeds that of a corresponding water system MXene energy storage device. Meanwhile, the high-temperature-resistant high-energy-density high-power-density high-energy-density high-capacitance high-energy-density high-density battery has excellent cycle performance, high area capacitance and excellent low-temperature resistance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings, which are to be understood as merely some embodiments of the present invention, and from which other drawings can be obtained by those skilled in the art without inventive faculty. Wherein:
FIG. 1MSA/PVA hydrogel impedance plot;
FIG. 2Ti 3 C 2 T x Electrode scanning electron microscope and element distribution map;
FIG. 3Ti 3 C 2 T x Electrode and comparative example 2X-ray photoelectron spectra;
FIG. 4Ti 3 C 2 T x Electrode and comparative example 2X-ray diffraction pattern;
FIG. 5 example 1 device cyclic voltammogram;
FIG. 6 is a magnification view of example 1 and comparative example 1;
FIG. 7 example 1 device impedance diagram;
FIG. 8 example 1 shows constant current charge and discharge curves for devices at different ionization densities;
FIG. 9 example 1 device 100mA cm -1 A long cycle chart at current density;
FIG. 10 example 1 low temperature resistance characterization;
FIG. 11 is a graph of energy density/power density comparison of example 1 and other solid state capacitors containing MXene.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings.
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 other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Next, the present invention will be described in detail with reference to the drawings, wherein the sectional view of the device structure is not partially enlarged to general scale for the convenience of description, and the drawings are only examples, 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 actual fabrication.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
The invention provides the following technical scheme: the solid-state energy storage device prepared by using the MXene as the electrode acid/PVA-based hydrogel as the electrolyte has excellent multiplying power performance, and the multiplying power performance of the solid-state energy storage device exceeds that of a corresponding water system MXene energy storage device. Meanwhile, the high-energy-density high-temperature-resistant high-power-density high-energy-density high-power-density high-density battery has excellent cycle performance, low-temperature resistance and high area capacitance;
example 1
1. 5 g of PVA was weighed out and dissolved in 28.3 g of water, heated to 90℃and stirred for approximately 20 minutes until PVA was completely dissolved. A colorless transparent homogeneous aqueous PVA solution was obtained.
2. After the aqueous PVA solution was cooled to room temperature, 7.38 ml of a methanesulfonic acid (MSA) solution was slowly added with stirring, and stirring was continued for ten minutes and then allowed to stand to obtain a colorless uniform aqueous acid/PVA solution.
3. After standing and defoaming, the MSA/PVA water solution is injected into a mold with the thickness of 1 cm to 1 mm, and the mold is put into a refrigerator freezing layer to be frozen for 20 hours, taken out and kept standing for 3 hours at room temperature. And then putting the mixture into a freezing layer of a refrigerator to freeze for 20 hours, taking out and standing for 3 hours at room temperature. And then putting the mixture into a refrigerator freezing layer for freezing for 20 hours, taking out the mixture, standing the mixture for 3 hours at room temperature, and demolding the mixture to obtain the self-supporting acid/PVA hydrogel film.
4. The obtained mud-like monolithic layer/less layer Ti 3 C 2 T x Divided into a mass ratio of 1 to 3.5Uniformly coating the two parts of the titanium foil on two sides of an acid/PVA hydrogel film respectively, and then sticking titanium foils which are scrubbed clean by alcohol cotton on the two sides to serve 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-like Ti in the step 4 3 C 2 T x The preparation process is as follows
7. 5 ml of water are added to a plastic beaker, 15 ml of concentrated hydrochloric acid are added with stirring, followed by 1.6 g of lithium fluoride and stirring for 5 minutes.
8. The mixed solution was stirred at 35 degrees celsius and 1 gram Ti was slowly added 3 AlC 2 This process lasts approximately 5 minutes.
9. The plastic beaker was sealed with a preservative film and stirred continuously for 24 hours at 35 ℃.
10. The mixed solution was transferred to a centrifuge tube and repeatedly rinsed with deionized water until the pH was approximately 6.
11. Argon is introduced into the mixed solution, the mixed solution is sealed, and ultrasonic treatment is carried out for 30 minutes at 25 ℃.
12. The mixed solution was centrifuged at 3500 rpm for 30 minutes, and the supernatant was taken.
13. Centrifuging the upper layer liquid 10000 turns for 30 min to obtain mud-like few layer/single layer Ti 3 C 2 T x A material.
Example 2
1. 5 g of PVA was weighed out and dissolved in 28.3 g of water, heated to 90℃and stirred for approximately 20 minutes until PVA was completely dissolved. A colorless transparent homogeneous aqueous PVA solution was obtained.
2. After the PVA aqueous solution was cooled to room temperature, 9 ml of trifluoromethanesulfonic acid was slowly added with stirring, and stirring was continued until complete dissolution was obtained to obtain a colorless uniform p-toluenesulfonic acid/PVA aqueous solution.
3. After standing and defoaming, the aqueous solution of the triflic acid/PVA is injected into a 1 cm-1 mm die, and the die is put into a refrigerator frozen layer to be frozen for 20 hours, taken out and kept stand for 3 hours at room temperature. And then putting the mixture into a freezing layer of a refrigerator to freeze for 20 hours, taking out and standing for 3 hours at room temperature. And then putting the mixture into a refrigerator freezing layer for freezing for 20 hours, taking out the mixture, standing the mixture for 3 hours at room temperature, and demolding the mixture to obtain the self-supporting p-trifluoromethanesulfonic acid/PVA hydrogel film.
4. The obtained mud-like monolithic layer/less layer Nb 4 C 3 T x Dividing into two parts with the mass ratio of 1 to 1, respectively and uniformly coating the two sides of a trifluoro methanesulfonic acid/PVA hydrogel film, and then pasting titanium foil which is scrubbed clean by alcohol cotton on the two sides to serve 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-like Nb in the step 4 4 C 3 T x The preparation process is as follows:
7. nb is set to 4 AlC 3 The material was stirred in a 49 mass% HF solution at room temperature for 140 hours. And 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. Then, the solid material obtained in the above step was added thereto, and the mixture was shaken at room temperature for 15 minutes.
9. And (3) repeatedly centrifugally cleaning the solid-liquid mixture obtained in the steps with deionized water until the pH value is 7. Obtaining clay-like Nb 4 C 3 T x A material.
Example 3
1. 5 g of PVA was weighed out and dissolved in 28.3 g of water, heated to 90℃and stirred for approximately 20 minutes until PVA was completely dissolved. A colorless transparent homogeneous aqueous PVA solution was obtained.
2. After the PVA aqueous solution was cooled to room temperature, 19.4933 g of p-toluenesulfonic acid was slowly added with stirring, and stirring was continued for ten minutes and then left to stand, to obtain a colorless uniform acid/PVA aqueous solution.
3. After standing and defoaming, the p-toluenesulfonic acid/PVA aqueous solution is injected into a 1 cm 1 mm die, and the die is put into a refrigerator frozen layer for freezing for 20 hours, taken out and kept standing for 3 hours at room temperature. And then putting the mixture into a freezing layer of a refrigerator to freeze for 20 hours, taking out and standing for 3 hours at room temperature. And then putting the mixture into a refrigerator freezing layer for freezing for 20 hours, taking out the mixture, standing the mixture for 3 hours at room temperature, and demolding the mixture to obtain the self-supporting p-toluenesulfonic acid/PVA hydrogel film.
4. The obtained mud-like monolithic layer/less layer Ti 3 C 2 T x Wherein Ti is 3 C 2 T x The preparation method of (2) is as described in example 1, uniformly coated on one side of an acid/PVA hydrogel film, and an activated carbon film is placed on the other side of the film, and then titanium foil which is scrubbed clean with alcohol cotton is attached to both sides of the film to serve as a current collector.
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. The procedure was repeated twice.
Comparative example 1
Comparative example 1 was prepared using a conventional MXene coating method and a conventional liquid electrolyte coating evaporation method, specifically as follows:
step 1: taking Ti prepared by the procedure described in example 1 3 C 2 T x Ti is applied by conventional coating methods 3 C 2 T x Coating the powder on clean dry carbon cloth, wherein the area is 1 cm to 1 cm, and the mass is 1:3.5 milligrams respectively.
Step 2: 1 g of PVA and 10 ml of water were added to the 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, followed by stirring for ten minutes, and standing for deaeration.
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 into the PVA solution after film formation, and assembling the full-solid energy storage device.
Comparative example 2
The mud-like Ti obtained in example 1 3 C 2 T x Dispersing with deionized water to obtain a uniform dispersion, vacuum filtering the dispersion, and drying to obtain the membrane material which is comparative example 2.
Although the invention has been described hereinabove with reference to embodiments, various modifications thereof may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the features of the disclosed embodiments may be combined with each other in any manner as long as there is no structural conflict, and the exhaustive description of these combinations is not given in this specification merely for the sake of omitting the descriptions and saving resources. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (3)
1. The preparation method of the solid-state energy storage device with the MXene as the electrode PVA-based hydrogel as the 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%, heating and stirring at 90 ℃ until the PVA is completely dissolved; after cooling, adding protonic acid with the relative water of 4M under stirring, and standing until defoaming, wherein the protonic acid is one or more of p-toluenesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and methanesulfonic acid;
step 2: injecting the solution obtained in the steps into an electrolyte mould with the corresponding size and shape requirements, putting the electrolyte mould into the lower layer of a refrigerator, freezing for 20 hours, taking out the electrolyte mould, and standing the electrolyte mould for 3 hours at room temperature;
step 3: repeating the step 2 for 2 times by cooling and standing, taking out and demolding to obtain PVA-based hydrogel electrolyte;
step 4: matching the quality of the anode and the cathode with the mud-like MXene material and the counter electrode material according to the theoretical capacitance, and smearing the mud-like MXene material with the corresponding quality on the surface of the PVA-based hydrogel electrolyte obtained in the step 3; attaching a clean titanium foil with a cut corresponding size and shape to the outer side of the MXene electrode;
step 5: placing the device obtained in the step 4 in the lower layer of the refrigerator for 20 hours and then in the normal temperature for 3 hours; repeating the steps twice to obtain the target solid-state MXene/PVA hydrogel solid-state energy storage device.
2. The method for preparing the solid-state energy storage device using the MXene as the electrode PVA-based hydrogel as the electrolyte, according to claim 1, is characterized in that: the MXene material in the step 4 is Ti 3 C 2 T x 、V 2 CT x 、Ti 2 CT x 、Nb 4 C 3 T x 、Nb 2 CT x 、Ti 3 (C,N) 2 、(Ti,Nb) 4 C 3 、(Ti,Zr) 4 C 3 、(Nb,Zr) 4 C 3 、Ti 4 N 3 、Ta 4 C 3 、Mo 2 C、(Ti,V) 2 C、(Ti,Nb) 2 C、(Ti,V) 3 C 2 、(Cr,V) 3 C 2 、(Cr 2 Ti)C 2 、(Mo 2 Ti)C 2 、(Mo 2 Ti 2 )C 3 、Ti 4 N 3 One or more of the electrodes and the anode are made of the same type of MXene material or different types of MXene materials, or one electrode is made of the MXene material, and the other electrode is made of other materials.
3. The method for preparing the solid-state energy storage device using the MXene as the electrode PVA-based hydrogel as the electrolyte, according to claim 1, is characterized in that: the mud-like 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 lithium fluoride hydrochloride etching method and an alkali etching method.
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