CN115246645A - V based on different layer numbers 2 CT x Preparation method of material and preparation method of capacitor - Google Patents

V based on different layer numbers 2 CT x Preparation method of material and preparation method of capacitor Download PDF

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CN115246645A
CN115246645A CN202211079709.6A CN202211079709A CN115246645A CN 115246645 A CN115246645 A CN 115246645A CN 202211079709 A CN202211079709 A CN 202211079709A CN 115246645 A CN115246645 A CN 115246645A
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powder
flexible
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CN115246645B (en
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刘世琦
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Hubei Wanrun New Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to V 2 CT x The technical field of materials, in particular to V based on different layer numbers 2 CT x A method for preparing the material and a method for preparing the capacitor; first, V was etched using a mixed solution of NaF and HCl 2 Preparing AlCrax phase powder, centrifuging, washing, and freeze drying to obtain V of accordion structure 2 CT x Preparing powder, intercalating with organic base TBAOH, and centrifuging by ultrasonic treatment and different rotation speeds to obtain multilayer V 2 CT x Powder of V 2 CT x As a novel two-dimensional material, the material has the advantages of large specific surface area, rich surface functional groups, good water solubility and the like;in addition, V is deposited by electrophoresis 2 CT x The flexible electrode is prepared and packaged with the zinc cathode and zinc sulfate hydrogel to obtain the flexible zinc ion hybrid capacitor which does not need to add any binder and conductive agent and has excellent electrochemical performance, the cost is lower than that of the traditional flexible electrode preparation process, and the flexible zinc ion hybrid capacitor is expected to be produced on a large scale.

Description

V based on different layer numbers 2 CT x Preparation method of material and preparation method of capacitor
Technical Field
The invention relates to V 2 CT x The technical field of materials, in particular to V based on different layer numbers 2 CT x A method for preparing the material and a method for preparing a capacitor.
Background
The rapid development of flexible electronic devices has prompted research into effective electrochemical energy storage devices with high energy density, high power density, long cycle life, and excellent safety; the aqueous zinc ion hybrid capacitor combines the advantages of a battery and a capacitor while exhibiting high energy density and power density, and is generally composed of a battery-type electrode, a capacitive-type electrode, and a zinc-based electrolyte, and according to its energy storage technology, the zinc ion hybrid capacitor can be classified into two types, a battery-type positive electrode// capacitive-type negative electrode and a capacitive-type positive electrode// battery-type negative electrode (mainly including metallic zinc or modified metallic zinc); because the abundant metal zinc has large theoretical capacity (volume: 5849mAh cm) -3 (ii) a Weight: 819mAh g -1 ) And a low redox potential (-0.76V vs. standard hydrogen electrode) in aqueous solution, so zinc-ion hybrid capacitors with metallic zinc as the negative electrode are considered to be excellent substitutes for lithium-ion batteries and supercapacitors; furthermore, zn is coated on the zinc negative electrode 2+ The rapid deposition and stripping of the silicon nitride ensures high energy density and excellent self-discharge resistance; therefore, the water system zinc ion hybrid capacitor taking zinc as a negative electrode is more suitable for the application of flexible wearable and integrated systems;
two-dimensional metal carbides and nitrides (MXenes) have been extensively studied for energy storage, particularly batteries and supercapacitors, due to their excellent electrical conductivity, large specific surface area, abundant surface functionality and tunability of microstructure, and to date, ti 3 C 2 T x MXene is extensively studied due to its relatively mature synthesis process, however, ti 3 C 2 T x MXene has a narrow voltage window (less than 0.6V in aqueous solution), so that the electrochemical performance is difficult to improve, and another newly-appeared V 2 CT x MXene not only has a high voltage window in aqueous solution of more than 1V, but also exhibits a low number of atomic layers and a variable valence state of vanadium, and in addition, V 2 CT x The nano-channel is composed of a large number of V-C-V monolayers, shows a plurality of ordered nano-channels, has more active sites, and is beneficial to the diffusion of zinc ions; thus, two dimensions V 2 CT x Shows excellent electrochemical performance to make it into zincMore promising candidates in ion-hybrid capacitors;
such as the article "refining Vanadium carbide for Zinc-Ion Storage: hydrate Precipitation and H + /Zn 2+ Co-Action mechanics. "(Wang C, wei S, chen S, et al. Small Methods,2019,3 (12): 1900495)", discloses V 2 CT x As an electrode material of a zinc ion energy storage device, the technology disclosed by the document has the following defects or shortcomings:
(1) Prepared V 2 CT x The high-performance electrode prepared by compounding the carbon nano tube has high cost and complex process;
(2) The manufactured buckle type zinc ion energy storage device cannot meet the development requirement of a flexible electronic device;
and V 2 CT x Has a forming energy higher than that of Ti 3 C 2 T x And other MXenes, hence V 2 CT x Higher temperatures and longer times are required for etching, resulting in a multilayer V 2 CT x Rather than a complete single nanosheet; thus, flexible and independent V 2 CT x The electrode is not easy to look like Ti 3 C 2 T x Thin films are obtained by simple vacuum filtration, spin coating or spray coating;
the present application is particularly proposed based on the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to make up for the deficiencies of the prior art and solve the technical problems in the background art, the invention provides V based on different layers 2 CT x A method for preparing the material and a method for preparing a capacitor.
The invention is realized by the following technical scheme: v based on different layer numbers 2 CT x The preparation method of the material comprises the following steps:
s1: weighing V 2 Adding AlC MAX precursor into etching solution composed of NaF and HCL for hydrothermal reaction, repeatedly centrifuging and washing the resultant, and freeze-drying at low temperature to form accordion structureV 2 CT x Powder;
s2: v of accordion structure in S1 2 CT x Adding the powder into TBAOH solution for intercalation, repeatedly centrifuging and washing the resultant, performing ultrasonic treatment at low temperature under protection of inert atmosphere, centrifuging at 3500r/min for 30min to obtain precipitate, and freeze-drying the precipitate to obtain multilayer V 2 CT x Powder;
s3: centrifuging the supernatant obtained in S2 at 8000r/min for 30min to obtain precipitate, and freeze drying the precipitate to obtain small layer V 2 CT x And (3) powder.
Preferably, V is as defined in S1 2 The grain size of AlC MAX phase powder is 400 meshes, the hydrothermal reaction temperature is 90 ℃, and the hydrothermal reaction time is 7d.
Preferably, V is as defined in S1 2 The mass ratio of AlC MAX phase powder to NaF is 1, and the concentration of HCL is 6mol/L.
Preferably, V of accordion structure described in S2 2 CT x The mass of the powder was 1g and the mass fraction of TBAOH solution was 25%.
Preferably, the inert atmosphere in S2 is argon atmosphere, and the ultrasonic treatment time is 1h.
Preferably, the freeze-drying time in each of S1, S2 and S3 is 24h.
The positive electrode of the capacitor adopts the V with different layers prepared by the method 2 CT x V made of powder 2 CT x The preparation method of the flexible electrode comprises the following steps:
p1: carving graphite paper into an interdigital shape by using a laser carving machine to serve as a flexible conductive substrate;
p2: will V 2 CT x Adding the powder and iodine into an acetone solution, and performing ultrasonic dispersion to form a uniform suspension;
p3: preparing V by electrophoretic deposition by taking a platinum electrode as a positive electrode, taking the interdigital graphite paper P1 as a negative electrode and taking the suspension P2 as electrophoretic liquid 2 CT x A flexible electrode;
p4: v as described under P3 2 CT x The flexible electrode is a positive electrode, the electrogalvanizing nano-sheet is a negative electrode, znSO 4 The hydrogel is an electrolyte and is assembled into a flexible water system zinc ion hybrid capacitor.
Preferably, the thickness of the graphite paper in the P1 is 0.05mm, and the interdigital area after engraving is 1.1723cm -2 。
Preferably, V is as described in P2 2 CT x The mass ratio of powder to iodine was 3:2 with a sonication time of 30min.
Preferably, the electrophoretic voltage of the electrophoretic deposition described in P3 is 24V, and the electrophoretic time is 2min.
The invention has the beneficial effects that:
1. v based on different layer numbers 2 CT x Method for preparing material and capacitor, etching V with NaF and HCl mixed solution 2 Preparing V with accordion structure from AlC MAX phase powder by centrifugal washing and freeze drying 2 CT x Preparing powder, intercalating with organic base TBAOH, and centrifuging by ultrasonic treatment and different rotation speeds to obtain multilayer V 2 CT x Powder of V 2 CT x As a novel two-dimensional material, the material has the advantages of large specific surface area, rich surface functional groups, good water solubility and the like, and is very suitable for being used as an electrochemical electrode material.
2. V based on different layer numbers 2 CT x Method for preparing material and capacitor by electrophoretic deposition of V 2 CT x The flexible electrode is prepared and packaged with a zinc cathode and zinc sulfate hydrogel to obtain a flexible zinc ion hybrid capacitor which does not need to be added with any binder and conductive agent and has excellent electrochemical performance, compared with the traditional flexible electrode preparation process, the flexible electrode preparation process has low cost and is expected to realize large-scale production, and meanwhile, acetone is used as an electrophoresis solution solvent, so that the electrode can be prevented from being oxidized, and the flexible electrode has great advantages in the field of flexible wearable.
Drawings
FIG. 1 shows V of the present invention based on different numbers of layers 2 CT x Process for the preparation of a materialA flow chart;
wherein the reference numbers:
A1：V 2 AlC；
b1: v of accordion structure 2 CT x ；
C1: few layers V 2 CT x ；
D1: multilayer V 2 CT x ；
T1：NaF+HCL；
T2：TBAOH；
T3: washing, ultrasonic treatment and centrifugation;
FIG. 2 is a flow chart of a capacitor process of the present invention;
wherein the reference numbers:
A2：Pt；
A3：Zn；
b2: graphite paper;
t11: acetone, iodine and V 2 CT x The mixed solution of (1);
t12: electrophoresis;
t21: acrylamide, potassium persulfate, and N, N-methylenebisamide;
t31: KCL and ZnSO 4 The mixed solution of (1);
t32: electroplating;
d: an aqueous zinc ion hybrid capacitor;
FIG. 3 is a SEM topography and TEM image of example III made in the present invention;
wherein:
(a) For making V of accordion structure 2 CT x SEM topography of;
(b) To obtain a multilayer V 2 CT x SEM topography of;
(c) To obtain few layers V 2 CT x A TEM image of (B);
FIG. 4 shows a graph based on V obtained in the third example of the present invention 2 CT x SEM appearance images of the flexible electrode and the electrogalvanizing negative electrode and a real object image of the capacitor;
wherein:
(a) To be made based on V 2 CT x SEM topography of the flexible electrode;
(b) Is an SEM topography of the electrogalvanizing cathode;
(c) A real object diagram of the water system zinc ion hybrid capacitor is shown;
FIG. 5 shows a graph based on V obtained in the third example of the present invention 2 CT x And (3) a cycle stability performance diagram of the water system zinc ion hybrid capacitor assembled by the flexible electrode.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to the drawings and specific examples so that those skilled in the art can better understand the present invention and can implement the present invention, but the examples are not intended to limit the present invention, and in addition, the specific weight, type, number, etc. appearing in the examples are only preferred examples.
Based on V 2 CT x The specific process steps of the flexible water system zinc ion hybrid capacitor of the electrode are as follows:
m1: etching V 2 AlC MAX, and preparing V of accordion structure by centrifugal cleaning and freeze drying 2 CT x Powder;
m2: v of accordion structure 2 CT x Performing intercalation, centrifugal cleaning and low-temperature ultrasonic treatment, and centrifuging at 3500r/min to prepare multilayer V 2 CT x Powder;
m3: centrifuging supernatant obtained from M2 at 8000r/min to obtain small-layer V 2 CT x A powder;
m4: preparation of V by electrophoretic deposition 2 CT x A flexible electrode;
m5: encapsulation based on V 2 CT x The flexible aqueous zinc ion hybrid capacitor of (1).
The first embodiment is as follows:
in the preferred embodiment of the invention, the V is based on an accordion structure 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
etching V 2 AlC MAX, centrifugal cleaning and freeze drying to prepare V of accordion structure 2 CT x Powder;
v of accordion structure 2 CT x The powder was V-etched selectively with a mixture of sodium fluoride (NaF, > 99%) and hydrochloric acid (HCl, 36-38%) 2 Synthesizing AlC; mixing 1g V 2 Slowly adding AlC MAX phase (Kai ceramic materials Co., ltd., laizhou, not less than 400 meshes) into a mixed solution of 1g NaF and 20mL HCl (6M), and continuously reacting for 7 days at 90 ℃; then, centrifugally washing the reaction product with deionized water for many times until the pH value is close to 7; finally, the precipitate is subjected to vacuum freeze drying to obtain V with an accordion structure 2 CT x A powder;
v with accordion structure prepared by adopting method 2 CT x Can be used for preparing V 2 CT x The flexible electrode is applied to the positive electrode of the flexible water system zinc ion hybrid capacitor.
The V based on the accordion structure 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
p1, carving graphite paper with the thickness of 0.05mm into an interdigital shape by using a laser carving machine to serve as a flexible conductive substrate, wherein the area of the carved interdigital is 1.1723cm 2 ；
P2 weighing V 2 CT x Powder and iodine, in a ratio of 3:2, adding the mixture into an acetone solution, and performing ultrasonic treatment for 30 minutes to form a uniform suspension as an electrophoresis solution;
p3, putting a platinum electrode as a positive electrode and the interdigital graphite paper of P1 as a negative electrode into the suspension liquid in the step P2 in parallel, and preparing V by electrophoretic deposition for 2 minutes under the voltage of 24V 2 CT x A flexible electrode;
p4 flexible V with P3 2 CT x The anode and the zinc cathode are placed on a polyimide film in parallel, then zinc sulfate polyacrylamide electrolyte is coated on the two electrodes, the flexible water system zinc ion hybrid capacitor is packaged by a polyethylene glycol terephthalate film, and the flexible water system zinc ion hybrid capacitor is placed overnight to test the electrochemical performance of the flexible water system zinc ion hybrid capacitor.
Example two:
in the preferred practice of the inventionIn the example, based on multiple layers V 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
s1: etching V 2 AlC MAX, centrifugal cleaning and freeze drying to prepare V of accordion structure 2 CT x Powder;
v of accordion structure 2 CT x The powder is V etched selectively with a mixture of sodium fluoride (> 99%) and hydrochloric acid (36-38%) 2 Synthesized from AlC, 1g V 2 Slowly adding AlC MAX phase (greater than or equal to 400 meshes, produced by Kai ceramic materials of Lyzhou) into a mixed solution of 1g NaF and 20mL HCl (6 mol/L), and continuously reacting for 7 days at 90 ℃; then, centrifugally washing the reaction product with deionized water for many times until the pH value is close to 7; finally, the precipitate is subjected to vacuum freeze drying to obtain V with an accordion structure 2 CT x Powder;
s2: for V of accordion structure obtained in S1 2 CT x Intercalation treatment is carried out, and intercalated V is prepared by centrifugal screening 2 CT x Powder;
1g of V in accordion structure obtained in S1 2 CT x The powder was intercalated with 10mL tetrabutylammonium hydroxide (TBAOH) solution (25%) for 8 hours at room temperature to increase the V of the accordion structure 2 CT x The intercalated precipitate was washed several times with ultrapure water to remove residual tetrabutylammonium hydroxide (TBAOH), followed by adding ultrapure water and ultrasonic treatment for 1 hour under an argon atmosphere to peel it off; centrifuging the suspension at 3500r/min for 30min, and freeze drying the obtained precipitate to obtain multilayer V 2 CT x A powder;
multilayer V prepared by the above method 2 CT x Can be used for preparing V 2 CT x The flexible electrode is applied to the positive electrode of the flexible water system zinc ion hybrid capacitor.
Said multilayer V 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
p1: using a laser to irradiate graphite paper with the thickness of 0.05mmThe optical engraving machine is engraved into the shape of an interdigital and used as a flexible conductive substrate, and the area of the engraved interdigital is 1.1723cm 2； ；
P2: weighing V 2 CT x Powder and iodine, in a ratio of 3:2, adding the mixture into an acetone solution, and performing ultrasonic treatment for 30 minutes to form a uniform suspension as an electrophoresis solution;
p3: putting a platinum electrode as a positive electrode and the interdigital graphite paper in the P1 as a negative electrode into the suspension liquid in the P2 in parallel, and preparing the V by electrophoretic deposition for 2 minutes under the voltage of 24V 2 CT x A flexible electrode;
p4: with the flexibility V described in P3 2 CT x The anode and the zinc cathode are placed on a polyimide film in parallel, then zinc sulfate polyacrylamide electrolyte is coated on the two electrodes, the flexible water system zinc ion hybrid capacitor is packaged by a polyethylene glycol terephthalate film, and the flexible water system zinc ion hybrid capacitor is placed overnight to test the electrochemical performance of the flexible water system zinc ion hybrid capacitor.
Example three:
in a preferred embodiment of the invention, based on multiple layers V 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
s1: etching V 2 AlC MAX, centrifugal cleaning and freeze drying to prepare V of accordion structure 2 CT x A powder;
v of accordion structure 2 CT x The powder was V-etched selectively with a mixture of sodium fluoride (NaF, > 99%) and hydrochloric acid (HCl, 36-38%) 2 Synthesizing AlC; 1g V 2 Slowly adding AlC MAX phase (Kai ceramic materials Co., ltd., laizhou, not less than 400 meshes) into a mixed solution of 1g NaF and 20mL HCl (6M), and continuously reacting for 7 days at 90 ℃; then, centrifugally washing the reaction product with deionized water for many times until the pH value is close to 7; finally, the precipitate is subjected to vacuum freeze drying to obtain V with an accordion structure 2 CT x Powder;
s2: for V of accordion structure obtained in S1 2 CT x Intercalation treatment and centrifugal screening are carried out to prepare intercalated V 2 CT x A powder;
1g of V in accordion structure obtained in S1 2 CT x The powder was intercalated with 10mL tetrabutylammonium hydroxide (TBAOH) solution (25%) for 8 hours at room temperature to increase the V of the accordion structure 2 CT x The intercalated precipitate was washed several times with ultrapure water to remove residual tetrabutylammonium hydroxide (TBAOH), followed by adding ultrapure water and ultrasonic treatment for 1 hour under an argon atmosphere to peel it off; centrifuging the suspension at rotation speed of 3500r/min and lifting rate of 5 for 30min, and freeze drying the obtained precipitate to obtain multilayer V 2 CT x Powder;
s3: centrifuging the supernatant 8000r/min obtained in S2 to prepare V with few layers 2 CT x Powder;
centrifuging the centrifuged solution obtained in S2 for 30min at a rotor speed of 7, a rotation speed of 8000r/min and a lifting rate of 5, and freeze-drying the obtained precipitate to obtain V with few layers 2 CT x And (3) powder.
Multilayer V prepared by the above method 2 CT x Can be used for preparing V 2 CT x The flexible electrode is applied to the positive electrode of the flexible water system zinc ion hybrid capacitor.
Said multilayer V 2 CT x The preparation method of the flexible water system zinc ion hybrid capacitor comprises the following steps:
p1: carving graphite paper with the thickness of 0.05mm into an interdigital shape by using a laser carving machine to serve as a flexible conductive substrate, wherein the area of the carved interdigital is 1.1723cm 2 ；
P2: weighing V 2 CT x Powder and iodine, in a ratio of 3:2, adding the mixture into an acetone solution, and performing ultrasonic treatment for 30 minutes to form a uniform suspension as an electrophoresis solution;
p3: putting a platinum electrode as a positive electrode and the interdigital graphite paper in the P1 as a negative electrode into the suspension liquid in the P2 in parallel, and preparing the V by electrophoretic deposition for 2 minutes under the voltage of 24V 2 CT x A flexible electrode;
p4: with P3 said flexible V 2 CT x The anode and the zinc cathode are arranged in parallelThe flexible water system zinc ion hybrid capacitor is placed on a polyimide film, then zinc sulfate polyacrylamide electrolyte is covered on the two electrodes, the flexible water system zinc ion hybrid capacitor is packaged by a polyethylene glycol terephthalate film, and the flexible water system zinc ion hybrid capacitor is placed overnight and then the electrochemical performance of the flexible water system zinc ion hybrid capacitor is tested.
The MXene flexible electrode prepared in the embodiment is used for assembling a water-based zinc ion hybrid capacitor, and fig. 5 is an electrochemical stability performance diagram of the water-based zinc ion hybrid capacitor assembled by the MXene flexible electrode prepared in the embodiment, and the study finds that the capacitor storage is as high as 80% after 8000 continuous charge-discharge cycle tests.
In the technical scheme of the invention, V with better effect is provided in the embodiment 2 CT x Concentration of electrophoretic fluid, but the present invention is not limited to V given in the above examples 2 CT x Concentration of electrophoretic fluid, V 2 CT x The concentration of the electrophoretic solution is 1.5mg/mL, and may be 0.5mg/mL, 1mg/mL, 2mg/mL or the like in examples, and specific V 2 CT x The concentration of the electrophoretic fluid is determined according to actual needs.
In the technical scheme of the invention, the centrifugal rotating speed with better effect is given in the embodiment, but the invention is not limited to 3500r/min and 8000r/min given in the embodiment so as to obtain multilayer and few-layer V 2 CT x 3500r/min, 8000r/min, 3000r/min, 9000r/min, etc. as given in the examples, and specific V 2 CT x The layer number screening is determined according to actual needs.
In the technical scheme of the invention, the current collector with a better effect is provided in the embodiment, but the invention is not limited to the current collector provided in the embodiment, the current collector used for conducting is titanium foil or other conducting current collectors, graphite paper in the embodiment can be taken, conducting current collectors can be taken, and the specific current collector is determined according to actual needs.
In the technical scheme of the invention, V is deposited by electrophoresis 2 CT x The flexible electrode is prepared and packaged with the zinc cathode and zinc sulfate hydrogel to obtain the flexible zinc ion hybrid capacitor which does not need to be added with any binder and conductive agent and has excellent electrochemical performance compared with the flexible zinc ion hybrid capacitorThe traditional flexible electrode preparation process is low in cost and expected to be produced in a large scale, and acetone is used as an electrophoresis solution solvent, so that the electrode can be prevented from being oxidized, and the flexible electrode preparation process has great advantages in the field of flexible wearable.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. V based on different layer numbers 2 CT x The preparation method of the material is characterized by comprising the following steps:
s1: weighing V 2 Adding AlC MAX precursor into etching solution composed of NaF and HCL for hydrothermal reaction, repeatedly centrifuging and washing the product, and freeze-drying at low temperature to form V with accordion structure 2 CT x Powder;
s2: v of accordion structure in S1 2 CT x Adding the powder into TBAOH solution for intercalation, repeatedly centrifuging and washing the resultant, performing ultrasonic treatment at low temperature under the protection of inert atmosphere, centrifuging at 3500r/min for 30min to obtain precipitate, and freeze-drying the precipitate to obtain multilayer V 2 CT x Powder;
s3: centrifuging the supernatant obtained in S2 at 8000r/min for 30min to obtain precipitate, and freeze drying the precipitate to obtain small layer V 2 CT x And (3) powder.
2. The V of claim 1 based on a different number of layers 2 CT x A method for producing a material, characterized in that V described in S1 2 The grain size of AlC MAX phase powder is 400 meshes, the hydrothermal reaction temperature is 90 ℃, and the hydrothermal reaction time is 7d.
3. The V of claim 1 based on a different number of layers 2 CT x MaterialCharacterized in that V is as described in S1 2 The mass ratio of AlC MAX phase powder to NaF is 1, and the concentration of HCL is 6mol/L.
4. The V of claim 1 based on a different number of layers 2 CT x The preparation method of the material is characterized in that the V of the accordion structure in S2 2 CT x The mass of the powder was 1g and the mass fraction of TBAOH solution was 25%.
5. The V of claim 1 based on a different number of layers 2 CT x The preparation method of the material is characterized in that the inert atmosphere in S2 is argon atmosphere, and the ultrasonic treatment time is 1h.
6. The V of claim 1 based on a different number of layers 2 CT x The preparation method of the material is characterized in that the freeze drying time of S1, S2 and S3 is 24h.
7. Method for producing a capacitor in which positive electrodes are provided with V in different layers, obtained according to any of claims 1 to 6 2 CT x V made of powder 2 CT x The flexible electrode is characterized in that the preparation method comprises the following steps:
p1: carving graphite paper into an interdigital shape by using a laser carving machine to serve as a flexible conductive substrate;
p2: will V 2 CT x Adding the powder and iodine into an acetone solution, and performing ultrasonic dispersion to form a uniform suspension;
p3: preparing V by electrophoretic deposition by taking a platinum electrode as a positive electrode, taking the interdigital graphite paper P1 as a negative electrode and taking the suspension P2 as electrophoretic liquid 2 CT x A flexible electrode;
p4: v as described under P3 2 CT x The flexible electrode is a positive electrode, the electrogalvanizing nano-sheet is a negative electrode, znSO 4 The hydrogel is an electrolyte to assemble the flexible water system zinc ion hybrid capacitor.
8. The method of claim 7 wherein the graphite paper in P1 has a thickness of 0.05mm and an interdigitated area of 1.1723cm after engraving -2 。
9. The method for preparing a capacitor according to claim 7 wherein V is defined in P2 2 CT x The mass ratio of powder to iodine was 3:2 with a sonication time of 30min.
10. The method of claim 7, wherein the electrophoretic voltage of the electrophoretic deposition in P3 is 24V, and the electrophoretic time is 2min.
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