CN112928342B - Multifunctional zinc ion micro battery and preparation method and application thereof - Google Patents

Multifunctional zinc ion micro battery and preparation method and application thereof Download PDF

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CN112928342B
CN112928342B CN202110181879.4A CN202110181879A CN112928342B CN 112928342 B CN112928342 B CN 112928342B CN 202110181879 A CN202110181879 A CN 202110181879A CN 112928342 B CN112928342 B CN 112928342B
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mxene
mwcnts
zinc ion
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micro battery
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CN112928342A (en
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王思亮
赵丙田
林洋
任信钢
曾玮
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Anhui University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
    • H01M50/136—Flexibility or foldability

Abstract

The invention discloses a multifunctional zinc ion micro battery and a preparation method thereof. The multifunctional miniature zinc ion battery mainly comprises MWCNTs-VO2(B) Positive electrode, MXene-TiS2Negative electrode and PAM-ZnSO4The preparation method of the hydrogel electrolyte mainly comprises the following steps: s1: MWCNTs-VO2(B) Preparing a positive electrode; s2: and MXene-TiS2Preparing a negative electrode; s3: PAM-ZnSO4Preparing a hydrogel electrolyte; s4: and (5) packaging the zinc ion micro battery. The multifunctional miniature zinc ion battery provided by the invention has the advantages of high energy density, excellent flexibility, high safety, variable specifications and high temperature resistance, and meanwhile, the preparation process is simple and the cost is low.

Description

Multifunctional zinc ion micro battery and preparation method and application thereof
Technical Field
The invention belongs to the field of micro batteries, and particularly relates to a multifunctional zinc ion micro battery and a preparation method and application thereof.
Background
There is an increasing demand in modern society for smart wearable devices and flexible electronic products, which are generally required to meet the diversity of shapes and good flexibility. Various products such as flexible displays, flexible electronic skins, intelligent electronic clothing, intelligent wearable devices and the like are in endlessly developed, and the requirements of the development of the emerging industries on flexible electronic devices are higher and higher. Although energy density of traditional energy storage devices such as lithium ion batteries, alkaline zinc manganese batteries and lead-acid batteries is high, defects such as large volume, heavy weight and fixed shape are difficult to solve for a while, so that the traditional energy storage devices cannot be used for directly supplying energy to flexible electronic devices, and an element capable of effectively supplying energy to emerging products is needed in society. Therefore, the advent of miniature flexible batteries is inevitable.
As the development of lithium ion battery technology has matured, researchers are struggling to develop lithium ion microbatteries with organic electrolytes as substrates. Despite the progress that has been made to date, these lithium ion micro batteries still have a number of significant drawbacks. For example, because the electrolyte is an organic solvent, lithium ion batteries have safety problems of flammability, volatility, toxicity and the like; the natural content of metallic lithium is not high and therefore the cost required for large-scale production of lithium ion batteries is high. Therefore, the development of a micro battery with high energy density, high flexibility, high safety, small size, high temperature resistance and low cost is urgent.
For example, the article "Scalable failure of printed Zn// MnO 2 planar micro-batteries with high volumetric energy density and experimental safety (Xiao Wang, shuanghao Zheng, feng Zhou et al. NATIONAL SCIENCE REVIEW,2020,7, 64-72) "discloses a planar printing type micro-zinc ion battery, the specific volumetric capacity of which can reach 19.3mAh cm -3 The maximum energy density can reach 17.3mWh cm -3 . However, the technology disclosed in this document still has the following disadvantages: (1) Prepared Zn// MnO 2 The planar micro battery has complex process and higher manufacturing cost; (2) Prepared Zn// MnO 2 The planar micro-battery has low specific capacity and insufficient energy density and can not continuously supply energy to electronic devices; (3) Prepared Zn// MnO 2 The planar micro-battery has no temperature resistance and damage prevention characteristics, and cannot meet more application scenes.
Disclosure of Invention
The invention provides a multifunctional zinc ion micro battery and a preparation method thereof, aiming at overcoming the defects of the prior art and the requirements of the flexible device industry, and aiming at providing the multifunctional zinc ion micro battery which has high energy density, high flexibility, high safety, variable specifications, high temperature resistance and low price, thereby solving the problems of poor mechanical property, large volume and mass, low energy density, low safety and the like of the conventional micro ion battery.
The invention provides a multifunctional zinc ion micro battery, which mainly comprises MWCNTs-VO 2 (B) (multiwalled carbon nanotube-vanadium dioxide) anode, MXene-TiS 2 (Mekkien-titanium disulfide) negative electrode and PAM-ZnSO 4 (polyacryl groupAmine-zinc sulfate) hydrogel electrolyte. The MWCNTs-VO 2 (B) Positive electrode and MXene-TiS 2 The negative electrode is preferably an interdigital electrode, and the PAM hydrogel electrolyte covers the surfaces of the positive electrode and the negative electrode.
The invention also provides a preparation method of the multifunctional zinc ion micro battery, which comprises the following steps: (1) MWCNTs-VO 2 (B) Preparation of Positive electrode, (2) MXene-TiS 2 Preparation of negative electrode, (3) PAM-ZnSO 4 Preparation of hydrogel electrolyte, and (4) encapsulation of zinc ion micro-batteries.
In the above preparation method, the preferable step (1) is to mix MWCNTs, SDS (sodium dodecyl sulfate) and VO 2 (B) Adding the mixture into deionized water, and obtaining a uniform mixed solution after ultrasonic crushing; vacuum filtering the mixed solution, then washing with deionized water, freezing, drying and peeling to obtain MWCNTs-VO 2 (B) Filter cake, MWCNTs-VO 2 (B) Laser engraving a filter cake to prepare MWCNTs-VO 2 (B) And (4) a positive electrode. Wherein, preferably, the mass ratio of MWCNTs to SDS is 1-5 2 (B) 1 to 3, more preferably 1; the ultrasonic crushing time is 0.5 to 1 hour; the deionized water is washed for 3-6 times. The VO 2 (B) Commercially available from professional manufacturers, but of course reference can also be made to: adv. Energy mater.2019,9,1901957 preparation: will V 2 O 5 (vanadium pentoxide) and H 2 C 2 O 4 ·2H 2 Adding O (oxalic acid dihydrate) into deionized water, and stirring in a water bath to obtain a mixed solution; transferring the mixed solution to a reaction kettle for high-temperature reaction; filtering and cleaning the reaction product by water and alcohol to prepare VO 2 (B) In that respect Wherein, V 2 O 5 And H 2 C 2 O 4 ·2H 2 The mass ratio of O is 2; the stirring time is 1-2 h, and the stirring temperature is 60-80 ℃; the high-temperature reaction time is 3-6 h, and the reaction temperature is 160-200 ℃; the washing times of water and alcohol are 3-6 times.
In the above production method, the step (2) is preferably to subject TiS to 2 Adding MXene and the MXene into deionized water, and performing ultrasonic treatment to obtain uniform mixed liquid; the mixed liquid is filtered in vacuum, dried and stripped to obtain MXene-TiS 2 Filter cake ofMXene-TiS 2 The filter cake is carved by laser to obtain MXene-TiS 2 And a negative electrode. Among them, preferred are MXene and TiS 2 3, more preferably 3:2; the ultrasonic time is 0.5-1 h. Preferably, the MXene material is at least one of transition two-dimensional metal carbide or carbonitride, preferably Ti 3 C 2 、Ti 2 C、Hf 3 C 2 、Ta 3 C 2 、Ta 2 C、Zr 3 C 5 、V 2 At least one of C, more preferably Ti 3 C 2 In general, MXene refers to Ti 3 C 2 It is available from professional manufacturers, although reference may be made to: nano-Micro Lett.2019,11, 70.
In the above production method, acrylamide and K are preferably used in the step (3) 2 S 2 O 4 And N, N' -methylenebisacrylamide with ZnSO 4 Putting the solution into a water bath kettle and stirring; transferring the stirred solution into a specific container, and carrying out high-temperature polymerization reaction to obtain PAM-ZnSO 4 A hydrogel electrolyte. Of these, preferably, the ZnSO 4 The concentration of the solution is 1 to 3mol L -1 The mass of the acrylamide is 5-15g 2 S 2 O 4 The mass is 30-80mg, and the mass of N, N' -methylene bisacrylamide is 1-5 mg; the stirring time of the water bath kettle is 1 to 3 hours, and the stirring temperature is 30 to 50 ℃; the polymerization temperature is 60-90 ℃, the polymerization time is 1-5 h, more preferably 75-85 ℃, and the reaction time is 2-4 h. In the invention, the hydrogel obtained by polymerization reaction can be coated with waterborne Polyurethane (PU) drop by drop on the surface, so that the bonding and healing capabilities of the hydrogel can be improved; the aqueous Polyurethane (PU) can be obtained from a professional manufacturer, such as a series of products selected from ADWEL series, LEASYS series, TEKSPRO series, etc. of Wanhua chemical group, inc.
In the above preparation method, the preferable step (4) is to subject MWCNTs-VO to 2 (B) Positive electrode and MXene-TiS 2 Transferring the negative electrode to a flexible substrate, and adding PAM-ZnSO 4 Preparing a zinc ion micro battery by using a hydrogel electrolyte; the flexible substrate is a common flexible material such as poly-pPolyethylene terephthalate (PET) films, polydimethylsiloxane (PDMS) films, polyimide (PI) films, polyetherimide (PEI) films, and the like.
The invention also provides application of the multifunctional zinc ion micro battery in intelligent wearable equipment or flexible electronic products, such as various products of flexible displays, flexible electronic skins, intelligent electronic clothes, intelligent wearable equipment and the like.
In summary, compared with the current micro battery technology, the micro battery of the present invention has the following advantages:
(1) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has better electrochemical performance at 0.2893mA cm -2 The specific capacity reaches 40.8 mu Ah cm under the current density -2 As shown in fig. 4.
(2) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has better flexibility, and can still maintain 95-98% of the initial capacity (when bent at 0 ℃) when bent at 150 ℃.
(3) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has higher safety, selects nontoxic PAM (polyacrylamide) as electrolyte and can be applied to wearable electronic equipment.
(4) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has better temperature resistance and can normally work at the ambient temperature of 25-100 ℃.
(5) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has the self-healing characteristic, and can still work after being cut and bonded again.
(6) Compared with the traditional micro battery, the micro battery designed on the basis of the invention has simpler preparation process and low cost.
Drawings
FIG. 1 is a general process for manufacturing a multi-functional micro zinc-ion battery according to the present invention;
FIG. 2 shows MWCNTs-VO with different mass ratios of the multifunctional miniature zinc ion battery 2 (B) CV curve of positive electrode at same scan rate, where MWCNTs and VO are 2 (B) When the mass ratio is 6;
FIG. 3 shows MXene-TiS of different mass ratios of a multifunctional miniature zinc ion battery 2 The CV curve of the negative electrode at the same scanning rate shows obvious oxidation-reduction peaks. Wherein, when MXene and TiS 2 The mass ratio is 6:4, namely 3;
fig. 4 is a GCD curve of the multifunctional micro zinc-ion battery of the present invention after assembly under different charging and discharging current densities, wherein the charging and discharging current densities are gradually increased from right to left.
Fig. 5 is a diagram showing the change of specific capacity after the multi-functional miniature zinc ion battery of the present invention is charged and discharged for a plurality of times, and the electrode is fully activated after the previous charging and discharging for a plurality of times, so that the front end of the image is obviously increased. As a whole, at 4.32mA cm -2 Under the current density of the battery, after hundreds of times of charging and discharging, the specific capacity of the battery has no obvious change, and the excellent cycling stability performance of the battery is shown;
fig. 6 is a graph of series voltage of a multifunctional miniature zinc ion battery of the present invention, which is measured during the experiment, wherein the voltage is not in a standard multiple relation and is caused by the self-discharge of the battery. The results show that each cell remained approximately at 1.51V after series connection;
fig. 7 is an experimental picture of the multifunctional micro zinc-ion battery of the present invention bent during an experiment, but the brightness of the LED lamp is not changed significantly;
FIG. 8 is a graph showing the change of the specific capacity of the multifunctional miniature zinc ion battery under different bending angles, wherein the graph shows the excellent bending performance of the multifunctional miniature zinc ion battery, and the charge-discharge current density is 1.1574mA cm -2 Under the condition of (2), the specific capacity is almost unchanged within the bending angle range of 0-150 degrees;
fig. 9 shows that the ambient temperature of a multifunctional micro zinc-ion battery of the present invention was changed during the experiment, and the brightness of the LED lamp was hardly changed when the ambient temperature was compared with 75 deg.c;
fig. 10 is a graph showing the specific capacity of the multifunctional micro zinc-ion battery according to the present invention at different temperatures, and generally speaking, the multifunctional micro zinc-ion battery can still work normally at higher ambient temperatures;
fig. 11 shows the operation of cutting and then bonding the multifunctional micro zinc-ion battery of the present invention in an experiment, and the experimental result shows that the bonded micro battery can still light the LED, which demonstrates the high self-healing capability of the present invention, the left diagram shows that the LED lamp is on before cutting, the middle diagram shows that the LED is off after cutting, and the right diagram shows that the LED lamp is turned on again after healing;
fig. 12 is a GCD curve of a multi-functional micro zinc-ion battery of the present invention after being cut for different times, and the image shows that the performance of the micro battery is comparable to the performance of the micro battery without being cut even after 8 times of cutting. The cutting method comprises the following steps: after the micro battery is cut, the two cut ends are put together and placed for a period of time under the combined action of the viscosity of PU and hydrogel, and the cut ends can be healed.
Detailed Description
In order to make the characteristics, experimental method and application scene of the present invention more intuitive, the present invention is further described in detail below according to the experimental contents of the accompanying drawings. It should be noted that the following experimental descriptions are only for further explaining the present invention and should not be construed as limiting the present invention. Meanwhile, each raw material such as V referred to in examples 2 O 5 、MWCNTs、SDS、MXene、TiS 2 PU, etc. are known conventional raw materials.
Example 1
(1) Preparation of MWCNTs-VO 2 (B) And (4) a positive electrode.
6mg of MWCNTs, 60mg of SDS and 6mg of VO 2 (B) Adding the mixture into 40mL of deionized water, and performing ultrasonic crushing to obtain a uniform mixed solution, wherein the ultrasonic crushing time is 1h, and the ultrasonic crushing power is 850W; vacuum filtering the mixed solution, washing with deionized water for 3 times, and freezingDrying to obtain MWCNTs-VO 2 (B) And (3) filtering a cake. MWCNTs-VO 2 (B) The filter cake is carved into an interdigital electrode by a laser carving machine to finally prepare the MWCNTs-VO 2 (B) And (4) a positive electrode.
(2) Preparation of MXene-TiS 2 And a negative electrode.
4mg of TiS 2 Carrying out ultrasonic treatment on the solution for 30min in 20mL of deionized water, then adding 6mg of MXene, and carrying out ultrasonic treatment again for 30min; the obtained product is filmed to obtain MXene-TiS 2 Filter cake of MXene-TiS 2 The filter cake is carved into an interdigital electrode by a laser carving machine to obtain MXene-TiS 2 And a negative electrode.
(3) Preparation of PAM-ZnSO 4 A hydrogel electrolyte.
12g of acrylamide, 5mg of N, N' -methylenebisacrylamide and 50mg of K 2 S 2 O 4 Adding the mixture into 30mL of the solution and 2mol L of the solution in sequence -1 ZnSO of 4 Stirring the solution in a water bath kettle for 2h at 40 deg.C, transferring the uniformly stirred solution into a specific container, performing polymerization reaction at 80 deg.C for 3h, and uniformly dripping waterborne Polyurethane (PU) on the surface of the formed hydrogel to obtain PAM-ZnSO 4 A hydrogel electrolyte.
(4) And packaging the multifunctional miniature zinc ion battery.
MWCNTs-VO 2 (B) Positive electrode and MXene-TiS 2 Transferring the negative electrode onto a flexible substrate, adding PAM-ZnSO 4 And (3) hydrogel electrolyte to finally prepare the multifunctional miniature zinc ion battery, wherein the flexible substrate is a polyethylene terephthalate (PET) film.
Example 2
Preparation of MWCNTs-VO 2 (B) And (3) positive electrode: with 2mg VO 2 (B) Otherwise, MWCNTs-VO was prepared in the same manner as in the step (1) of example 1 2 (B) And (4) a positive electrode.
Example 3
Preparation of MWCNTs-VO 2 (B) And (3) positive electrode: with 4mg VO 2 (B) Otherwise, MWCNTs-VO was prepared in the same manner as in the step (1) of example 1 2 (B) And (4) a positive electrode.
Example 4
Preparation of MXene-TiS 2 Negative electrode: using 2mg of TiS 2 MXene-TiS was obtained in the same manner as in the step (2) in example 1 2 And a negative electrode.
Example 5
Preparation of MXene-TiS 2 Negative electrode: with 6mg TiS 2 MXene-TiS was obtained in the same manner as in the step (2) in example 1 2 And a negative electrode.
The multifunctional miniature zinc ion battery prepared by the invention has the characteristics of high specific capacity (high energy density), high flexibility, high self-healing property, high safety, high temperature resistance, low cost and the like. MWCNTs-VO with different mass ratios in examples 2 (B) The CV curve of the positive electrode at the same scanning rate is shown in FIG. 2, and MXene-TiS with different mass ratios 2 The CV curve of the negative electrode at the same scanning rate is shown in FIG. 3, the change graph of the specific capacity of the micro battery packaged in the example after being charged and discharged for multiple times is shown in FIG. 5, the micro battery packaged in the example is connected in series, the experimental result of measuring the series voltage of the micro battery is shown in FIG. 6, the micro battery packaged in the example is bent, the change of the LED lamp is shown in FIG. 7, the change image of the specific capacity of the micro battery in the example under different bending angles is shown in FIG. 8, the environment temperature of the micro battery packaged in the example is changed, and the change of the LED lamp is shown in FIG. 9; the graph of the specific capacity of the micro battery of the example at different temperatures is shown in fig. 10, the effect of lighting the LED when the micro battery of the example is cut first and then bonded is shown in fig. 11, and the GCD curve of the micro battery of the example after being cut for different times is shown in fig. 12.
Tests show the excellent characteristics of the micro-battery of the invention, flexibility, temperature resistance and self-healing, which enable the micro-battery of the example to work normally under various complex conditions, and the following specific scenarios are given for several applications:
(1) Flexible wearable devices have become popular in the market, and for this new type of electronic device, it is difficult for a conventional battery to power it, and therefore flexible batteries have been developed. Under the bending angle of 0-150 degrees, all parameters of the micro battery are not obviously changed, and the micro battery can adapt to external force extrusion under most conditions; the invention can be used for wearable electronic products by virtue of good flexibility and bendability, and has a strong pushing effect on the smart clothes industry which is invisibly emerging.
(2) For natural reasons, most products in life cannot always work in a constant temperature environment, and the products are required to work normally in a certain temperature range. Obviously, the micro battery of the present invention can meet this requirement well, as shown in fig. 9, and can work normally at an ambient temperature of 25 ℃ to 100 ℃.
(3) The flexible product is likely to be damaged and torn in use, and the micro battery can better solve the situations. After the battery is torn, the battery can be continuously operated in a bonding mode, and therefore some emergency situations can be solved, and time is taken for replacing the battery.
It should be noted that in the technical solution of the present invention, although some preferred amounts are given in the embodiments, for example: tiS 2 And MXene, but the invention is not limited to TiS given in the examples above 2 And MXene due to MXene and TiS 2 The mass ratio is within the range of 3. The scope of the invention is defined by the appended claims. It should be understood by those skilled in the art that any modification, equivalent replacement, and improvement made based on the spirit of the present invention should be considered to be within the spirit and scope of the present invention.

Claims (3)

1. A preparation method of a multifunctional zinc ion micro battery comprises the following steps: (1) MWCNTs-VO 2 (B) Preparation of Positive electrode, (2) MXene-TiS 2 Preparation of negative electrode, (3) PAM-ZnSO 4 Preparing a hydrogel electrolyte, and (4) packaging a zinc ion micro battery;
said step (c) is(1) MWCNTs, SDS and VO 2 (B) Adding the mixture into deionized water, and obtaining a uniform mixed solution after ultrasonic crushing; vacuum filtering the mixed solution, washing with deionized water, drying and peeling to obtain MWCNTs-VO 2 (B) Filter cake, MWCNTs-VO 2 (B) The filter cake is carved by laser to obtain MWCNTs-VO 2 (B) A positive electrode; the mass ratio of the MWCNTs to the SDS is 1 to 5-1 2 (B) The mass ratio of (A) to (B) is 3; the ultrasonic grinding time is 0.5 to 1 hour, and the ultrasonic grinding power is 800W to 1000W; the deionized water cleaning times are 3 to 6;
the step (2) is to mix TiS 2 Adding MXene and the MXene into deionized water, and performing ultrasonic treatment to obtain uniform mixed liquid; the mixed liquid is filtered in vacuum and dried and stripped to obtain MXene-TiS 2 Filter cake, mixing MXene-TiS 2 The filter cake is carved by laser to obtain MXene-TiS 2 A negative electrode; the MXene and TiS 2 The mass ratio is 3; the ultrasonic time is 0.5 to 1 hour, and the ultrasonic power is 400W to 550W;
the step (3) is that acrylamide and K are mixed 2 S 2 O 4 And N, N' -methylenebisacrylamide with ZnSO 4 Adding the solution into a water bath kettle, and stirring; transferring the stirred solution into a specific container, and carrying out high-temperature polymerization reaction; to prepare PAM-ZnSO 4 A hydrogel electrolyte; the ZnSO 4 The concentration of the solution is 1 to 3mol L -1 The mass of the acrylamide is 5 to 15g 2 S 2 O 4 The mass is 30 to 80mg, and the mass of N, N' -methylene bisacrylamide is 1 to 5mg; stirring in a water bath kettle for 1 to 3 hours at the stirring temperature of 30 to 50 ℃; the polymerization temperature is 60 to 90 ℃, and the polymerization time is 1 to 5 hours;
the step (4) is to mix MWCNTs-VO 2 (B) Positive electrode and MXene-TiS 2 Transferring the negative electrode to a flexible substrate, and adding PAM-ZnSO 4 And (3) uniformly dripping water-based polyurethane on the surface of the formed hydrogel to prepare the zinc ion micro battery.
2. The multifunctional zinc ion micro battery prepared by the preparation method of claim 1.
3. Use of the multifunctional zinc ion micro battery of claim 2 in smart wearable devices or flexible electronics.
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CN110010862B (en) * 2019-03-15 2022-03-29 辽宁科技大学 MXene-Ti as positive electrode material of magnesium secondary battery3C2/TiS2And method for preparing the same
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CN110289452B (en) * 2019-07-25 2021-06-25 安徽大学 Flexible zinc ion micro battery and preparation method thereof
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CN111180694B (en) * 2019-12-31 2021-11-19 广东工业大学 MXene/metal sulfide composite material, negative electrode material, preparation and application
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CN112018347A (en) * 2020-08-10 2020-12-01 五邑大学 NbS2/MXene composite material and preparation method thereof
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