NL2030752A - Multi-functional zinc ion micro-battery and preparation method and application thereof - Google Patents
Multi-functional zinc ion micro-battery and preparation method and application thereof Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 230000009975 flexible effect Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000010147 laser engraving Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 4
- 239000011686 zinc sulphate Substances 0.000 abstract 2
- 235000009529 zinc sulphate Nutrition 0.000 abstract 1
- 230000008859 change Effects 0.000 description 12
- 238000013461 design Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- -1 K:S:0: Chemical compound 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium 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
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/136—Flexibility or foldability
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed a multi—functional zinc ion micro—battery and a preparation method thereof. The multi—functional zinc ion micro— battery consists of an MWCNTs—V02 (B) anode, an MXene—Ti82 cathode, and a PAM—ZnSO4 hydrogel electrolyte. The preparation method includes the following steps: Sl, preparing the MWCNTs—V02 (B) anode; SZ, preparing the MXene—Ti82 cathode; S3, preparing the PAM— ZnSO4 hydrogel electrolyte; and S4, encapsulating the zinc ion micro—battery. The multi—functional zinc ion micro—battery has advantages of high energy density, excellent flexibility, high safety, varied specifications, and high temperature resistance, and a preparation process thereof is simple and low in costs.
Description
TECHNICAL FIELD The present disclosure belongs to the field of a micro- battery, and particularly relates to a multi-functional zinc ion micro-battery and a preparation method and application thereof.
BACKGROUND ART In a modern society, there are increasing needs in smart wearable equipment and a flexible electronic product. Such prod- uct, generally, needs to meet requirements of diversified shapes and an excellent flexibility. A variety of products, such as a flexible display, a flexible electronic skin, a smart electronic clothing, and smart wearable equipment, emerge in endlessly. With a development of these emerging industries, a requirement on a flexible electronic device is higher and higher. Although tradi- tional energy storage devices, such as a lithium ion battery, an alkaline zinc-manganese battery, and a lead acid battery, are high in an energy density, such traditional energy storage elements fail to supply an energy to the flexible electronic device direct- ly due to a large volume, a large weight, a fixed shape, and other defects which are difficult to overcome. Therefore, there is a need for an element that can provide the energy for these newly- developing products effectively in the society. Therefore, it is inevitable for an emergence of a flexible micro-battery. As a lithium ion battery technology has been developed ma- turely, a researcher is developing a lithium ion micro-battery taking an organic electrolyte as a substrate with great efforts. Although a certain progress has been made, there still be a lot of defects that should be noticeable in the lithium ion micro- battery. For example, as an organic solvent is used as the elec- trolyte, the lithium ion battery is flammable, volatile, and tox- ic, and have other safety problems; and due to a low natural con- tent of a lithium metal, costs for a mass production of the lithi- um ion batteries are high. In view of the above, developing the micro-battery with a high energy density, a high flexibility, a high safety, a small volume, high temperature resistance, and a low cost has been extremely urgent. For example, a paper “Scalable fabrication of printed %Zn//MnQ, planar micro-batteries with high volumetric energy density and exceptional safety (Xiao Wang, Shuanghao Zheng, Feng Zhou et al .NATIONAL SCIENCE REVIEW, 2020,7,64-72)" discloses a planar printed zinc ion micro-battery. A volume specific capacity of the zinc ion micro-battery can be up to 19.3 mAh cm™, and a maximum energy density can be up to 17.3 mWh cm™. There are still several defects in a technology disclosed in the literature: (1) a prepa- ration process of a Zn//MnC, planar micro-battery is complex, and high in a cost; (2) the prepared 2Zn//Mn0: planar micro-battery is low in a specific capacity, and can’t provide an energy for the electronic device continuously due to the insufficient energy den- sity; and (3) the prepared Zn//Mn0; planar micro-battery can’t be applied in more application scenes due to lack of characteristics of temperature resistance and damage prevention.
SUMMARY The present disclosure provides a multi-functional zinc ion micro-battery and a preparation method thereof based on defects in the prior art and needs in an industry of a flexible device, which aims to provide the multi-functional zinc ion micro-battery with a high energy density, a high flexibility, a high safety, varied specifications, high temperature resistance, and a low cost, thereby solving problems of poor mechanical performance, large volume and mass, low energy density, low safety, and the like in the current micro-ion battery. The present disclosure provides a multi-functional zinc ion micro-battery, which consists of an MWCNTs-VO, (B) (multiwalled carbon nanotube-vanadium dioxide) anode, an Xene-TiS, (Mxene- titanium disulfide) cathode, and a PAM-ZnS0,; (polyacrylamide-zinc sulfate) hydrogel electrolyte. The MWCNTs-V0: (B) anode and the MXene-TiS: cathode are interdigital electrodes preferably, and the PAM hydrogel electrolyte covers on surfaces of the anode and the cathode. The present disclosure further provides a preparation method for the multi-functional zinc ion micro-battery, which includes the following steps: (1) preparing the MWCNTs-VO, (B) anode; (2) preparing the MXene-TiS: cathode; (3) preparing the PAM-ZnS0: hy- drogel electrolyte; and (4) encapsulating the zinc ion micro- battery. Preferably, in the step (1) of the preparation method, adding MWCNTs, SDS (sodium dodecyl sulfate), and VO; (B) into deionized water, conducting an ultrasonic dispersion, and obtaining a uni- form hybrid solution; filtering the hybrid solution under a vacu- um, cleaning with the deionized water, freeze-drying, peeling off, and obtaining an MWCNTs-VO, (B) filter cake; and conducting a laser engraving on the MWCNTs-VO, {B} filter cake, and obtaining the MWCNTs-VO, (B) anode, where preferably, a mass ratio of the MWCNTs to the SDS ranges from 1: 5 to 1: 15, a mass ratio of the MWCNTs to the VO, (B) ranges from 3: 1 to 3: 3, and more preferably 1: 1; time for the ultrasonic dispersion ranges from 0.5 to 1 h; and times of cleaning with the deionized water range from 3 to 6. The VO: (B) can be either purchased from a professional manufacturer, or prepared with reference to a reference: Adv. Energy Mater. Sep.
2019, 1901957, that is, adding V,0; (vanadium pentoxide) and H:C.04 « 2H:0 (oxalic acid dihydrate) into the deionized water, stirring in a water bath, and obtaining a hybrid solution; transferring the hybrid solution to a reaction still for a high-temperature reac- tion; and conducting a fine filtration on a reaction product with water and an alcohol, cleaning, and obtaining the VO, (B), where a mass ratio of the V,0; to the H,C,0;, « 2H.0 is 2: 3; stirring time ranges from 1 to 2 h, and a stirring temperature ranges from 60 to 80°C; time for the high-temperature reaction ranges from 3 to 6 h, and a reaction temperature ranges from 160 to 200°C; and times of cleaning with the water and the alcohol range from 3 to 6.
Preferably, in the step (2) of the preparation method, adding TiS: and MXene into the deionized water, conducting an ultrasound, and obtaining a uniform hybrid solution; filtering the hybrid so- lution under the vacuum, drying, peeling off, and obtaining an MXene-TiS, filter cake; and conducting the laser engraving on the MXene-TiS, filter cake, and obtaining the MXene-TiS, cathode, where preferably, a mass ratio of the Mxene to the TiS: ranges from 3: 1 to 3: 3, and more preferably 3: 2; and ultrasound time ranges from
0.5 to 1 h. Preferably, the MXene material is at least one of a two-dimensional transition metal carbide or carbonitride, prefera- bly at least one of TisC:, TiC, HfsC:, TasC;, Ta:C, Zr:C:, and VC, and more preferably Ti:C:. Generally, the MXene refers to Ti:C,, which can be either purchased from the professional manufacturer, or prepared with reference to a reference: Nano-Micro Lett. Nov. 2019, 70.
Preferably, in the step (3) of the preparation method, adding acrylamide, K:S:0:, and N, N'-methylene bisacrylamide into a ZnS04 solution, and stirring in a water bath kettle; and transferring the stirred solution to a specific container, performing a high temperature polymerization reaction, and obtaining the PAM-ZnSO0, hydrogel electrolyte, where preferably, a concentration of the ZnSO: solution ranges from 1 to 3 mol L*, a mass of the acrylamide ranges from 5 to 15 g, a mass of the K;S;0, ranges from 30 to 80 mg, and a mass of the N, N'-methylene bisacrylamide ranges from 1 to 5 mg; time for stirring in the water bath kettle ranges from 1 to 3 h, and a stirring temperature ranges from 30 to 50°C; and a temperature of the polymerization reaction ranges from 60 to 90°C, time for the polymerization reaction ranges from 1 to 5 h, and more preferably, the temperature ranges from 75 to 85°C, and the reaction time ranges from 2 to 4 h. In the present disclosure, a waterborne polyurethane (PU) was dispersed on a surface of hydro- gel acquired in the polymerization reaction by drop-casting, which can improve bonding and healing abilities of the hydrogel, where the waterborne polyurethane (PU) can be purchased from the profes- sional manufacturer, which can, for example, be selected from an ADWEL series, an LEASYS series, a TEKSPRO series, and other series of products of Wanhua Chemical Group Co.,Ltd. Preferably, in the step (4) of the preparation method, trans- ferring the MWCNTs-V0: (B) anode and the MXene-TiS: cathode to a flexible substrate, adding the PAM-ZnS0, hydrogel electrolyte, and obtaining the zinc ion micro-battery, where the flexible substrate is a common flexible material, such as a polyethylene tereph- thalate (PET) membrane, a polydimethylsiloxane (PDMS) membrane, a polyimide (PI) membrane, and a polyetherimide (PEI) membrane.
The present disclosure further provides application of the multi-functional zinc ion micro-battery in smart wearable equip- ment or a flexible electronic product, for example, the micro- battery can be used for a flexible display, a flexible electronic 5 skin, a smart electronic clothing, the smart wearable equipment, and other products.
In general, compared with the current micro-battery technolo- gy, the micro-battery of the present disclosure has the following obvious advantages that {1) Compared with the traditional micro-battery, the micro- battery based on a design of the present disclosure has a better electrochemical performance, that is a specific capacity is up to
40.8 pAh em under a current density of 0.2893 mA cm*, as shown in Fig. 4.
(2) Compared with the traditional micro-battery, the micro- battery based on the design of the present disclosure has a more excellent flexibility, which can still keep 95% to 98% of an ini- tial capacity (a 0° bend) in case of a 150° bend.
(3) Compared with the traditional micro-battery, the micro- battery based on the design of the present disclosure has a higher safety, that is, with non-toxic PAM (polyacrylamide) as the elec- trolyte, the micro-battery can be applied in the wearable elec- tronic equipment.
(4) Compared with the traditional micro-battery, the micro- battery based on the design of the present disclosure has a better temperature resistance, that is, the micro-battery can operate normally at an ambient temperature ranging from 25 to 100°C.
(5) Compared with the traditional micro-battery, the micro- battery based on the design of the present disclosure has a self- healing performance, that is, the micro-battery can be bonded again after being cut, which can still operate.
(6) Compared with the traditional micro-battery, the micro- battery based on the design of the present disclosure is simpler in a preparation process, and lower in a cost.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a general making process of a multi-functional zinc ion micro-battery of the present disclosure;
Fig. 2 is CV curves of MWCNTs-VO. (B) anodes with different mass ratios of a multi-functional zinc ion micro-battery at the same scanning rate in the present disclosure, where when a mass ratio of MWCNTs to VO: (B) is 6: 6, that is, 1: 1, an oxidation- reduction peak is the most significant; Fig. 3 is CV curves of MXene-TiS. cathodes with different mass ratios of a multi-functional zinc ion micro-battery at the same scanning rate in the present disclosure, and an oxidation- reduction peak is the most significant, where when a mass ratio of MXene to TiS: is 6: 4, that is, 3: 2, a performance is more excel- lent; Fig. 4 is GCD curves of a multi-functional zinc ion micro- battery which is assembled under different charge-discharge cur- rent densities in the present disclosure, in which the charge- discharge current density is increased gradually from right to left in each curve.
Fig. 5 is a change chart of a specific capacity of the multi- functional zinc ion micro-battery which was subjected to a charge- discharge for multiple times in the present disclosure. Upon the charge-discharge for several times, an electrode is activated ful- ly, resulting in a significant ascending at a front end of an im- age. In general, there is no any obvious change in the specific capacity of the battery which is subjected to the charge-discharge for hundreds of times under a current density of 4.32 mA cm%, showing an excellent cycling stability of the battery; Fig. 6 is a picture of a measured series voltage of multi- functional zinc ion micro-batteries which are connected in series in the present disclosure. The voltage doesn’t show a standard multiplied relationship, which is caused by a self-discharge of the battery. A result displays that the voltage of the batteries which are connected in series maintains at 1.51 V roughly; Fig. 7 is an experimental picture in which there is no sig- nificant change in a luminance of an LED lamp after a multi- functional zinc ion micro-battery is bent in an experiment in the present disclosure; Fig. 8 is a change chart of a specific capacity of a multi- functional zinc ion micro-battery under different bending angles in the present disclosure, in which an excellent bending property is shown, and there is almost no change in the specific capacity within the bending angle ranging from 0° to 150° at a charge- discharge current density of 1.1574 mA cm; Fig. 9 shows that there is almost no any change in an LED lamp upon a comparison between a room temperature and 75°C if an ambient temperature of a multi-functional zinc ion micro-battery of the present disclosure is changed in an experiment; Fig. 10 is a change chart of a specific capacity of a multi- functional zinc ion micro-battery at different temperatures in the present disclosure. In general, such micro-battery can still oper- ate normally at the high ambient temperature; Fig. 11 shows operations of cutting a multi-functional zinc ion micro-battery ahead of bonding in an experiment in the present disclosure. An experimental result shows that an LED lamp can still be on by the bonded micro-battery, exhibiting a high self- healing ability of the present disclosure. A left picture shows the LED lamp which is on before cutting, a middle picture shows the LED lamp which is off after cutting, and a right picture shows the LED lamp which is on again after healing; Fig. 12 is GCD curves of a multi-functional zinc ion micro- battery which is cut for different times in the present disclo- sure, in which there is not much difference in a performance be- tween the micro-battery that is cut for 8 times and the micro- battery without cutting. Cutting method: after the micro-battery is cut, two notch ends are put together for a period of time, which can be bonded under a combined action of stickiness of PU and hydrogel.
DETAILED DESCRIPTION OF THE EMBODIMENTS To make the characteristics, experiment methods, and applica- tion scenes of the present disclosure more intuitive, the follow- ing will further illustrate the present disclosure with reference to experiment contents of the drawings. It is worthwhile to note that the contents described in the following experiments are not intended to limit the present disclosure, but are merely illustra- tive of the present disclosure. Meanwhile, raw materials involved in the embodiments, such as V.05, MWCNTs, SDS, MXene, TiS,, and PU,
have become the known conventional raw materials.
Embodiment 1 (1) An MWCNTs-VO, (B) anode was prepared. 6 mg of MWCNTs, 60 mg of SDS, and 6 mg of VO, (B) were added in 40 mL of deionized water, an ultrasonic dispersion was conduct- ed at an ultrasonic dispersion power of 850 W for 1 h, and a uni- form hybrid solution was obtained; and after the hybrid solution was filtered under an vacuum, a hybrid was cleaned for 3 times with the deionized water, and freeze-dried, and an MWCNTs-VO. (B) filter cake was obtained.
The MWCNTs-VO; (B) filter cake was en- graved into an interdigital electrode with a laser engraving ma- chine, and the MWCNTs-VO. (B) anode was obtained. (2) An MXene-TiS: cathode was prepared. 4 mg of TiS: was added into 20 mL of the deionized water, a solution was subjected to an ultrasonic treatment for 30 min, and 6 mg of Mxene was added for the ultrasonic treatment for 30 min; an obtained product was subjected to a membrane suction filtra- tion, and an MXene-TiS, filter cake was obtained; and the MXene- TiS: filter cake was engraved into the interdigital electrode with the laser engraving machine, and the MXene-TiS; cathode was ob- tained. (3) A PAM-Zn30; hydrogel electrolyte was prepared. 12 g of acrylamide, 5 mg of N,N’-methylene bisacrylamide, and 50 mg of K-S:0, were added into 30 mL of 2 mol L™' ZnSO, solution sequentially, while being stirred in a water bath kettle at a tem- perature of 40°C for 2 h; the uniformly stirred solution was transferred to a specific container for a polymerization reaction at 80°C for 3 h; and a waterborne polyurethane (PU) was dispersed uniformly on a surface of formed hydrogel by drop-casting, and the PAM-ZnS0,: hydrogel electrolyte was obtained. (4) A multi-functional zinc ion micro-battery was encapsulat- ed.
The MWCNTs-VO; (B) anode and the MXene-TiS, cathode were transferred to a flexible substrate, the PAM-ZnS0O; hydrogel elec- trolyte was added, and the zinc ion micro-battery was obtained, where the flexible substrate was a polyethylene terephthalate (PET) membrane.
Embodiment 2 A preparation of an MWCNTs-VO, (B) anode: besides 2 mg of VO: (B) was used, other operations were the same as the step (1) in the embodiment 1, and the MWCNTs-VO: (B) anode was obtained.
Embodiment 3 A preparation of an MWCNTs-VO, (B) anode: besides 4 mg of VO: (B) was used, other operations were the same as the step (1) in the embodiment 1, and the MWCNTs-VO. (B) anode was obtained.
Embodiment 4 A preparation of an MXene-TiS; cathode: besides 2 mg of TiS: was used, other operations were the same as the step (2) of the embodiment 1, and the MXene-TiS, cathode was obtained.
Embodiment 5 A preparation of an MXene-TiS, cathode: besides 6 mg of TiS: was used, other operations were the same as the step (2) in the embodiment 1, and the MXene-TiS, cathode was obtained.
The obtained multi-functional zinc ion micro-battery in the present disclosure has characteristics of high specific capacity (high energy density), high flexibility, high self-healing nature, high safety, high temperature resistance, low costs, and the like. In the embodiments, CV curves of the MWCNTs-V0: (B) anodes with different mass ratios at the same scanning rate were shown in Fig. 2, and CV curves of the MXene-TiS, cathodes with different mass ratios at the same scanning rate were shown in Fig. 3; a change chart of a specific capacity of the encapsulated micro-battery which was subjected to a charge-discharge for multiple times in the embodiments was shown in Fig. 5; an experimental result of a measured series voltage of the micro-batteries which were connect- ed in series in the embodiments was shown in Fig. 6; a change in an LED lamp after the micro-battery were bent in the embodiments was shown in Fig. 7; a change chart of the specific capacity of the micro-battery under different bending angles in the embodi- ments was shown in Fig. 8; a change in the LED lamp after an ambi- ent temperature of the micro-battery was changed in the embodi- ments was shown in Fig. 9; a change chart of the specific capacity of the micro-battery at different temperatures in the embodiments was shown in Fig. 10; an effect of the LED which was on after the micro-battery was cut and bonded sequentially in the embodiments was shown in Fig. 11; and GCD curves of the micro-battery which was cut for different times in the embodiments were shown in Fig.
12.
In a test, the micro-battery in the present disclosure can operate normally under multiple complex conditions by excellent characteristics, that is, flexibility, temperature resistance, and self-sealing. Scenes of several applications were as follow: (1) Flexible wearable equipment has been popularized in the market. As such new electronic equipment can’t be powered easily by the traditional battery, a flexible battery is developed. For the micro-battery in the present disclosure, parameters were not changed significantly under the bending angle ranging from 0° to 150°, making it withstand an external extrusion force in most cas- es. With the excellent flexibility and an excellent bendability, not only the micro-battery can be used for a wearable electronic product, but can also achieve a powerful promoting effect on a quietly emerging smart clothing industry.
(2) For a natural reason, most of products can’t operate in a constant-temperature environment all the time in life, and thus, there is a requirement that the products should operate normally within a certain temperature range. Obviously, the micro-battery in the present disclosure meets this requirement. As shown in the Fig. 9, the micro-battery can operate normally at the ambient tem- perature ranging from 25°C to 100°C.
(3) There is a possibility of damage and tearing for a flexi- ble product during use, and the micro-battery in the present dis- closure can solve such problem. After being torn, the battery in the present disclosure can continue to operate by bonding in some emergencies, thereby making time for replacing the battery.
It is worthwhile to note that in the technical solution of the present disclosure, although any better using amount is pro- vided, such as the using amount of the TiS; and the MXene, the pre- sent disclosure is not limited to masses of the TiS; and the MXene in the embodiments, since the mass ratio of the MXene to the TiS, ranges from 3: 1 to 3: 5; and the specific using amount depends on actual needs. The technical solution of the present disclosure is not intended to limit the scope of protection of the present dis- closure, but is merely the explanation and illustration for a skilled in the art to learn the technical essence of the present disclosure.
The essential scope of protection of the present dis- closure should be based on the claims.
A skilled in the art should understand that any amendment, equivalent replacement, improve- ment, etc. that are made based on the essence and spirit of the present disclosure should fall within the essential scope of pro- tection of the present disclosure.
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