CN114530633B - Wearable and rechargeable fabric and its preparation method and method for fabric charging and discharging - Google Patents
Wearable and rechargeable fabric and its preparation method and method for fabric charging and discharging Download PDFInfo
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- CN114530633B CN114530633B CN202210043301.7A CN202210043301A CN114530633B CN 114530633 B CN114530633 B CN 114530633B CN 202210043301 A CN202210043301 A CN 202210043301A CN 114530633 B CN114530633 B CN 114530633B
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- fabric
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- negative electrode
- positive electrode
- conductive
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- 239000004744 fabric Substances 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007599 discharging Methods 0.000 title claims description 10
- 229920000767 polyaniline Polymers 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000007769 metal material Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 18
- 239000002861 polymer material Substances 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 38
- 229910052725 zinc Inorganic materials 0.000 claims description 38
- 239000011701 zinc Substances 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 21
- 210000004243 sweat Anatomy 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005452 bending Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229920002334 Spandex Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000004151 quinonyl group Chemical group 0.000 description 3
- 238000009958 sewing Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明涉及电化学领域，公开了一种可穿戴和可充放电的织物及其制备方法和织物进行充放电的方法。所述织物包括：织物基底和负载在所述织物基底表面上的至少一个电池单元；其中，所述电池单元包括正极片和负极片；所述正极片包括正极材料，所述正极材料为导电高分子材料；所述负极片包括负极材料，所述负极材料为金属材料；所述织物基底在被含有氯离子的电解液润湿时，所述电池单元进行充放电；所述导电高分子材料选自聚苯胺或聚吡咯。所述织物的制备方法包括以下步骤：将正极片和负极片负载在同一织物基底上，得到所述织物。本发明提供的织物可进行充放电，免封装，满足水洗、弯曲等情况。
The invention relates to the field of electrochemistry, and discloses a wearable and rechargeable fabric, a preparation method thereof, and a fabric charge-discharge method. The fabric includes: a fabric base and at least one battery cell loaded on the surface of the fabric base; wherein, the battery unit includes a positive electrode sheet and a negative electrode sheet; the positive electrode sheet includes a positive electrode material, and the positive electrode material is a highly conductive Molecular material; the negative electrode sheet includes a negative electrode material, and the negative electrode material is a metal material; when the fabric substrate is wetted by an electrolyte solution containing chloride ions, the battery unit is charged and discharged; the conductive polymer material is selected From polyaniline or polypyrrole. The preparation method of the fabric comprises the following steps: loading the positive electrode sheet and the negative electrode sheet on the same fabric base to obtain the fabric. The fabric provided by the invention can be charged and discharged, free from encapsulation, and meets conditions such as washing with water and bending.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a wearable and chargeable and dischargeable fabric, a preparation method thereof and a method for charging and discharging the fabric.
Background
With the development of wearable electronic equipment technology, a wearable energy storage device plays a crucial role as a main device for providing energy for the wearable electronic equipment, and also puts higher requirements on the wearable electronic equipment. Most of traditional energy storage devices use metal foil as a current collector, are rigid, and are easy to fall off of active materials during bending deformation, so that capacity loss is caused, electrolyte leakage is even caused, and a battery is invalid; in addition, scientific researchers combine active substances with a flexible substrate to prepare a flexible energy storage device, but most of the active substances are electrolyte which is organic, inflammable and explosive or strong acid and alkali and the like and has damage to skin, and strict packaging design is needed to prevent the electrolyte from leaking, so that the comfort of the wearable equipment is also affected; a major challenge in designing and preparing a suitable wearable energy storage device is thus to meet the power requirements for small electronic devices without sacrificing flexibility, comfort, and safety.
Disclosure of Invention
The invention aims to solve the problems that the traditional battery electrolyte in the prior art has large toxicity and can not be charged in the wearable field, and provides a wearable and chargeable and dischargeable fabric, a preparation method thereof and a method for charging and discharging the fabric; meanwhile, extra tight encapsulation is not needed, and the air permeability of the fabric is not affected; in addition, the wearable and chargeable and dischargeable fabric may also be rinsed with water. Therefore, the wearable and chargeable and dischargeable fabric of the present invention offers a wide prospect and possibility for the future development of safe, sustainable, environmentally friendly wearable energy storage devices.
To achieve the above object, a first aspect of the present invention provides a wearable and chargeable and dischargeable fabric comprising: a fabric substrate and at least one battery cell supported on a surface of the fabric substrate; wherein,,
the battery unit comprises a positive plate and a negative plate;
the positive plate comprises a positive electrode material which is a conductive high polymer material;
the negative electrode plate comprises a negative electrode material, and the negative electrode material is a metal material;
the fabric substrate is charged and discharged by the battery unit when being wetted by electrolyte containing chloride ions;
the conductive polymer material is selected from polyaniline or polypyrrole.
In a second aspect, the present invention provides a method of making a wearable and chargeable and dischargeable fabric, the method comprising the steps of: loading the positive electrode plate and the negative electrode plate on the same fabric to obtain the fabric; the positive plate comprises a positive electrode material, wherein the positive electrode material is a conductive high polymer material; the negative electrode plate comprises a negative electrode material, and the negative electrode material is a metal material; the conductive polymer material is selected from polyaniline or polypyrrole.
A third aspect of the present invention provides a method for charging and discharging a fabric according to the first aspect, wherein the charging process includes the following steps: wetting a fabric substrate contained in the fabric with electrolyte containing chloride ions, and switching on an external power supply to charge a positive plate and a negative plate contained in the fabric;
the discharging process comprises the following steps: and wetting a fabric substrate contained in the fabric with an electrolyte containing chloride ions, and connecting a positive electrode plate and a negative electrode plate contained in the fabric with electronic equipment to discharge.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The wearable and chargeable and dischargeable fabric provided by the invention can complete conventional charge and discharge, cycle test and the like;
(2) The wearable and chargeable and dischargeable fabric provided by the invention can ensure that the battery works normally again by adding new electrolyte after the electrolyte is dried;
(3) The wearable and chargeable and dischargeable fabric provided by the invention can meet the conditions of water washing, bending and the like.
Drawings
FIG. 1 is an X-ray diffraction chart of a zinc/carbon cloth negative electrode sheet prepared in example 1;
FIG. 2 is a scanning electron microscope image of the zinc/carbon cloth negative electrode sheet prepared in example 1;
FIG. 3 is a scanning electron microscope image of the polyaniline/carbon cloth positive electrode sheet produced in example 1;
FIG. 4 is a Raman spectrum of the polyaniline/carbon cloth positive electrode sheet produced in example 1:
FIG. 5 is an infrared spectrum of the polyaniline/carbon cloth positive electrode sheet produced in example 1.
FIG. 6 is a constant current charge and discharge curve of the sweat excited zinc/polyaniline cell prepared in example 1;
fig. 7 is a graph of the cycling stability of the sweat-excited zinc/polyaniline cell made in example 1.
FIG. 8 is a constant current charge and discharge curve of a sweat-excited zinc/polypyrrole cell made in example 2;
fig. 9 is a graph of the cycling stability of the sweat-activated zinc/polypyrrole cell made in example 2.
Fig. 10 is a constant current charge-discharge curve of the sweat battery prepared in example 3 in series.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect the present invention provides a wearable and chargeable and dischargeable fabric comprising: a fabric substrate and at least one battery cell supported on a surface of the fabric substrate; wherein,,
the battery unit comprises a positive plate and a negative plate;
the positive plate comprises a positive electrode material which is a conductive high polymer material;
the negative electrode plate comprises a negative electrode material, and the negative electrode material is a metal material;
the fabric substrate is charged and discharged by the battery unit when being wetted by electrolyte containing chloride ions;
the conductive polymer material is selected from polyaniline or polypyrrole.
In some embodiments of the present invention, the battery cell may be charged and discharged when polyaniline or polypyrrole is used as a positive electrode sheet, a metal material is used as a negative electrode sheet, and an aqueous solution containing chloride ions is used as an electrolyte.
The inventors of the present invention found in the study that the mechanism by which the battery cell can be charged and discharged is: for the positive electrode, the positive electrode emitsThe reaction is intercalation and deintercalation of chloride ions. During charging, -NH is oxidized to =nh + At the same time with Cl in the electrolyte - Bonding, in contrast, during discharge, cl - And can fall out of the positive electrode into the electrolyte. For the negative electrode, when charged, hydrogen evolution reaction and electroplating of metal ions occur on the surface of the metal material. During the discharge phase, metal ions are extracted from the surface of the metal material into the electrolyte.
In some embodiments of the invention, the fabric substrate is a hydrophilic material. Preferably, the hydrophilic material is selected from dacron and/or spandex.
The kind of the metal material is not particularly limited in the present invention, and may be selected by those skilled in the art according to actual demands. Preferably, the metallic material is selected from zinc, magnesium, aluminium, silver or sodium, preferably zinc. The embodiment of the present invention is exemplified by zinc, but the present invention is not limited thereto.
In some embodiments of the invention, the positive electrode sheet and the negative electrode sheet each further comprise a conductive base material for supporting the positive electrode material or the negative electrode material, respectively.
In some embodiments of the present invention, the conductive base material may be a conventional choice in the art, and one skilled in the art may choose according to actual needs. Preferably, the conductive base material is at least one selected from carbon cloth, conductive nickel cloth and conductive silver cloth, and is preferably carbon cloth.
In some embodiments of the present invention, in order to achieve charge and discharge of the fabric, chloride ions should be included in the electrolyte. Preferably, the electrolyte is selected from the group consisting of NaCl, KCl and NH 4 The liquid of at least one of Cl is preferably sweat, more preferably may be artificial sweat or real sweat, wherein the artificial sweat comprises sodium chloride, ammonium chloride, urea, acetic acid and lactic acid.
In some embodiments of the present invention, in order to ensure that the battery cell has excellent rate performance, a distance between the positive electrode tab and the negative electrode tab is 0.1 to 2cm.
In a second aspect, the present invention provides a method of making a wearable and chargeable and dischargeable fabric, the method comprising the steps of: loading the positive electrode plate and the negative electrode plate on the same fabric substrate to obtain the fabric; the positive plate comprises a positive electrode material, wherein the positive electrode material is a conductive high polymer material; the negative electrode plate comprises a negative electrode material, and the negative electrode material is a metal material; the conductive polymer material is selected from polyaniline or polypyrrole.
In some embodiments of the present invention, the method of making the wearable and chargeable and dischargeable fabric comprises the steps of: and directly loading the conductive high polymer material and the metal material on the same fabric substrate to obtain the fabric.
In some embodiments of the present invention, it is preferable that the positive electrode sheet and the negative electrode sheet further each include a conductive base material for supporting the positive electrode material or the negative electrode material, respectively.
In some embodiments of the present invention, preferably, the method for preparing the positive electrode sheet includes the steps of: and modifying the conductive high polymer material on the conductive base material to obtain the positive plate.
In some embodiments of the present invention, preferably, the preparation method of the negative electrode sheet includes the steps of: and modifying the metal material on the conductive substrate material to obtain the negative plate.
The modification mode is not particularly limited in the present invention, and may be performed according to conventional technical means in the art. Preferably, the modification means includes: electroplating, coating and printing, preferably electroplating.
In some embodiments of the present invention, the conductive base material may be a conventional choice in the art, and one skilled in the art may choose according to actual needs. Preferably, the conductive base material is at least one selected from carbon cloth, conductive nickel cloth and conductive silver cloth, and is preferably carbon cloth.
The kind of the metal material is not particularly limited in the present invention, and may be selected by those skilled in the art according to actual demands. Preferably, the metallic material is selected from zinc, magnesium, aluminium, silver or sodium, preferably zinc. The embodiment of the present invention is exemplified by zinc, but the present invention is not limited thereto.
In some embodiments of the present invention, preferably, the method for preparing the wearable and chargeable and dischargeable fabric comprises the steps of:
(1) Applying voltage to a carbon cloth substrate in a hydrochloric acid solution through an electrochemical workstation to carry out hydrophilization treatment, and then electroplating in a solution containing zinc ions through constant current to obtain a zinc/carbon cloth negative plate;
(2) Applying voltage to a carbon cloth substrate in a hydrochloric acid solution through an electrochemical workstation to carry out hydrophilization treatment, and then electroplating in a solution containing aniline or pyrrole monomers through constant current to obtain a polyaniline/carbon cloth positive plate or a polypyrrole/carbon cloth positive plate;
(3) And sewing the zinc/carbon cloth negative electrode sheet and the polyaniline/carbon cloth positive electrode sheet or the polypyrrole/carbon cloth positive electrode sheet on the same fabric substrate to obtain the fabric.
A third aspect of the present invention provides a method for charging and discharging a fabric according to the first aspect, wherein the charging process includes the following steps: wetting a fabric substrate contained in the fabric with electrolyte containing chloride ions, and switching on an external power supply to charge a positive plate and a negative plate contained in the fabric;
the discharging process comprises the following steps: and wetting a fabric substrate contained in the fabric with an electrolyte containing chloride ions, and connecting a positive electrode plate and a negative electrode plate contained in the fabric with electronic equipment to discharge.
The present invention will be described in detail by examples. In the following examples of the present invention,
and characterizing the composition of the negative plate by adopting an X-ray analyzer with the model of X' Pert 3 Powder. Test conditions: the scanning range is 10-80 degrees, the accelerating voltage is 40kV, and the accelerating current is 40mA;
characterizing the morphology of the positive plate and the negative plate by adopting a Scanning Electron Microscope (SEM) with the model of Hitachi SU 8200;
carrying out Raman characterization on the positive plate by adopting a Raman spectrometer with the model of HORIBA Lab RAM HR Evolution;
and carrying out infrared characterization on the positive plate by adopting a Fourier transform infrared spectrometer with the model of VERTEX80 v.
In the following examples and comparative examples, all the raw materials are commercially available unless otherwise specified; wherein,,
artificial sweat was purchased from Shanghai Seiyaka Biotechnology Co., ltd under the designation R22790.
Example 1
(1) Preparing a zinc/carbon cloth negative plate:
firstly, ultrasonically cleaning the carbon cloth for 30min by using a mixed solution containing water, ethanol and acetone, ultrasonically cleaning the carbon cloth for 15min by using deionized water, repeating the steps for several times, and cleaning and airing. Secondly, in a hydrochloric acid solution containing 0.5M, a saturated calomel electrode is used as a reference electrode, pt is used as a counter electrode, carbon cloth is used as a working electrode, a constant voltage of 5V is applied for 3min through an electrochemical workstation, and deionized water is used for washing after the sample is taken out. Then, in the presence of 0.5M ZnSO 4 、1M NaSO 4 And 0.3M H 3 BO 3 In the mixed solution of (1), ag/AgCl is used as a reference electrode, pt is used as a counter electrode, carbon cloth is used as a working electrode, constant current of-40 mA is applied for 1h through an electrochemical workstation, and then the mixed solution is taken out and washed clean by deionized water, so that a zinc/carbon cloth negative plate is obtained.
And carrying out X-ray diffraction and SEM test on the prepared zinc/carbon cloth negative plate. Fig. 1 is an X-ray diffraction diagram of a zinc/carbon cloth negative plate, and fig. 1 shows the presence of zinc phase and carbon phase, wherein the peaks of the carbon substrate are near 22 °, and the rest of the peaks correspond to zinc (JCPDS No. 87-0713) card, without other phases and impurity peaks. Fig. 2 is a scanning electron microscope image of a zinc/carbon cloth negative plate, and fig. 2 shows that zinc presents a shape of a nano-plate, and the size of the zinc nano-plate is about several hundred nanometers.
(2) Preparing polyaniline/carbon cloth positive plates:
firstly, ultrasonically cleaning the carbon cloth for 30min by using a mixed solution containing water, ethanol and acetone, ultrasonically cleaning the carbon cloth for 15min by using deionized water, repeating the steps for several times, and cleaning and airing. Secondly, in a hydrochloric acid solution containing 0.5M, a saturated calomel electrode is used as a reference electrode, pt is used as a counter electrode, carbon cloth is used as a working electrode, a constant voltage of 5V is applied for 3min through an electrochemical workstation, and deionized water is used for washing after the sample is taken out. Then, in a mixed solution containing 5g of aniline monomer, 5.4mL of sulfuric acid, 14.2g of sodium sulfate and 200mL of deionized water, using Ag/AgCl as a reference electrode, pt as a counter electrode and carbon cloth as a working electrode, applying a constant current of 0.5mA for 1h through an electrochemical workstation, and then taking out and washing with deionized water to obtain a polyaniline/carbon cloth positive plate.
SEM, raman and infrared tests are carried out on the prepared polyaniline/carbon cloth positive electrode plate. FIG. 3 is an SEM image of a polyaniline/carbon cloth positive electrode sheet, the polyaniline being shown in FIG. 3 as exhibiting a nanorod structure, the nanorod having a size of about 50nm; FIG. 4 is a Raman spectrum of a polyaniline/carbon cloth positive plate at 1161cm -1 (C-H bending)、1341cm -1 (c=n stranding) and 1467cm -1 The raman peak at (c=c stretching) represents a characteristic peak of the benzene ring; at 1215cm -1 (C-H bending vibrations) and 1584cm -1 (c=c stretching) represents a characteristic peak of the quinone ring, indicating the presence of the quinone ring and the benzene ring in polyaniline; FIG. 5 is a Fourier infrared spectrum of a polyaniline/carbon cloth positive plate, 1629cm -1 The absorption peak at which is represented by c=c stretch on the quinone ring; 1493cm -1 、1328cm -1 And 1200cm -1 The absorption peaks at represent c=c stretching, c=n stretching and C-H bending on the benzene ring. The above results verify that the conductive polymer polyaniline is successfully prepared on the carbon cloth substrate.
(3) Preparation of the fabric:
and sewing the prepared polyaniline/carbon cloth positive electrode sheet and zinc/carbon cloth negative electrode sheet on the same polyester/spandex fabric substrate at intervals of 0.2cm to obtain the fabric.
And (3) dripping the artificial sweat on a fabric substrate to make the fabric substrate wet and conductive, so as to obtain the sweat-excited zinc/polyaniline cell. The sweat-excited zinc/polyaniline cell was connected to an electrochemical workstation for constant current charge and discharge testing. The zinc/polyaniline sweat-stimulated electricityThe open circuit voltage of the cell was about 1.4V. FIG. 6 is a constant current charge and discharge curve for a sweat-excited zinc/polyaniline cell with a maximum area specific capacity of 0.132mAh cm -2 . Fig. 7 is a graph of cycling stability of a sweat-activated zinc/polyaniline cell, and fig. 7 shows that after 500 cycles, the capacity retention was 51%.
Example 2
(1) Preparing a zinc/carbon cloth negative plate:
a zinc/carbon cloth negative electrode sheet was prepared as in example 1.
(2) Preparing a polypyrrole/carbon cloth positive plate:
firstly, ultrasonically cleaning the carbon cloth for 30min by using a mixed solution containing water, ethanol and acetone, ultrasonically cleaning the carbon cloth for 15min by using deionized water, repeating the steps for several times, and cleaning and airing. Secondly, in a hydrochloric acid solution containing 0.5M, a saturated calomel electrode is used as a reference electrode, pt is used as a counter electrode, carbon cloth is used as a working electrode, a constant voltage of 5V is applied for 3min through an electrochemical workstation, and deionized water is used for washing after the sample is taken out. Then, in a solution containing 5% of pyrrole monomer and 0.2M sodium perchlorate by volume fraction, pt is used as a counter electrode, ag/AgCl is used as a reference electrode, 0.8V voltage is applied for electroplating for 30 minutes, and then the solution is taken out and washed clean by deionized water, so that the polypyrrole/carbon cloth positive plate is obtained.
(3) And sewing the prepared polypyrrole/carbon cloth positive electrode plate and zinc/carbon cloth negative electrode plate on the same polyester/spandex fabric substrate at intervals of 0.2cm to obtain the fabric.
And (3) dripping the artificial sweat on a fabric substrate to make the fabric substrate wet and conductive, so as to obtain the sweat-excited zinc/polypyrrole battery. The sweat-excited zinc/polypyrrole battery is connected with an electrochemical workstation for constant-current charge and discharge test. The open circuit voltage of the sweat-excited cell is about 1.2V; FIG. 8 is a constant current charge and discharge curve for a sweat-excited zinc/polypyrrole cell having a maximum area specific capacity of 0.123mAh cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Fig. 9 is a graph of cycling stability of a sweat-activated zinc/polypyrrole cell, after 200 cycles, with a capacity retention of 12%.
Example 3
(1) Preparation of electrode materials:
a zinc/carbon cloth negative electrode sheet and a polyaniline/carbon cloth positive electrode sheet were prepared according to the method in example 1.
(2) The prepared electrode materials are assembled into three independent sweat batteries, positive and negative electrodes of the sweat batteries are sequentially connected by using wires, so that the three sweat batteries are connected in series, and the voltage of the three sweat batteries becomes three times (4.8V) of that of a single battery after the three sweat batteries are connected in series according to a constant current charge-discharge curve of the sweat batteries shown in figure 10.
In summary, the fabric prepared by the method provided by the invention can be charged and discharged.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066314A (en) * | 2012-12-25 | 2013-04-24 | 武汉纺织大学 | Fabric morphological polymer battery and preparation method thereof |
| KR20160026577A (en) * | 2014-09-01 | 2016-03-09 | 주식회사 제낙스 | Fabric-friendly rechargeable battery package |
| CN108400392A (en) * | 2018-01-29 | 2018-08-14 | 东华理工大学 | Chargeable flexible Zinc ion battery of one kind and preparation method thereof |
| KR20210013974A (en) * | 2019-07-29 | 2021-02-08 | 이규민 | Warming Clothes which contain wireless technique and high capability thin-film batteries |
| CN113707840A (en) * | 2021-08-19 | 2021-11-26 | 深圳德夏科技发展有限公司 | Manufacturing method of flexible battery, flexible battery and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066314A (en) * | 2012-12-25 | 2013-04-24 | 武汉纺织大学 | Fabric morphological polymer battery and preparation method thereof |
| KR20160026577A (en) * | 2014-09-01 | 2016-03-09 | 주식회사 제낙스 | Fabric-friendly rechargeable battery package |
| CN108400392A (en) * | 2018-01-29 | 2018-08-14 | 东华理工大学 | Chargeable flexible Zinc ion battery of one kind and preparation method thereof |
| KR20210013974A (en) * | 2019-07-29 | 2021-02-08 | 이규민 | Warming Clothes which contain wireless technique and high capability thin-film batteries |
| CN113707840A (en) * | 2021-08-19 | 2021-11-26 | 深圳德夏科技发展有限公司 | Manufacturing method of flexible battery, flexible battery and application |
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