CN111009420B - Composite energy device with full textile structure and manufacturing method thereof - Google Patents
Composite energy device with full textile structure and manufacturing method thereof Download PDFInfo
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- CN111009420B CN111009420B CN201911344617.4A CN201911344617A CN111009420B CN 111009420 B CN111009420 B CN 111009420B CN 201911344617 A CN201911344617 A CN 201911344617A CN 111009420 B CN111009420 B CN 111009420B
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- 239000004753 textile Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 144
- 125000006850 spacer group Chemical group 0.000 claims abstract description 94
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 111
- 239000000243 solution Substances 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229920000128 polypyrrole Polymers 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 16
- 238000011065 in-situ storage Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 239000011245 gel electrolyte Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920000767 polyaniline Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000002019 doping agent Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 claims description 4
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- 229920004933 Terylene® Polymers 0.000 claims 1
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- 239000003990 capacitor Substances 0.000 abstract description 23
- 238000013461 design Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 239000002783 friction material Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a composite energy device with a full textile structure and a manufacturing method thereof. The preparation of the composite energy device with the full textile structure comprises two parts, namely, firstly, the preparation of the flexible friction generator is completed by taking the spacer fabric as a substrate, then, the preparation of the super capacitor is completed by taking the same spacer fabric as a substrate, and finally, the two parts are assembled to complete the preparation of the integrated composite energy device. The wearable self-powered device disclosed by the invention uniformly uses the three-dimensional spacer fabric as the substrate, realizes the integrated friction generator and the super capacitor, has a uniform integrated structure, and provides a new design idea for the wearable self-powered device.
Description
Technical Field
The invention belongs to the technical field of flexible electronic devices, and relates to a composite energy device with a full textile structure and a manufacturing method thereof.
Background
The flexible electronics has wide application prospect in the fields of information, energy, medical treatment, national defense and the like, and is increasingly concerned by people. All flexible electronic devices require a power supply, the conventional power supply is of a rigid structure, and the non-flexible power supply device makes the wearability of the whole system greatly challenging. To achieve ideal wearability, it is necessary to develop a flexible, lightweight, portable energy conversion or storage device. As textile materials are known to have natural flexibility and wearability, building energy devices based on textile materials is one of the ideal strategies to make energy devices flexible. In the last few years, many reports have been made on the production of energy devices based on textile materials, mainly on the production of triboelectric generators and supercapacitors.
Although people make more and more breakthroughs in developing flexible wearable friction generators, the performance of devices is better and better, for example, a vertical contact separation friction generator is prepared by Zhu et al (Nano Lett.2013,13,847) by taking a Polydimethylsiloxane (PDMS) film as a friction material and a gold electrode as another friction material; seung et al (Acs Nano 2015,9,3501) prepared a fabric-like friction generator by combining different friction materials (one piece silver plated, one piece dip coated PDMS) on two pieces of fabric; however, there is still a certain distance from the practical application because most substrates of the current flexible friction generators are polymer films, the structures are generally vertical separation (sandwich) type, springs or separators are needed to assist in realizing the separation of upper and lower layers after the external force is removed, and devices using textile materials as substrates have the defects of high preparation cost and incomplete flexibility because the electrodes are made of metal. Therefore, besides improving the materials of the two poles of the friction surface, there is also a need for new ideas on the generator structure to develop a flexible friction generator with a completely new structure.
Because the friction generator is determined by the property, the electric energy converted by the device belongs to an alternating current signal with smaller current, and the energy device can stably output direct current. The super capacitor can stably output electric energy as an energy storage device, but needs to rely on an external charging system. In order to fully utilize the electric energy generated by the friction generator, the micro signals can be rectified and accumulated and stored in the super capacitor, so that the irregular pulse current is converted into stable and continuous direct current, and the complementary advantages of the friction generator and the super capacitor are realized.
At present, research aiming at the composite integration of a flexible friction generator and a super capacitor is just started, wherein a composite Energy device integrating a friction piezoelectric device and an Energy storage device is prepared for the first time in 2012 by Yang et al (Energy Environ Sci 2012,5,9462), an electrochromic electronic element is driven, and the research proves that the integrated device can realize self-driving by converting mechanical Energy and has quick driving response. Pu et al (adv.mater.2015,28,98) prepared a friction power generator device with a fabric as a unit by a weaving method, and simultaneously prepared a fibrous supercapacitor, and the friction power generator device and the fibrous supercapacitor are connected into a whole by a lead to prepare a composite energy device of the friction power generator and the supercapacitor. The invention tries to integrate the friction generator and the super capacitor through a flexible lead to finally obtain the composite energy device with a full textile structure, and the prepared energy device with the full textile structure has excellent performance and outstanding performance in the aspects of flexibility and stability. The method provides a solution for the research and development of wearable friction piezoelectric generators and flexible supercapacitors, and provides a new research direction for the research and development of textile energy devices.
Disclosure of Invention
The invention aims to provide a preparation method of a composite energy device with a full textile structure, which comprises a friction generator based on a three-dimensional space fabric, a super capacitor based on the three-dimensional space fabric and conductive fibers prepared based on textile yarns.
The technical scheme of the invention is as follows:
the preparation of the composite energy device with the full textile structure comprises two parts, namely, firstly, the preparation of the flexible friction generator is completed by taking the spacer fabric as a substrate, then, the preparation of the super capacitor is completed by taking the same spacer fabric as a substrate, and finally, the two parts are assembled to complete the preparation of the integrated composite energy device. Wherein the preparation of the friction generator comprises:
cleaning and drying the three-dimensional spaced fabric, placing the lower layer of the fabric in a mixed solution of PDMS and a curing agent, turning the fabric over, enabling the fabric to penetrate through pores on the surface layer of the fabric to form irregular conical bulges under the action of the self gravity of liquid, and forming a friction surface after the curing is finished; and then, laying a conductive layer on the outer surfaces of the upper layer and the lower layer of the spacer fabric to be used as an induction electrode. In order to protect the sensing electrode from damage during pressing, a layer of PDMS may be finally coated outside the sensing electrode as a protection layer.
The preparation of the supercapacitor based on the three-dimensional spacing fabric comprises the following steps:
one side of the spacer fabric is immersed in pyrrole monomer solution with certain concentration and volume, and the mixture is stirred for a period of time to ensure that the pyrrole solution is fully dispersed into the fabric surface fibers. Then dropwise adding a certain volume of mixed solution of ferric trichloride and anthraquinone-2-sodium sulfonate with a certain concentration into the solution to initiate in-situ polymerization reaction. And after the reaction is finished, processing the other surface in a relative mode, and finally filling gel electrolyte in the middle of the upper layer and the lower layer, namely the spacing layer, in an injection mode to obtain the integrated supercapacitor. And finally, the prepared friction generator is used as a power generation part, the super capacitor is used as an energy storage part, and the prepared flexible conductive fibers are connected to assemble a composite energy device with a full textile structure.
The drying temperature for preparing the combined friction material PDMS of the friction generator needs to be controlled between 60 and 110 ℃, the drying time can be controlled between 8 and 15min, and the used induction electrode material can be conductive silver colloid, conductive carbon nano tubes or other flexible conductive materials; the polymerization reaction involved in the preparation of the supercapacitor is not limited to polypyrrole, and polyaniline or other active materials capable of being polymerized in situ can be used. The composite energy device can be assembled in a plurality of assembling modes, for example, different numbers of super capacitors are connected in series and parallel with the friction generator.
The invention relates to a composite energy device with a full textile structure, which comprises a friction generator based on a three-dimensional space fabric, a super capacitor based on the three-dimensional space fabric and a flexible lead;
the friction generator based on the three-dimensional spacer fabric is a friction generator constructed on the three-dimensional spacer fabric and sequentially comprises an upper conductive layer, an upper friction layer, a spacer layer, a lower friction layer and a lower conductive layer; the upper conducting layer covers the outer surface of the upper layer of the three-dimensional spacer fabric, the upper friction layer is the upper layer of the three-dimensional spacer fabric coated with the auxiliary friction material, the spacer layer is the middle spacer layer of the three-dimensional spacer fabric, the lower friction layer is the lower layer of the three-dimensional spacer fabric coated with the auxiliary friction material, and the lower conducting layer covers the outer surface of the lower layer of the three-dimensional spacer fabric;
the supercapacitor based on the three-dimensional spacing fabric is constructed on the three-dimensional spacing fabric and sequentially comprises an upper conductive active material layer, a gel electrolyte layer and a lower conductive active material layer; the conductive active material upper layer is a three-dimensional spacer fabric upper layer coated with a conductive active material, the gel electrolyte layer is a three-dimensional spacer fabric middle spacing layer filled with gel electrolyte, and the conductive active material lower layer is a three-dimensional spacer fabric lower layer coated with a conductive active material;
the outer surface of the upper fabric of the friction generator based on the three-dimensional spacing fabric is coated with silver colloid or carbon nano tubes to serve as a leading electrode, and the bonding material of the lower conducting layer is consistent with that of the upper conducting layer to serve as a lower leading electrode;
the outer surface of the upper fabric layer of the conductive active material of the supercapacitor based on the three-dimensional space fabric is adhered with conductive fibers by silver glue to be used as a lead electrode, and the outer surface of the lower fabric layer of the conductive active material is adhered with the conductive fibers by the silver glue to be used as the lead electrode;
the flexible lead is common textile yarn with the surface coated with a conductive active material;
the friction generator based on the three-dimensional space fabric is connected with the super capacitor based on the three-dimensional space fabric after being connected in series and in parallel through the flexible lead, and the output positive electrode and the output negative electrode of the friction generator are respectively connected with the positive electrode and the negative electrode of the super capacitor through the lead.
As a preferred technical scheme:
the composite energy device with the full textile structure comprises a three-dimensional spacer fabric, a middle spacer yarn, an upper layer and a lower layer, wherein the three-dimensional spacer fabric is a warp-knitted spacer fabric, the middle spacer yarn is a single-fiber polyester filament with the diameter range of 100-300D, and the upper layer and the lower layer are polyester fibers with the diameter range of 100-300D;
the auxiliary friction material is polydimethylsiloxane, polyvinyl chloride, polytetrafluoroethylene or polyvinyl alcohol;
the surface of the lead electrode is coated with conductive silver adhesive, conductive polypyrrole or carbon nano tubes, and the lead electrode is required to be well combined with the substrate fabric;
the conductive active material is polypyrrole or polyaniline;
the gel electrolyte is PVA/phosphoric acid or PVA/sulfuric acid;
the outer surfaces of the upper conductive layer and the lower conductive layer of the friction generator based on the three-dimensional spacing fabric are also coated with a layer of polydimethylsiloxane as a protective layer.
The flexible lead is a high polymer fiber coated with graphene.
The height of the middle spacing layer of the three-dimensional spacing fabric is more than or equal to 2 mm.
The invention relates to a manufacturing method of a composite energy device with a full textile structure, which comprises the following steps:
(1) manufacturing of a triboelectric generator based on a three-dimensional spacer fabric;
the preparation method comprises the steps of adopting a three-dimensional spacer fabric as a substrate, firstly, designing the upper surface and the lower surface of the three-dimensional spacer fabric as friction layers, mixing PDMS (polydimethylsiloxane) silicon rubber and a curing agent according to a certain mass ratio (5-10:1), uniformly soaking the obtained mixed solution at the bottom of the three-dimensional spacer fabric, inverting the spacer fabric, drying and curing after soaking is finished, controlling the curing temperature to obtain friction surfaces with different shapes, and finishing the preparation of the friction surfaces; secondly, the parameters (mainly fineness and density) of the spacing yarns are regulated and controlled so that the parameters can not only ensure the tight connection of an upper friction layer and a lower friction layer, but also effectively separate charges generated after friction; finally, in-situ depositing a conductive material on the surfaces of the upper and lower fabrics to form a flexible conductive layer (polypyrrole, polyaniline, carbon nano tube and the like), wherein the conductivity of the conductive layer is more than 0.1S/m, so that the effective transfer of induced charges is ensured, and the friction generator with a full textile structure, which has a stable structure and meets the performance of practical application, is prepared;
(2) the manufacture of a spacer fabric-based supercapacitor;
the upper surface and the lower surface of the spacer fabric are respectively loaded with the conductive polypyrrole, and the middle spacer layer of the spacer fabric is filled with the gel electrolyte, so that the super capacitor has good stability and capacity retention;
(3) connecting;
the connection refers to connecting one or more three-dimensional spacer fabric based triboelectric generators in series and/or in parallel with one or more spacer fabric based supercapacitors.
The supporting refers to in-situ polymerization of conductive polypyrrole or polyaniline on the upper surface and the lower surface of the spacer fabric respectively.
The in-situ polymerization conductive polymer is prepared by soaking the upper surface or the lower surface of the three-dimensional space fabric in a 0.02M-0.1M solution of polymer monomer pyrrole or aniline with the v/M being 50, and stirring for a period of time to fully disperse the monomer solution into the fabric surface fibers; then, the mixed solution of 0.04M-0.25M ferric trichloride as an oxidant and 0.005M-0.01M sodium anthraquinone-2-sulfonate as a dopant is added into the solution drop by drop to initiate in-situ polymerization reaction.
The connecting lead is made of graphene/polyester conductive yarns, the substrate yarns are soaked in 1M sodium hydroxide solution for 10-30min to be subjected to simple alkali treatment, then are soaked in 1-5mg/mL graphene oxide solution for 5-10 times, the soaked yarns are dried in an oven and wound into coils, and finally the yarns are placed in a reducing agent to be reduced to obtain the composite conductive yarns.
The connection is performed by converting the alternating current signal generated by the friction generator into direct current through a rectifier.
Has the advantages that:
compared with the prior art, the composite energy device with the full textile structure provided by the invention has the following advantages:
1. the friction power generation device is prepared by taking the spacer fabric as a base material, the structure of the device is optimized, the process is simple, and a novel design and manufacturing approach is provided for the development of a flexible power generation device.
2. The upper layer and the lower layer of the spacer fabric are used as positive and negative electrodes, the spacer layer is used as a diaphragm, the prepared super capacitor is novel in structure and simple in process, and a novel design and preparation way is provided for the flexible fabric-shaped super capacitor.
3. The conventional composite energy device is mostly simply connected with two devices, and the substrates are mostly independent and different, so that the coordination of the two devices cannot be guaranteed.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The invention relates to a composite energy device with a full textile structure, which comprises a friction generator based on a three-dimensional space fabric, a super capacitor based on the three-dimensional space fabric and a flexible lead;
the friction generator based on the three-dimensional spacer fabric is a friction generator constructed on the three-dimensional spacer fabric and sequentially comprises an upper conductive layer, an upper friction layer, a spacer layer, a lower friction layer and a lower conductive layer; the upper conducting layer covers the outer surface of the upper layer of the three-dimensional spacer fabric, the upper friction layer is the upper layer of the three-dimensional spacer fabric coated with the auxiliary friction material, the spacer layer is the middle spacer layer of the three-dimensional spacer fabric, the lower friction layer is the lower layer of the three-dimensional spacer fabric coated with the auxiliary friction material, and the lower conducting layer covers the outer surface of the lower layer of the three-dimensional spacer fabric;
the supercapacitor based on the three-dimensional spacing fabric is constructed on the three-dimensional spacing fabric and sequentially comprises an upper conductive active material layer, a gel electrolyte layer and a lower conductive active material layer; the conductive active material upper layer is a three-dimensional spacer fabric upper layer coated with a conductive active material, the gel electrolyte layer is a three-dimensional spacer fabric middle spacing layer filled with gel electrolyte, and the conductive active material lower layer is a three-dimensional spacer fabric lower layer coated with a conductive active material;
the outer surface of the upper fabric of the friction generator based on the three-dimensional spacing fabric is coated with silver colloid or carbon nano tubes to serve as a leading electrode, and the bonding material of the lower conducting layer is consistent with that of the upper conducting layer to serve as a lower leading electrode;
the outer surface of the upper fabric layer of the conductive active material of the supercapacitor based on the three-dimensional space fabric is adhered with conductive fibers by silver glue to be used as a lead electrode, and the outer surface of the lower fabric layer of the conductive active material is adhered with the conductive fibers by the silver glue to be used as the lead electrode;
the flexible lead is common textile yarn with the surface coated with a conductive active material;
the friction generator based on the three-dimensional space fabric is connected with the super capacitor based on the three-dimensional space fabric after being connected in series and in parallel through the flexible lead, and the output positive electrode and the output negative electrode of the friction generator are respectively connected with the positive electrode and the negative electrode of the super capacitor through the lead.
The three-dimensional spacer fabric is a warp-knitted spacer fabric, the middle spacer yarn is a single-fiber polyester filament with the diameter range of 100-300D, and the upper and lower layer surfaces are polyester fibers with the diameter range of 100-300D;
the auxiliary friction material is polydimethylsiloxane, polyvinyl chloride, polytetrafluoroethylene or polyvinyl alcohol;
the surface of the lead electrode is coated with conductive silver adhesive, conductive polypyrrole or carbon nano tubes, and the lead electrode is required to be well combined with the substrate fabric;
the conductive active material is polypyrrole or polyaniline;
the gel electrolyte is PVA/phosphoric acid or PVA/sulfuric acid;
the outer surfaces of the upper conductive layer and the lower conductive layer of the friction generator based on the three-dimensional spacing fabric are also coated with a layer of polydimethylsiloxane as a protective layer.
The flexible lead is a high polymer fiber coated with graphene.
The height of the middle spacing layer of the three-dimensional spacing fabric is more than or equal to 2 mm.
The invention relates to a manufacturing method of a composite energy device with a full textile structure, which comprises the following steps:
(1) manufacturing of a triboelectric generator based on a three-dimensional spacer fabric;
the preparation method comprises the steps of adopting a three-dimensional spacer fabric as a substrate, firstly, designing the upper surface and the lower surface of the three-dimensional spacer fabric as friction layers, mixing PDMS (polydimethylsiloxane) silicon rubber and Dow Corning 184B curing agent according to a certain mass ratio (5-10:1), uniformly soaking the obtained mixed solution at the bottom of the three-dimensional spacer fabric, after soaking, inverting the spacer fabric, drying and curing, and controlling the curing temperature to obtain friction surfaces with different shapes so as to finish the preparation of the friction surfaces; secondly, the parameters (mainly fineness and density) of the spacing yarns are regulated and controlled so that the parameters can not only ensure the tight connection of an upper friction layer and a lower friction layer, but also effectively separate charges generated after friction; finally, in-situ depositing a conductive material on the surfaces of the upper and lower fabrics to form a flexible conductive layer (polypyrrole, polyaniline, carbon nano tube and the like), wherein the conductivity of the conductive layer is more than 0.1S/m, so that the effective transfer of induced charges is ensured, and the friction generator with a full textile structure, which has a stable structure and meets the performance of practical application, is prepared;
(2) the manufacture of a spacer fabric-based supercapacitor;
the upper surface and the lower surface of the spacer fabric are respectively loaded with the conductive polypyrrole, and the middle spacer layer of the spacer fabric is filled with the gel electrolyte, so that the super capacitor has good stability and capacity retention;
(3) connecting;
the connection refers to connecting one or more three-dimensional spacer fabric based triboelectric generators in series and/or in parallel with one or more spacer fabric based supercapacitors.
The supporting refers to in-situ polymerization of conductive polypyrrole or polyaniline on the upper surface and the lower surface of the spacer fabric respectively.
The in-situ polymerization conductive polymer is prepared by soaking the upper surface or the lower surface of the three-dimensional space fabric in a 0.02M-0.1M solution of polymer monomer pyrrole or aniline with the v/M being 50, and stirring for a period of time to fully disperse the monomer solution into the fabric surface fibers; then, the mixed solution of 0.04M-0.25M ferric trichloride as an oxidant and 0.005M-0.01M sodium anthraquinone-2-sulfonate as a dopant is added into the solution drop by drop to initiate in-situ polymerization reaction.
The connecting lead is made of graphene/polyester conductive yarns, the substrate yarns are soaked in 1M sodium hydroxide solution for 10-30min to be subjected to simple alkali treatment, then are soaked in 1-5mg/mL graphene oxide solution for 5-10 times, the soaked yarns are dried in an oven and wound into coils, and finally the yarns are placed in a reducing agent to be reduced to obtain the composite conductive yarns.
The connection is performed by converting the alternating current signal generated by the friction generator into direct current through a rectifier.
Example 1
Preparing a flexible lead: soaking 108tex/72F polyimide yarn in 1M sodium hydroxide solution for 30min for alkali treatment, dip-coating in 2mg/mL graphene oxide solution for 8 times, drying the soaked yarn in an oven and winding into a coil, and finally reducing the yarn in hydroiodic acid for 30min to obtain a flexible lead with the conductivity of 800S/M as a subsequent connecting lead.
Preparing a three-dimensional spacer fabric friction generator: selecting 3mm thick, 5 × 5cm area, 850g/m for upper and lower layer fabric2The polyester fabric takes warp-knitted three-dimensional space fabric with 150D polyester monofilament as a substrate, and PDMS silicone rubber and Dow Corning 184B curing agent are mixed according to a certain ratio of 10:1, uniformly soaking the obtained mixed solution at the bottom of the three-dimensional space fabric, inverting the space fabric, drying and curing at the curing temperature of 80 ℃ for 0.5h after soaking is finished, and drying to form a friction surface at the bottom; secondly, respectively depositing conductive polypyrrole on the surfaces of the upper fabric and the lower fabric in situ, wherein the concentration of pyrrole monomer is 0.04M, the oxidant is 0.08M ferric chloride, the dopant is 0.009M sodium anthraquinone sulfonate, and the reaction temperature is 0Obtaining a conductive layer with the conductivity of 0.2S/cm at the temperature of 2 hours to finish the preparation of the induction electrode; coating silver colloid at the tail ends of the upper and lower induction electrodes, adhering the prepared fiber lead to complete the preparation of the leading electrode, wherein the friction layer containing PDMS is an output negative electrode, the opposite is an output positive electrode, and the friction generator based on the three-dimensional spacing fabric is obtained, and the output power of the friction generator can reach 160mW/m2(ii) a Preparing a three-dimensional spacer fabric supercapacitor: taking a three-dimensional spacer fabric with the same parameters as a substrate, respectively carrying conductive polypyrrole on the upper surface and the lower surface of the three-dimensional spacer fabric, completing the preparation of the anode and the cathode of the supercapacitor by the same preparation process, filling PVA/phosphoric acid gel electrolyte with the concentration of 10% in the middle spacer layer of the spacer fabric, testing that the supercapacitor can realize 150F/g, and finally connecting the prepared flexible lead serving as an extraction electrode with the output end of a friction generator to complete the preparation of the composite energy device.
Example 2
Preparing a flexible lead: soaking 80tex/36F polyester yarn in 1M sodium hydroxide solution for 30min for alkali treatment, then dip-coating in 3mg/mL graphene oxide solution for 10 times, drying the soaked yarn in an oven and winding into a coil, and finally reducing the yarn in hydroiodic acid for 30min to obtain a flexible lead with the conductivity of 600S/M as a subsequent connecting lead.
Preparing a three-dimensional spacer fabric friction generator: selecting 5mm thick, 5 × 5cm area, 850g/m for upper and lower layer fabric2The polyester fabric takes warp-knitted three-dimensional space fabric with 150D polyester monofilament as a substrate, and PDMS silicone rubber and Dow Corning 184B curing agent are mixed according to a certain ratio of 10:1, uniformly soaking the obtained mixed solution at the bottom of the three-dimensional space fabric, inverting the space fabric, drying and curing at the curing temperature of 80 ℃ for 0.5h after soaking is finished, and drying to form a friction surface at the bottom; secondly, in-situ depositing conductive polyaniline on the surfaces of the upper fabric and the lower fabric respectively, wherein the concentration of an aniline monomer is 0.4M, an oxidant is 0.4M ammonium persulfate, a dopant is 1.2M hydrochloric acid, the reaction temperature is 25 ℃, the reaction time is 2 hours, so that a conductive layer with the conductivity of 0.1S/cm is obtained, and the preparation of the induction electrode is completed; the tail ends of the upper and lower layer induction electrodes are coated with silver colloid,adhering the prepared fiber lead to finish the preparation of the leading electrode, wherein the friction layer containing PDMS is an output negative electrode, the opposite is an output positive electrode, and the friction generator based on the three-dimensional spacing fabric is obtained, and the output power of the friction generator can reach 185mW/m2；
Preparing a three-dimensional spacer fabric supercapacitor: taking a three-dimensional spacer fabric with the same parameters as a substrate, respectively carrying conductive polyaniline on the upper surface and the lower surface of the three-dimensional spacer fabric, completing the preparation of the anode and the cathode of the super capacitor by the same preparation process, filling PVA/phosphoric acid gel electrolyte with the concentration of 10% in the middle spacer layer of the spacer fabric, testing that the super capacitor can realize 180F/g, and finally connecting the prepared flexible lead serving as an extraction electrode with the output end of a friction generator to complete the preparation of the composite energy device.
Claims (5)
1. A manufacturing method of a composite energy device with a full textile structure is characterized by comprising the following steps:
(1) manufacturing of a triboelectric generator based on a three-dimensional spacer fabric;
the preparation method comprises the steps of adopting a three-dimensional spacer fabric as a substrate, firstly, designing the upper surface and the lower surface of the three-dimensional spacer fabric as friction layers, mixing PDMS (polydimethylsiloxane) silicon rubber and a curing agent according to the mass ratio of 5-10:1, uniformly soaking the obtained mixed solution at the bottom of the three-dimensional spacer fabric, inverting the spacer fabric, drying and curing the spacer fabric after the soaking is finished, enabling the mixed solution to penetrate through pores on the surface layer of the fabric to form irregular conical bulges, and controlling the curing temperature to obtain friction surfaces with different shapes so as to finish the preparation of the friction surfaces; secondly, the fineness and the density parameter of the spacing yarn are regulated and controlled to ensure that the upper friction layer and the lower friction layer are tightly connected and the charges generated after friction can be effectively separated; finally, respectively depositing a conductive material polypyrrole, polyaniline or carbon nano tubes on the surfaces of the upper fabric and the lower fabric in situ to form a flexible conductive layer, wherein the conductivity of the conductive layer is more than 0.1S/m, so that the effective transfer of induced charges is ensured, and the friction generator with a full textile structure, which is stable in structure and meets the actual application performance, is prepared; coating a layer of polydimethylsiloxane as a protective layer on the surface of the flexible conductive layer;
(2) the manufacture of a spacer fabric-based supercapacitor;
respectively carrying conductive polypyrrole on the upper and lower surfaces of the spacer fabric, and filling gel electrolyte in the middle spacer layer of the spacer fabric;
(3) connecting;
the connection refers to connecting one or more three-dimensional spacer fabric based triboelectric generators in series and/or in parallel with one or more spacer fabric based supercapacitors.
2. The method of claim 1, wherein the supporting means in-situ polymerization of the conductive polypyrrole on the upper and lower surfaces of the spacer fabric.
3. The method for manufacturing a composite energy device with a full textile structure according to claim 2, wherein the in-situ polymerization of the conductive polypyrrole means that the upper surface or the lower surface of the three-dimensional spacer fabric is immersed in a 0.02M-0.1M v/M-50 polymer monomer pyrrole solution, and the monomer solution is sufficiently dispersed into the surface fibers of the fabric after stirring for a period of time; then, the mixed solution of 0.04M-0.25M ferric trichloride as an oxidant and 0.005M-0.01M sodium anthraquinone-2-sulfonate as a dopant is added into the solution drop by drop to initiate in-situ polymerization reaction.
4. The method for manufacturing a composite energy device with a full textile structure according to claim 1, wherein the lead used for connection in step (3) is graphene/polyester conductive yarn, specifically: the method comprises the steps of soaking base yarns in 1M sodium hydroxide solution for 10-30min for simple alkali treatment, then dip-coating the base yarns in 1-5mg/mL graphene oxide solution for 5-10 times, drying the soaked yarns in an oven and winding the yarns into coils, and finally reducing the yarns in a reducing agent to obtain the graphene/terylene conductive yarns.
5. The method of claim 1, wherein the connection is performed by first converting an ac signal generated from the friction generator into a dc signal through a rectifier.
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| CN112968625B (en) * | 2021-03-09 | 2022-06-24 | 上海交通大学 | Glass fiber cloth material with positive friction polarity and preparation method and application thereof |
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