CN114835931B - Interface-enhanced multilayer composite conductive gel and preparation method thereof - Google Patents
Interface-enhanced multilayer composite conductive gel and preparation method thereof Download PDFInfo
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- CN114835931B CN114835931B CN202210322272.8A CN202210322272A CN114835931B CN 114835931 B CN114835931 B CN 114835931B CN 202210322272 A CN202210322272 A CN 202210322272A CN 114835931 B CN114835931 B CN 114835931B
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000001879 gelation Methods 0.000 title description 2
- 238000003475 lamination Methods 0.000 claims abstract description 5
- 239000000499 gel Substances 0.000 claims description 204
- 239000002243 precursor Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 40
- 239000006258 conductive agent Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229920001940 conductive polymer Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002086 nanomaterial Substances 0.000 claims description 14
- 239000002019 doping agent Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
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- 230000004044 response Effects 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 182
- 239000002245 particle Substances 0.000 description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 229910052737 gold Inorganic materials 0.000 description 14
- 239000010931 gold Substances 0.000 description 14
- 239000002356 single layer Substances 0.000 description 13
- 229920000144 PEDOT:PSS Polymers 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 229920000767 polyaniline Polymers 0.000 description 10
- 239000003607 modifier Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RQAFMLCWWGDNLI-UHFFFAOYSA-N 2-[4-[bis(2-chloroethyl)amino]phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(N(CCCl)CCCl)C=C1 RQAFMLCWWGDNLI-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 239000011544 gradient gel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C08K3/16—Halogen-containing compounds
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- 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
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Abstract
The invention discloses an interface-enhanced multilayer composite conductive gel and a preparation method thereof. The multilayer composite conductive gel comprises n gel layers and n-1 interface layers, wherein the n gel layers and the n-1 interface layers are alternately laminated, and the first gel layer, the first interface layer, the second gel layer, the second interface layer, … …, the n-1 interface layer and the n-1 interface layer are sequentially arranged along the lamination direction, wherein n is an integer greater than or equal to 2. The interface layer is used as a bonding interface between gel layers, and an interlocking structural unit is constructed between adjacent gel layers, so that the multi-layer composite conductive gel has excellent stretchability, good tensile strength, good elastic modulus and higher toughness, and also has excellent interface stability and good fatigue resistance. As a tensile strain sensor, it also has good conductivity, sensitive strain sensing performance, a wide strain response range, and excellent response stability.
Description
Technical Field
The invention relates to the technical field of conductive gel, in particular to an interface-enhanced multilayer composite conductive gel and a preparation method thereof.
Background
Conductive gels are three-dimensional polymer networks, physically or chemically crosslinked, with network structures resembling human cell matrices, most gels have similar young's modulus to muscle and skin tissue, good mechanical flexibility, environmental stability, biocompatibility, and thus find wide research and application in flexible conductive materials such as wearable electrodes, energy conversion and storage devices, sensors, implantable medical and biological devices, actuators. As an emerging conductive gel structure, the conductive gel with gradient modulus is similar to a gradual change structure from high modulus to low modulus from epidermis to dermis in a human skin structure, and is expected to have a great improvement effect on the sensitivity and the range of sensor signals.
However, the preparation method of the gradient modulus gel reported at present often realizes the gradient modulus by an electric field induction method or a particle sedimentation method and the like. For example, researchers reported a multi-stage gradient modulus ionogel polymer material (ADVANCED MATERIALS,2021,2008486) that achieved a gradient change in modulus from 0.3kPa to 2.5 MPa. However, this work is mainly achieved by applying a single electric field across the precursor solution during the preparation process to induce charged material in the precursor to accumulate in the vicinity of the electric field electrodes to form a gradient concentration and to undergo a curing crosslinking reaction. CN109096504B disclosed in the chinese patent office mainly prepares gradient gel with different sedimentation rates of particles such as hydrophobic white carbon black, hydrophobic silica, hydrophobic polymer particles, hydrophobic carbon nanoparticles, hydrophobic metal silica particles, hydrophobic aerogel particles, etc. in the gel. The above method, although realizing a gel material with gradient modulus gradient, has the following problems: the application of the electric field has certain limitation, so that the specific modulus combination and distribution in the material have the defect of unknown property; also, gradient modulus gels, which rely on differences in sedimentation velocity of the material, have uncontrollable material modulus depending on particle sedimentation.
In addition, CN113769120A, CN112457449a discloses a preparation scheme of a bilayer gel in the literature published by the chinese patent office, and mainly adopts a method of polymerizing one layer and then polymerizing the other layer, so that the two layers of gel are combined together. Such bilayer gels tend to have a poor interface, which results in poor stability during use, greatly affecting their useful life and limiting their field of application.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide an interface-enhanced multi-layer composite conductive gel and a preparation method thereof, which aims to solve the problem of unstable interface between the gel layers.
The technical scheme of the invention is as follows:
The interface-enhanced multilayer composite conductive gel comprises n gel layers and n-1 interface layers, wherein the n gel layers and the n-1 interface layers are alternately laminated, and sequentially comprise a first gel layer, a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n-1 interface layer along the lamination direction, wherein n is an integer greater than or equal to 2;
each interface layer independently comprises an interface conductive agent, and the interface conductive agent is a micro-nano material.
Optionally, the n gel layers have a mechanical modulus from large to small: the first gel layer is greater than the second gel layer is greater than … … and greater than the nth gel layer.
Optionally, the multilayer composite conductive gel is composed of a first gel layer, a first interface layer and a second gel layer which are sequentially stacked.
Optionally, each interface layer independently comprises an interface conductive agent, wherein the interface conductive agent is one or more selected from metal salts, metal nano materials (such as nano silver wires, nano silver particles, nano silver sheets and the like), conductive polymers containing doping agents and conductive carbon materials;
the thickness of each interface layer is between 50 nanometers and 50 micrometers.
Optionally, each gel layer has a thickness between 100 nanometers and 10 millimeters.
The preparation method of the interface-enhanced multilayer composite conductive gel comprises the following steps:
Preparing a first gel layer;
sequentially preparing a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n gel layer on the first gel layer to obtain the multilayer composite conductive gel, wherein n is an integer greater than or equal to 2.
Alternatively, the preparation method of each gel layer is independently selected from one of a template method, a spin coating method, a spray coating method and a printing method,
The preparation method of each interface layer is independently selected from one of a template method, a spin coating method, a spraying method and a printing method.
Optionally, n is 2, and the preparation method of the multilayer composite conductive gel comprises the following steps:
mixing 100 parts of a first solvent, 5-50 parts of a first polymer precursor, 0.1-10 parts of a first cross-linking agent, 0-20 parts of a first conductive agent and 0.01-20 parts of a first modulus regulator to obtain a first precursor solution;
Stirring the first precursor solution, and then carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to obtain a first gel layer;
Taking interface conductive agent dispersion liquid on the first gel layer to form a first interface layer;
Mixing 100 parts of a second solvent, 5-50 parts of a second polymer precursor, 0.1-10 parts of a second crosslinking agent, 0-20 parts of a second conductive agent and 0.01-20 parts of a second modulus regulator to obtain a second precursor solution;
stirring the second precursor solution, and then taking the second precursor solution on the first interface layer, and carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to form a second gel layer.
Optionally, the first polymer precursor and the second polymer precursor are each independently selected from one or more of acrylamide (abbreviated as AAm), N-methylolacrylamide (abbreviated as NMA), dimethylacrylamide, and polyvinyl alcohol;
The first crosslinking agent and the second crosslinking agent are respectively and independently selected from one or more of N, N' -dimethyl diacrylamide, polyethylene glycol diacrylate, methacryloylated gelatin, acryloylated xanthan gum and ammonium persulfate;
the first conductive agent and the second conductive agent are each independently selected from one or more of metal salts, metal nanomaterials, conductive polymers containing dopants, conductive carbon materials;
The metal salt is one or more selected from potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl 2), copper chloride (CuCl 2) and ferric chloride (FeCl 3);
The metal nano material is one or more selected from nano silver wires, nano silver particles, nano silver sheets, nano gold wires, nano gold particles, nano gold sheets, nano copper wires, nano copper particles and nano copper sheets;
The conductive polymer is selected from one or more of Polyaniline (PANi), polypyrrole (Ppy) and poly 3, 4-ethylenedioxythiophene (PEDOT);
the doping agent is selected from one or more of poly (styrenesulfonic acid), hydrochloric acid, sulfuric acid and citric acid;
The first modulus modifier and the second modulus modifier are each independently selected from one or more of polyvinylpyrrolidone (abbreviated PVP), carboxylated cellulose nanowhiskers (abbreviated C-CNWs), carboxymethyl chitosan, metal oxide micro-nanoparticles.
The metal oxide micro-nano particles are selected from one or more of silicon dioxide, titanium dioxide, barium titanate, ferroferric oxide, zinc oxide, nickel oxide and other metal oxide micro-nano particles.
The first solvent and the second solvent are respectively and independently selected from one or more of deionized water, ethanol, methanol, isopropanol, isobutanol, glycerol and ethylene glycol.
Optionally, the interfacial conductive agent dispersion is composed of an interfacial conductive agent and an interfacial solvent;
The interface conductive agent is one or more selected from metal salt, metal nano material (such as nano silver wire, nano silver particle, nano silver sheet, nano gold wire, nano gold particle, nano gold sheet, nano copper wire, nano copper particle, nano copper sheet, etc.), conductive polymer containing doping agent, conductive carbon material (such as conductive carbon black, conductive carbon nano tube, conductive graphene, etc.);
the conductive polymer is selected from one or more of Polyaniline (PANi), polypyrrole (Ppy), poly 3, 4-ethylenedioxythiophene (PEDOT) and the like;
The interfacial solvent is one or more selected from deionized water, ethanol, methanol, isopropanol, isobutanol, glycerol and ethylene glycol.
The beneficial effects are that: the invention introduces an interface layer between the gel layers, which acts as a bonding interface between the gel layers, creating interlocking structural units between adjacent gel layers. The interfacial strength and stability of the double-layer gel can be enhanced by introducing the interfacial layer, so that the multi-layer composite conductive gel containing the interfacial layer has excellent stretchability, good tensile strength, good elastic modulus and higher toughness. Due to modulus matching between gel layers, an interface interlocking network and patch effect of interfaces, the multilayer composite conductive gel has excellent interface stability and good fatigue resistance. As a tensile strain sensor, it also has good conductivity, sensitive strain sensing performance, a wide strain response range, and excellent response stability.
Drawings
Fig. 1 is a schematic structural diagram of an interface-enhanced multi-layer composite conductive gel.
Fig. 2 is a stress-strain curve of a bilayer conductive gel with and without an added interfacial layer.
Fig. 3 is a cyclic stretching response of a bilayer conductive gel with and without an added interfacial layer.
Fig. 4 is a peel strength test of a bilayer conductive gel with and without an added interfacial layer.
FIG. 5 shows a strain sensing test of a double-layer conductive gel with and without an additional interfacial layer.
Detailed Description
The invention provides an interface-enhanced multilayer composite conductive gel and a preparation method thereof. The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides an interface-enhanced multilayer composite conductive gel, which comprises n gel layers and n-1 interface layers, wherein the n gel layers and the n-1 interface layers are alternately laminated, and sequentially comprise a first gel layer, a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n gel layer along the lamination direction, wherein n is an integer greater than or equal to 2;
each interface layer independently comprises an interface conductive agent, and the interface conductive agent is a micro-nano material.
For example, when n is 5, the multi-layer composite conductive gel includes 5 gel layers and 4 interface layers, wherein the 5 gel layers and the 4 interface layers are alternately laminated, and the first gel layer 11, the first interface layer 12, the second gel layer 13, the second interface layer 14, the third gel layer 15, the third interface layer 16, the fourth gel layer 17, the fourth interface layer 18, and the fifth gel layer 19 are sequentially laminated along the lamination direction, as shown in fig. 1.
In this embodiment, the multi-layer composite conductive gel comprises a series of gel layers, and an interface layer introduced between the gel layers. The interfacial layer serves as a bonding interface between the gel layers, and an interlocking structural unit is constructed between adjacent gel layers. This is because effective hydrogen bonds and covalent bonds (e.g., hydrogen bonds between the PAAM host polymer segment and PEDOT: PSS) can be formed between the interfacial layer and the polymer material and other materials of the adjacent gel, and at the same time, since the interfacial layer material is micro-nano structure, a layer of interfacial structure with a rough surface can be formed, further increasing the contact area between the adjacent gel and the interfacial layer. The two functions effectively improve the contact area and the mutual bonding force between the adjacent gel layers by introducing the interface layer. The multi-layer composite conductive gel containing the interface layer of the embodiment has excellent stretchability, good tensile strength, good elastic modulus and higher toughness. Due to modulus matching between gel layers, an interface interlocking network and patch effect of interfaces, the multilayer composite conductive gel of the embodiment has excellent interface stability and good fatigue resistance. As a tensile strain sensor, it also has good conductivity, sensitive strain sensing performance, a wide strain response range, and excellent response stability.
In one embodiment, the n gel layers have a mechanical modulus from large to small: the first gel layer is greater than the second gel layer is greater than … … and greater than the nth gel layer. The n gel layers are arranged from the bottom layer to the top layer according to the size of the mechanical modulus, so that the multi-layer composite conductive gel has the characteristic of gradual change of modulus. Due to modulus matching between gel layers, an interface interlocking network and patch effect of interfaces, the multilayer composite conductive gel of the embodiment has excellent interface stability and good fatigue resistance.
In one embodiment, the multi-layer composite conductive gel is composed of a first gel layer, a first interface layer and a second gel layer which are sequentially stacked. That is, the multilayer composite conductive gel of the present embodiment is composed of a double-layer gel layer and an interface layer between the double-layer gel layers. The interfacial layer acts as a bonding interface between the gel layer and the gel layer, creating interlocking structural units between the double layer gel layer. The conductive gel of the double-layer structure containing the interface layer of this example has excellent stretchability, good tensile strength, good elastic modulus and higher toughness. The conductive gel of the embodiment has excellent interface stability and good fatigue resistance due to modulus matching between two gel layers, an interface interlocking network and a patch effect of an interface. As a tensile strain sensor, it also has good conductivity, sensitive strain sensing performance, a wide strain response range, and excellent response stability.
In one embodiment, each interface layer independently includes an interface conductive agent, which may be selected from one or more of a metal salt, a metal nanomaterial, a conductive polymer containing a dopant, a conductive carbon material, and the like. Wherein the metal salt is selected from one or more of potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl 2), copper chloride (CuCl 2), ferric chloride (FeCl 3) and the like; the metal nano material can be one or more selected from nano silver wires, nano silver particles, nano silver flakes, nano gold wires, nano gold particles, nano gold flakes, nano copper particles, nano copper wires, nano copper sheets and the like; the conductive polymer is selected from one or more of Polyaniline (PANi), polypyrrole (Ppy) and poly 3, 4-ethylenedioxythiophene (PEDOT); the doping agent is selected from one or more of poly (styrenesulfonic acid), hydrochloric acid, sulfuric acid and citric acid. Wherein the materials of the interface layers of the layers can be the same or different.
In one embodiment, the thickness of each interfacial layer is between 50 nanometers and 50 microns, such as 50 nanometers, 0.01 microns, 3 microns, 10 microns, 20 microns, etc. The thickness of each interface layer can be the same or different. Further, the thickness of each interface layer is the same.
In one embodiment, each gel layer has a thickness of between 100 nanometers and 10 millimeters, such as a thickness of 100 nanometers, 500 nanometers, 800 nanometers, 1 micrometer, 10 micrometers, 1 millimeter, 10 millimeters, or the like. Wherein the thickness of each gel layer can be the same or different. Further, the thickness of each interface layer is the same.
The embodiment of the invention provides a preparation method of the interface-enhanced multilayer composite conductive gel, which comprises the following steps:
Preparing a first gel layer;
and sequentially preparing a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n gel layer on the first gel layer to obtain the conductive gel, wherein n is an integer greater than or equal to 2.
In one embodiment, the method of preparing each gel layer is independently selected from one of a stencil method, a spin coating method, a spray coating method, a printing method, and the like.
The template method is to use a template of a fixed shape to surround the periphery of the gel layer, and to obtain a desired shape and thickness by pouring an appropriate amount of gel precursor solution and then solidifying.
The spin coating method is to spin-coat an appropriate amount of gel precursor solution on a substrate, followed by curing to obtain a desired shape and thickness.
The spraying method is to spray a proper amount of gel precursor solution on a substrate and then cure the gel precursor solution to obtain a required shape and thickness.
The printing method is to print gel precursor solution on a substrate in different shapes by using printing technologies such as 3D printing, screen printing or ink-jet printing, and then solidifying to obtain the required gel layer.
In one embodiment, the method of preparing the interfacial layer of each layer is independently selected from one of a template method, a spin coating method, a spray coating method, a printing method, and the like.
In one embodiment, n is 2, and the preparation method of the multilayer composite conductive gel comprises the following steps:
mixing 100 parts of a first solvent, 5-50 parts of a first polymer precursor, 0.1-10 parts of a first cross-linking agent, 0-20 parts of a first conductive agent and 0.01-20 parts of a first modulus regulator to obtain a first precursor solution;
Stirring the first precursor solution, and then carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to obtain a first gel layer;
Taking interface conductive agent dispersion liquid on the first gel layer to form a first interface layer;
Mixing 100 parts of a second solvent, 1-50 parts of a second polymer precursor, 0.01-10 parts of a second crosslinking agent, 0-20 parts of a second conductive agent and 0.01-20 parts of a second modulus regulator to obtain a second precursor solution;
stirring the second precursor solution, and then taking the second precursor solution on the first interface layer, and carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to form a second gel layer.
In this embodiment, the interfacial conductive agent dispersion liquid is composed of an interfacial conductive agent and an interfacial solvent. In one embodiment, the interfacial conductive agent is selected from one or more of metal salts, metal nanomaterials, conductive polymers containing dopants, conductive carbon materials, and the like. Wherein the metal salt is selected from one or more of potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl 2), copper chloride (CuCl 2) and ferric chloride (FeCl 3); the metal nano material can be one or more selected from nano silver wires, nano silver particles, nano silver flakes, nano gold wires, nano gold particles, nano gold flakes, nano copper particles, nano copper wires, nano copper sheets and the like; the conductive polymer is selected from one or more of Polyaniline (PANi), polypyrrole (Ppy) and poly 3, 4-ethylenedioxythiophene (PEDOT); the doping agent is selected from one or more of poly (styrenesulfonic acid), hydrochloric acid, sulfuric acid and citric acid.
In one embodiment, the interfacial solvent is selected from one or more of deionized water, ethanol, methanol, isopropanol, isobutanol, and the like.
In one embodiment, the first and second polymer precursors are each independently selected from one or more of acrylamide, N-methylolacrylamide, dimethylacrylamide, polyvinyl alcohol, and the like.
In one embodiment, the first and second crosslinking agents are each independently selected from one or more of N, N' -dimethyl diacrylamide, polyethylene glycol diacrylate, methacryloylated gelatin, acrylated xanthan gum, ammonium persulfate, and the like.
In one embodiment, the first and second conductive agents are each independently selected from one or more of a metal salt, a metal nanomaterial, a conductive polymer containing a dopant, a conductive carbon material, and the like.
Wherein the metal salt is selected from one or more of potassium chloride (KCl), sodium chloride (NaCl), calcium chloride (CaCl 2), copper chloride (CuCl 2) and ferric chloride (FeCl 3); the metal nano material is one or more selected from nano silver wires, nano silver particles, nano silver sheets, nano gold wires, nano gold particles, nano gold sheets, nano copper wires, nano copper particles and nano copper sheets; the conductive polymer is selected from one or more of Polyaniline (PANi), polypyrrole (Ppy) and poly 3, 4-ethylenedioxythiophene (PEDOT); the doping agent is selected from one or more of poly (styrenesulfonic acid), hydrochloric acid, sulfuric acid and citric acid.
In one embodiment, the first and second modulus modifiers are each independently selected from one or more of polyvinylpyrrolidone (PVP), carboxylated cellulose nanowhiskers, carboxymethyl chitosan, metal-oxide micro-nanoparticles, and the like. Wherein the metal oxide micro-nano particles are selected from one or more of silicon dioxide, titanium dioxide, barium titanate, ferroferric oxide, zinc oxide, nickel oxide and other metal oxide micro-nano particles.
The embodiment of the invention provides a method for applying the interface-enhanced multilayer composite conductive gel to stretchable electronic equipment, soft robots and wearable equipment.
The invention is further illustrated by the following specific examples.
Example 1
This example proposes a bilayer composite conductive gel with an aqueous dispersion of poly (styrenesulfonic acid) -doped poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS) microspheres (PEDOT: PSS microspheres 3 microns in diameter) as an interface, the preparation steps of the bilayer composite conductive gel being as follows:
first, a PANC precursor solution and PAVK precursor solution were prepared:
PANC precursor solution: 5.00g deionized water as solvent, 1.20g AAm polymer precursor, 0.05g NMA polymer precursor, 0.10g C-CNWs as modulus modifier were weighed into a glass beaker and subsequently stirred continuously at 70℃for 4 hours to dissolve all materials completely.
PAVK precursor solution: 5.00g deionized water as solvent, 1.20g AAm as polymer precursor, 0.10g PVP as modulus modifier, 0.03g KCl as conductive agent, 0.001g acrylated xanthan gum as crosslinking agent were weighed into a glass beaker and stirred for 2 hours to dissolve the mixture completely.
Then, 0.03g of PANC precursor solution is taken, 0.03g of ammonium persulfate is added as a cross-linking agent, the mixture is poured into a template after being uniformly stirred, and the template is put into an oven at 80 ℃ for pre-polymerization for 7 minutes, so that the PANC pre-polymerized gel layer is obtained. Next, 300. Mu.l of PEDOT/PSS aqueous dispersion (PEDOT: PSS concentration 1.2 wt%) was measured with a pipette and transferred to a spray gun. And after adjusting the distance and the speed of the spray gun, spraying the PANC prepolymer gel layer to form a PEDOT-PSS interface layer, wherein the thickness of the interface layer is 6 microns. Finally, 0.03g of ammonium persulfate cross-linking agent is added into the precursor solution of 0.03g PAVK g, and the mixture is poured onto the PEDOT/PSS interface layer after being uniformly stirred. And then, putting the mixture into an oven at 80 ℃ to be completely polymerized for 40 minutes for template method curing to form PAVK/PEDOT: PSS/PANC double-layer composite conductive gel.
Comparative example 1
This comparative example proposes a PANC monolayer conductive gel prepared by the following steps:
5.00g deionized water solvent, 1.20g AAm polymer precursor, 0.05g NMA polymer precursor, 0.10g C-CNWs modulus modifier were weighed into a glass beaker and stirred continuously at 70℃for 4 hours to allow complete dissolution of all materials. Then 0.03g of ammonium persulfate cross-linking agent is added, after being stirred uniformly, the mixture is poured into a template and put into an oven at 80 ℃ to be completely polymerized for 40 minutes, so as to form PANC single-layer conductive gel.
Comparative example 2
This comparative example proposes a PAVK single layer conductive gel prepared by the following steps:
5.00g deionized water as solvent, 1.20g AAm as polymer precursor, 0.10g PVP as modulus modifier, 0.03g KCl as conductive agent, 0.001g acrylated xanthan gum as crosslinking agent were weighed into a glass beaker and stirred for 2 hours to dissolve the mixture completely. Then 0.03g of ammonium persulfate cross-linking agent is added, after being stirred uniformly, the mixture is poured into a template and put into an oven at 80 ℃ to be completely polymerized for 40 minutes, so as to form PAVK single-layer conductive gel.
Comparative example 3
The comparative example proposes PAVK/PANC double-layer conductive gel, and the preparation steps of the conductive gel are as follows:
first, a PANC precursor solution and PAVK precursor solution were prepared:
PANC precursor solution: 5.00g deionized water as solvent, 1.20g AAm polymer precursor, 0.05g NMA polymer precursor, 0.10g C-CNWs as modulus modifier were weighed into a glass beaker and subsequently stirred continuously at 70℃for 4 hours to dissolve all materials completely.
PAVK precursor solution: 5.00g deionized water as solvent, 1.20g AAm as polymer precursor, 0.10g PVP as modulus modifier, 0.03g KCl as conductive agent, 0.001g acrylated xanthan gum as chemical cross-linking agent were weighed into a glass beaker and stirred for 2 hours to dissolve the mixture completely.
Then, 0.03g of PANC precursor solution is taken, 0.03g of ammonium persulfate cross-linking agent is added, the mixture is poured into a template after being stirred uniformly, and the template is put into an oven at 80 ℃ for pre-polymerization for 7 minutes, so that PANC pre-polymerized gel layer is obtained. Next, 0.03g of ammonium persulfate cross-linking agent was added to the precursor solution of 0.03g PAVK, and after stirring uniformly, poured onto the PANC pre-polymerized gel layer. Then, the mixture is put into an oven at 80 ℃ to be completely polymerized for 40 minutes for template method curing, and PAVK/PANC double-layer conductive gel is formed.
The conductive gels of example 1 and comparative examples 1 to 3 described above were tested and the test results were as follows:
FIG. 2 is a stress-strain curve of PANC, PAVK single layer conductive gel and PAVK/PANC and PAVK/PEDOT PSS/PANC double layer conductive gel. As shown in fig. 2 (a), the mechanical properties of the PANC single layer conductive gel are greater than those of the PAVK single layer conductive gel, and the mechanical properties of the PAVK/PANC double layer conductive gel prepared from these two layers of conductive gel lie between them. Subsequently, the introduction of the PEDOT/PSS interface layer can effectively enhance the interface toughness and the interface strength of PAVK/PANC double-layer conductive gel, so that the PAVK/PEDOT/PSS/PANC double-layer conductive gel has good mechanical properties (shown in (b) of fig. 2), the breaking strain is 1763.85%, the tensile strength is 0.92MPa, the elastic modulus is 69.16KPa, and the toughness is 9.27MJ/m 3.
FIG. 3 shows the cyclic stretching response of PAVK/PANC and PAVK/PEDOT: PSS/PANC bilayer conductive gels. As shown in fig. 3, when the PAVK/PANC double-layer conductive gel was tested for cyclic tensile response without any interface treatment, it was found to be less stable and only able to respond less than 2500 cycles. After the PEDOT-PSS interface layer is introduced, PAVK/PEDOT-PSS/PANC double-layer conductive gel can stably respond more than 12500 stretching loading-unloading cycles, which shows that the introduction of the PEDOT-PSS interface layer improves the interface strength and the interface stability of the PVAK/PANC double-layer conductive gel (see shown in figure 4).
FIG. 5 is a strain sensing test of PAVK/PEDOT: PSS/PANC bilayer conductive gel. The relationship between the applied strain during stretching and the relative resistance change of the sample is shown in fig. 5 (a), and a linear fit is performed. From the results, PAVK/PEDOT PSS/PANC bilayer conductive gel can respond to strain with a broad linear response range (0-445%). Through linear fitting results, a strain range of 0-445% can be obtained, and the strain coefficient (GF) is 4.28; for a strain range of 445-905%, the GF value increases to 9.71; after the strain reaches 1600%, the GF value reaches a maximum value of 18.14. The relative resistance change of the PANC/PEDOT: PSS/PAVK bilayer gel showed stable response peak shapes under both small and large strains (FIG. 5 (b)), indicating that the gel had good reproducibility and high sensitivity. Furthermore, PAVK/PEDOT PSS/PANC bilayer conductive gel was subjected to more than 12500 load-unload stretching cycles from 0 to 200% strain (FIG. 5 (c)). Experimental results show that PAVK/PEDOT-PSS/PANC double-layer gel has excellent cycle stability and durability.
Table 1 below shows the mechanical properties of the individual single-layer gels in comparison with the double-layer gels. As can be taken from table 1, the PANC monolayer gel exhibits the properties of a hard hydrogel, such as high modulus, high tensile strength, but lower ductility. PAVK single layer gels exhibit typical soft gel properties such as low modulus, low tensile strength, low toughness, but strong stretchability. After the two single-layer gels are compounded, the prepared PANC/PAVK double-layer conductive gel has good mechanical property and modulus adaptability. Subsequently, PEDOT and PSS interface layer are further introduced, so that the mechanical property of the double-layer hydrogel is further improved. In summary, by compounding the high modulus PANC monolayer gel with the low modulus PAVK monolayer gel and introducing the PEDOT: PSS interfacial layer, the PAVK/PEDOT: PSS/PANC composite bilayer gel combines soft water gel properties (good ductility and moderate modulus) with hard water gel properties (maintaining a certain strength and toughness), has a breaking strain of 1763.85%, a tensile strength of 0.92MPa, an elastic modulus of 69.16kPa, and a toughness of 9.27MJ/m 3.
TABLE 1
In summary, the invention provides a multilayer structure conductive gel with excellent mechanical interface stability, fatigue resistance, electrical stability and strain sensitivity. The multi-layer conductive gel is composed of a series of gel layers, and interlocking structural units are constructed between the two layers of gel by a prepolymerization technique and a spray technique. The conductive gel with the double-layer structure containing the PEDOT and PSS interface has excellent stretchability, good tensile strength, good elastic modulus and higher toughness. The resulting double-layer conductive gel exhibits excellent interfacial stability and good fatigue resistance due to modulus matching between the two-layer gels, interfacial interlocking network, and the patch effect of PEDOT: PSS. As a tensile strain sensor, it also exhibits good conductivity (not less than 1.76S/m), sensitive strain sensing performance (at least up to a strain coefficient of 10.46), a broad strain response range (0-445%) and excellent response stability (> 12,500 cycles). The above-described double-layer structured conductive gel with PEDOT: PSS interface can be used for promising materials for use in stretchable electronics, soft robots, and next generation wearable devices.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
1. The interface-enhanced multilayer composite conductive gel is characterized by comprising n gel layers and n-1 interface layers, wherein the n gel layers and the n-1 interface layers are alternately laminated, and sequentially comprise a first gel layer, a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n gel layer along the lamination direction, wherein n is an integer greater than or equal to 2;
each interface layer is independently composed of an interface conductive agent, wherein the interface conductive agent is a micro-nano material;
the interface conductive agent is selected from one or more of metal salt, conductive polymer and conductive polymer containing doping agent; the thickness of each interface layer is between 50 nanometers and 50 micrometers.
2. The interface enhanced multi-layer composite conductive gel of claim 1, wherein the n-layer gel layer has a mechanical modulus from large to small: the first gel layer is greater than the second gel layer is greater than … … and greater than the nth gel layer.
3. The interface-enhanced multilayer composite conductive gel of claim 1 or 2, wherein the multilayer composite conductive gel is composed of a first gel layer, a first interface layer, and a second gel layer, which are sequentially stacked.
4. The interface enhanced multi-layer composite conductive gel of claim 1, wherein each gel layer has a thickness between 100 nanometers and 10 millimeters.
5. A method of preparing the interface-enhanced multi-layer composite conductive gel of any one of claims 1-4, comprising the steps of:
Preparing a first gel layer;
sequentially preparing a first interface layer, a second gel layer, a second interface layer, … …, an n-1 interface layer and an n gel layer on the first gel layer to obtain the multilayer composite conductive gel, wherein n is an integer greater than or equal to 2.
6. The method for preparing the interface-enhanced multi-layer composite conductive gel according to claim 5, wherein the method for preparing each layer of gel layer is independently selected from one of a template method, a spin coating method, a spray coating method and a printing method, and the method for preparing each layer of interface layer is independently selected from one of a template method, a spin coating method, a spray coating method and a printing method.
7. The method for preparing an interface-enhanced multi-layer composite conductive gel according to claim 5, wherein n is 2, the method for preparing the multi-layer composite conductive gel comprising:
mixing 100 parts of a first solvent, 5-50 parts of a first polymer precursor, 0.1-10 parts of a first cross-linking agent, 0-20 parts of a first conductive agent and 0.01-20 parts of a first modulus regulator to obtain a first precursor solution;
Stirring the first precursor solution, and then carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to obtain a first gel layer;
Taking interface conductive agent dispersion liquid on the first gel layer to form a first interface layer;
Mixing 100 parts of a second solvent, 1-50 parts of a second polymer precursor, 0.01-10 parts of a second crosslinking agent, 0-20 parts of a second conductive agent and 0.01-20 parts of a second modulus regulator to obtain a second precursor solution;
stirring the second precursor solution, and then taking the second precursor solution on the first interface layer, and carrying out prepolymerization for 1-60 minutes under the condition of heating at 25-90 ℃ or ultraviolet irradiation to form a second gel layer.
8. The method for preparing an interface-enhanced multilayer composite conductive gel according to claim 7, wherein the first polymer precursor and the second polymer precursor are each independently selected from one or more of acrylamide, N-methylolacrylamide, dimethylacrylamide, polyvinyl alcohol;
The first crosslinking agent and the second crosslinking agent are respectively and independently selected from one or more of N, N' -dimethyl diacrylamide, polyethylene glycol diacrylate, methacryloylated gelatin, acryloylated xanthan gum and ammonium persulfate;
the first conductive agent and the second conductive agent are each independently selected from one or more of a metal salt, a conductive polymer containing a dopant;
The first modulus regulator and the second modulus regulator are respectively and independently selected from one or more of polyvinylpyrrolidone, carboxylated cellulose nanowhisker, carboxymethyl chitosan and metal oxide micro-nano particles;
The first solvent and the second solvent are respectively and independently selected from one or more of deionized water, ethanol, methanol, isopropanol, isobutanol, glycerol and ethylene glycol.
9. The method for preparing an interface-enhanced multi-layer composite conductive gel according to claim 7, wherein the interface conductive agent dispersion liquid is composed of an interface conductive agent and an interface solvent;
The interface conductive agent is selected from one or more of metal salt, conductive polymer and conductive polymer containing doping agent;
The interfacial solvent is one or more selected from deionized water, ethanol, methanol, isopropanol, isobutanol, glycerol and ethylene glycol.
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CN113773445A (en) * | 2021-08-31 | 2021-12-10 | 北京工业大学 | Preparation method and application of hydrogel flexible touch sensor |
CN113769120A (en) * | 2021-09-18 | 2021-12-10 | 北京脑陆科技有限公司 | Preparation method of double-layer conductive hydrogel |
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