CN105887054B - A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof - Google Patents
A kind of highly conductive biomass/nano metal flexible compound film and preparation method thereof Download PDFInfo
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- CN105887054B CN105887054B CN201610414363.9A CN201610414363A CN105887054B CN 105887054 B CN105887054 B CN 105887054B CN 201610414363 A CN201610414363 A CN 201610414363A CN 105887054 B CN105887054 B CN 105887054B
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- deionized water
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 239000002028 Biomass Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title description 4
- 238000007747 plating Methods 0.000 claims abstract description 38
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003638 dopamine Drugs 0.000 claims abstract description 18
- 229920001690 polydopamine Polymers 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007853 buffer solution Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 101150003085 Pdcl gene Proteins 0.000 claims abstract 3
- 239000002932 luster Substances 0.000 claims abstract 2
- 239000002905 metal composite material Substances 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 229920001661 Chitosan Polymers 0.000 claims description 22
- 239000000872 buffer Substances 0.000 claims description 14
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- -1 CuSO 4 ·5H 2 O Chemical compound 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims 2
- 241000080590 Niso Species 0.000 claims 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims 2
- 239000004964 aerogel Substances 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000002310 reflectometry Methods 0.000 abstract 1
- 229920000742 Cotton Polymers 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 9
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 229910052927 chalcanthite Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000012620 biological material Substances 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910003204 NH2 Inorganic materials 0.000 description 1
- 229910017912 NH2OH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
本发明公开了一种高导电生物质/纳米金属柔性复合膜及其制备方法，包括如下步骤：(1)将生物质基底浸渍于多巴胺缓冲溶液中，连续搅拌，将所得薄膜用去离子水多次冲洗，得到表面覆盖有聚多巴胺的复合薄膜；(2)将上述复合薄膜浸渍于(NH4)2PdCl4的水溶液中，搅拌，使得基底表面固定上催化剂；(3)将步骤(2)所得复合薄膜用去离子水多次冲洗后，在室温下浸渍于铜或银或金或镍的镀液中至少5min，所得薄膜用去离子水洗涤干净，最后经干燥得到表面具有金属光泽的生物质/纳米金属/纳米金属复合薄膜。本发明操作简单，耗时较短，成本较低；所得到的生物质/纳米金属复合薄膜有高导电率或高反射率。
The invention discloses a highly conductive biomass/nano metal flexible composite membrane and a preparation method thereof, comprising the following steps: (1) immersing a biomass substrate in a dopamine buffer solution, stirring continuously, and adding deionized water to the obtained membrane Rinse for several times to obtain a composite film whose surface is covered with polydopamine; (2) immerse the composite film in an aqueous solution of (NH 4 ) 2 PdCl 4 and stir to fix the catalyst on the surface of the substrate; (3) apply step (2) The obtained composite film was rinsed several times with deionized water, then immersed in a plating solution of copper or silver or gold or nickel at room temperature for at least 5 min, the obtained film was washed with deionized water, and finally dried to obtain a raw material with metallic luster on the surface. Substance/nanometal/nanometal composite films. The method has the advantages of simple operation, short time consumption and low cost; the obtained biomass/nano metal composite film has high conductivity or high reflectivity.
Description
Technical field
The invention belongs to chemical deposition metals, optical electro-chemistry field, and in particular to a kind of biomass/nano metal THIN COMPOSITE
Film and preparation method thereof.
Background technique
It is portable and wearable electronic devices field rapid development cause people to highly conductive, flexible material demand rapidly
Rise.The conductive material of polymer matrix is at low cost because of its outstanding flexibility, multifunction and be widely used in this.It is conductive
Fexible film or fabric can be prepared by conducting polymer or flexible polymer, such as PET, paper, rubber etc..Due to ore
The exhaustion of resource and the exacerbation of environmental problem, boiomacromolecule are increasingly becoming the important sources of substitution petroleum based material.With petroleum
Sill is compared, and boiomacromolecule has its unique advantage, such as biodegradability, and biocompatibility is environmentally friendly, it is low at
This, it is renewable etc..Wherein, cellulose has been widely used in the fields such as packaging as the most abundant resource of nature, especially
It is important that because of its stronger mechanical strength, inherent flexibility has cellulose in fields such as compliant conductive, energy stores
Huge potentiality.
There is a large amount of research that the conductive materials such as graphene, carbon nanotube and cellulose are compounded to form conductive flexible thin
Film, however the preparation of these conductive products generally requires complicated operating process and the filler of valuableness is added often to increase
Application cost limits its extensive use.From conductivity, cost angularly for, metal be still manufacture conductive material it is best
Selection.
The method of metallising mainly includes physical vapour deposition (PVD) at present, chemical vapor deposition, electrochemical deposition of metal, with
And chemical deposition metal.Wherein chemical deposition metal is that one kind can prepare high-test metal in flexible, stretchable substrate
The method of structure, this method do not need high-temperature process, and without expensive equipment and conductive substrates, therefore cost is relatively low.Change
Learning deposition process includes two steps: (1) fixation of the substrate surface anchor layer to metallic catalyst；(2) in plating solution metal growth.Its
Middle anchor layer is most important, because it not only determines the fixed efficiency of catalyst, so that subsequent redox reaction is influenced,
Anchor layer, which copes with plated metal, simultaneously good adhesion effect.It therefore need to be in substrate surface graft polymers molecular brush conduct
Anchor layer, but its grafting method is complicated, required expensive equipment, higher cost.
Summary of the invention
The present invention provides a kind of highly conductive biomass/nano metal flexible compound films of poly-dopamine auxiliary electroless deposition
Preparation method, using the method simply impregnated, using biological material as substrate, poly-dopamine is Anchor Agent, effectively fixed gold
Metal catalyst, so that redox reaction and deposited metal occur on the surface of biological material.Solves existing surface metal
Change technical operation is cumbersome, and time-consuming, poorly conductive, the caducous problem of surface metal, simultaneously for various biomass material institutes
Manufactured material of various shapes is applicable in.
The present invention is realized especially by following technical scheme:
A kind of highly conductive biomass/nano metal flexible compound film preparation method of poly-dopamine auxiliary electroless deposition,
Include the following steps:
(1) biomass-based bottom is impregnated in dopamine buffer solution, and is continuously stirred under 100-500rpm revolving speed
Gained film is repeatedly rinsed with deionized water, obtains to surface and be covered with the laminated film of poly-dopamine by 0.5-24h；
(2) above-mentioned laminated film is impregnated in (NH4)2PdCl4Aqueous solution in, stir 0.5- under 100-500rpm revolving speed
4h, so that the fixed upper catalyst of substrate surface；
(3) after repeatedly rinsing laminated film obtained by step (2) with deionized water, it is impregnated in copper or silver or gold at room temperature
Or at least 5min in the plating solution of nickel, gained film are washed with deionized completely, are most dried to obtain surface afterwards with metal light
Biomass/nano metal/nano metal the laminated film in pool.
TrisHCl buffer of the dopamine buffer described in step (1) for dopamine, concentration 0.5-5mg/ml,
The pH=6.0-10.0 of TrisHCl buffer.
(NH described in step (2)4)2PdCl4Aqueous solution concentration be 0.1mg/ml-1mg/ml.
Dip time described in step (3) is 10~60min.
Dry to air-dry or being dried in vacuo described in step (3), vacuum drying temperature is 25-60 DEG C.
The biomass-based bottom includes with two dimension made of biomass material or three-dimensional material.
The biomass-based bottom be cellulose paper, cellulose, chitosan, hemicellulose or its be modified transparent membrane,
Aeroge, hydrogel, fabric.
The plating solution of the copper is NaOH, CuSO4·5H2O, the mixed solution of sodium potassium tartrate tetrahydrate and reducing agent formaldehyde；The silver
Plating solution be [Ag (NH3)2]NO3With the mixed liquor of sodium potassium tartrate tetrahydrate, the plating solution of the nickel is NiSO4·5H2O, sodium citrate, cream
The mixed liquor of acid and dimethylamine borane；The plating solution of the gold is HAuCl4, NaOH, NH2OHHCl, Na2HPO4, NaS2O3·
5H2O and Na2SO3Mixed liquor.
The plating solution of the copper is by 12g/L NaOH, 13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent
9.5ml/L formaldehyde composition；The plating solution of the silver is by 1g/L [Ag (NH3)2]NO3It is formed with 5g/L sodium potassium tartrate tetrahydrate；The plating of the nickel
Liquid is by 40g/L NiSO4·5H2O, 20g/L sodium citrate, the lactic acid of 10g/L and the dimethylamine borane of 1g/L are mixed with volume ratio 4:1
It closes, while adjusting pH with ammonium hydroxide is 8；The plating solution of gold is 3.3g/L HAuCl4, 0.4g/L NaOH, 6.95g/L NH2OH·
HCl, 11g/L Na2HPO4, 16g/L NaS2O3·5H2O and 40g/L Na2SO3It mixes.
The above method preparation biomass/nano metal laminated film, be formed by metal can secure adhesion in biology
In matter substrate.The nitrogen-containing group of poly-dopamine can be firmly combined with catalyst metal ion, while play firm deposited
The effect of metal.
The present invention is using the method that simply impregnates, using poly-dopamine as anchor layer, in cellulose substrate (or other biological matter
Raw material is substrate) surface chemistry deposited metal.Prepared biomass/nano metal laminated film has good electric conductivity,
The metal of deposition can be firmly attached to substrate surface simultaneously.Operation is simple for the preparation process, can be completed under room temperature.
Prepared biomass/nano metal laminated film has very big application potential in fields such as energy storage, electronic equipments.
Compared with existing polymer surfaces metallization processes, the invention has the following advantages that
(1) operation of the present invention is simple, and time-consuming shorter, cost is relatively low；
(2) there is very strong adhesion strength between the metal and substrate on the laminated film surface prepared by the present invention, metal is not easy
The metal layer even compact for falling off, and being formed.
(3) biomass material and dopamine (belonging to biomass) used in be all it is environmental-friendly, it is biodegradable and biological
The material of compatibility, obtained biomass/nano metal laminated film have high conductivity or high reflectance, can be used for metallurgy,
Photoelectric device, wearable electronic, chemical industry, bio-sensing, implantable electronic device, energy storage, military industrial technology etc. are important
The application range of biological material has been widened in field significantly.
Detailed description of the invention
Fig. 1 be in 1-4 of the embodiment of the present invention filter paper and cotton with the mass-change curve of copper facing time change.
Fig. 2 is that filter paper and cotton change with the square resistance of copper facing time change in 1-4 of the embodiment of the present invention.
Fig. 3 is that filter paper/Nanometer Copper laminated film SEM schemes (a) and energy spectrum diagram (b) in the embodiment of the present invention 2.
Fig. 4 is that cotton/Nanometer Copper conductive fabric SEM schemes (a) and energy spectrum diagram (b) in the embodiment of the present invention 2.
Fig. 5 is chitosan film/Nanometer Copper conductive composite film SEM figure in the embodiment of the present invention 5.
Fig. 6 is filter paper/Nanometer Copper laminated film resistance stability test chart in the embodiment of the present invention 3.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but not limited to this.
Embodiment 1
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml
In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching
Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the filter paper or cotton of agent are repeatedly washed with deionized water, it is impregnated in 5min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/
L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with metal
Filter paper or after cotton rinsed well with deionized water, be placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton reaction
The quality of front and back, and its resistance is tested with four probe sheet resistance testers.
Embodiment 2
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml
In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching
Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 10min in the plating solution of copper, plating solution by 12g/L NaOH,
13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with
After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton
The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 3
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml
In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching
Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 30min in the plating solution of copper, plating solution by 12g/L NaOH,
13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with
After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton
The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 4
Clip a certain size filter paper or cotton be soaked in dopamine/TrisHCl buffer (pH=8.5) of 1mg/ml
In, 6h is stirred under 300rpm revolving speed.After the resulting filter paper for being covered with poly-dopamine or cotton deionized water are repeatedly rinsed, leaching
Steep (the NH in 0.1mg/ml4)2PdCl4Aqueous solution in, stir 1h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the filter paper or cotton of agent are repeatedly washed with deionized water, be impregnated in 60min in the plating solution of copper, plating solution by 12g/L NaOH,
13g/L CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with
After the filter paper or cotton of metal are rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.Weigh filter paper and cotton
The quality of front and back is reacted, and tests its resistance with four probe sheet resistance testers.
Embodiment 5
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml
In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching
Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the chitosan film of agent is repeatedly washed with deionized water, it is impregnated in 5min in the plating solution of copper, plating solution is by 12g/L NaOH, 13g/L
CuSO4·5H2O, 29g/L sodium potassium tartrate tetrahydrate and reducing agent 9.5ml/L formaldehyde composition.After the reaction was completed, surface is coated with metal
After chitosan film is rinsed well with deionized water, it is placed in 50 DEG C of vacuum ovens dry.It is tested with four probe sheet resistance testers
Its resistance.
Embodiment 6
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml
In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching
Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the chitosan film of agent is repeatedly washed with deionized water, it is impregnated in 10min in the plating solution of nickel.After the reaction was completed, surface is coated with
After the chitosan film of metal is rinsed well with deionized water, its resistance is tested with four probe sheet resistance testers after drying at room temperature.
Embodiment 7
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml
In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching
Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the chitosan film of agent is repeatedly washed with deionized water, first it is impregnated in the plating solution for being impregnated in silver in the plating solution of copper after several seconds again
30min.After the reaction was completed, after the chitosan film that surface is coated with metal being rinsed well with deionized water, with four after drying at room temperature
Probe sheet resistance tester tests its resistance.
Embodiment 8
A certain size chitosan film of clip is soaked in dopamine/TrisHCl buffer (pH=8.5) of 2mg/ml
In, 12h is stirred under 300rpm revolving speed.After the resulting chitosan film for being covered with poly-dopamine is repeatedly rinsed with deionized water, leaching
Steep (the NH in 0.5mg/ml4)2PdCl4Aqueous solution in, stir 3h under 300rpm revolving speed.Metal catalytic is adsorbed with by resulting
After the chitosan film of agent is repeatedly washed with deionized water, first it is impregnated in the plating solution for being impregnated in gold in the plating solution of copper after several seconds again
30min.After the reaction was completed, after the chitosan film that surface is coated with metal being rinsed well with deionized water, with four after drying at room temperature
Probe sheet resistance tester tests its resistance.
Fig. 1 is the mass-change curve of filter paper and cotton with copper facing time change.As seen from the figure, with biomass-based bottom
The tenor of the extension of time in the plating solution, substrate surface plating is higher and higher.Illustrate that substrate surface can successfully adhere to gold
Metal catalyst, so as to successfully plate metal.
Fig. 2 filter paper and cotton change with the square resistance of copper facing time change.It can be seen from the figure that either filter paper is also
Cotton, with the extension of its time in metal plating liquid, square resistance is gradually reduced, the variance of surface square resistance by
It is decrescence small, illustrate that coating is more and more uniform.In conjunction with Fig. 1, illustrate to increase with the time, coat of metal progressive additive and gradually
It is even, cause resistance to be gradually reduced.It can reach 0.13 Ω/ when especially filter paper impregnates 10min in the plating solution, show that it is preferably led
Electrically.
Fig. 3 filter paper/Nanometer Copper laminated film SEM figure and energy spectrum diagram.It can be seen from the figure that the inner fiber of filter paper is equal
Metal nanoparticle is plated, illustrating filter paper, dipping is abundant when impregnating dopamine and subsequent metallic catalyst, to make
Subsequent surface metalation it is also abundant, this is the superior reason of its electric conductivity.And coating is uniform, this is surface resistive square
The lesser reason of difference.The surface known to energy spectrum diagram has plated one layer of copper particle.
Fig. 4 cotton/Nanometer Copper conductive fabric SEM figure and energy spectrum diagram.It can be seen from the figure that the inner fiber of filter paper is equal
Metal nanoparticle is plated, illustrating filter paper, dipping is abundant when impregnating dopamine and subsequent metallic catalyst, to make
Subsequent surface metalation it is also abundant, this is the superior reason of its electric conductivity.By the SEM of cotton and filter paper scheme comparison it is found that
The hole of cotton is more, fine and close not as good as filter paper, therefore to enter the time required inside cotton longer for plating solution.So to reach phase
Same electric conductivity, cotton are longer than the time needed for filter paper.
Fig. 5 chitosan film/Nanometer Copper conductive composite film SEM figure.As seen from the figure, the surface of chitosan film is equal
It is even to plate one layer of copper nano particles, and copper nano particles are uniform in size, arrangement is fine and close.Compared to filter paper and cotton, chitosan is thin
Film surface is more smooth, therefore the coating formed is also more smooth.
Fig. 6 filter paper/Nanometer Copper laminated film resistance stability test chart.As seen from the figure, conductive filter paper is in bending degree
Resistance hardly changes in the case where difference, and it is stronger to show that conductive layer is bonded with filter paper, conductive in curved situation
Layer will not fall off to will not influence its resistance variations.However in the case where multiple fold, because the folding strength of paper is limited,
After folding 50 times or more, paper has been broken, and discontinuous so as to cause conductive layer, resistance greatly improves.
The resistance value of conductive composite film in 1 embodiment 5-8 of table
As shown in Table 1, the resistance of the film of copper is minimum in deposition, may be comparatively fast related with the deposition velocity of copper.Therefore thin
Film needs the longer time to can be only achieved smaller resistance when depositing nickel, gold, silver.
Claims (10)
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| CN111827000A (en) * | 2020-08-04 | 2020-10-27 | 济南大学 | A copper composite conductive paper based on multi-site catalytic in-situ reduction technology |
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