CN108048824A

CN108048824A - A kind of preparation process at the dendritic interface of ionomer/metal

Info

Publication number: CN108048824A
Application number: CN201711344832.5A
Authority: CN
Inventors: 王延杰; 赵春; 朱灯林; 徐望舒; 骆敏舟
Original assignee: Changzhou Campus of Hohai University
Current assignee: Changzhou Campus of Hohai University
Priority date: 2017-12-15
Filing date: 2017-12-15
Publication date: 2018-05-18
Anticipated expiration: 2037-12-15
Also published as: CN108048824B; WO2019114011A1

Abstract

The invention discloses a kind of preparation processes at the dendritic interface of ionomer/metal, the technique is using ionomer as matrix membrane material, using metal composite as main salt, combined using physics roughening, chemical plating and plating and prepare the ionic polymer metal composite material with dendritic interface.The present invention is realized by following technology：Base film surface roughening treatment.In order to ensure roughened uniformity, using sandblasting, carried out under conditions of set time, fixation pressure and fixed sandblasting type.Chemical plating：Including two step processes of ion exchange and redox, which forms layer of surface electrode, reduces base film sheet resistance, and carrier is provided for follow-up plating.Plating：Present invention introduces electro-plating method be necessary condition that dendritic electrode interface is formed.Chemical plating joint electroplating technology ionomer/dendritic interface of metal proposed by the invention has efficient, at low cost advantage, and the effective contact area in the dendritic interface of ionomer/metal of preparation is big.

Description

A kind of preparation process at the dendritic interface of ionomer/metal

Technical field

The invention belongs to physical chemistry technical field, more particularly to a kind of preparation at the dendritic interface of ionomer/metal Technique.

Background technology

Ionomer (also known as solid polymer electrolyte) can realize the selection and conveying of ion.Ionomer With covalent phase and ion phase two phase structure, is covalently mutually made of-[C-C]-long-chain, ion phase is by being fixed on-[C-C]-long-chain The anion such as collateral sulfonic group, carboxylic acid group (or other cations) are formed.After ionomer absorbs water ,-[C-C]-is long The collateral fixed anion self-assemble of chain forms spherical ions cluster, is the aqueous solution for including cation among ion cluster, these from It is connected between submanifold by microchannel, forms solid-liquid two phase structure.If adhere to respectively in ionomer film upper and lower surface Double layer of metal electrode forms ionomer/metal composite membrane material.This membrane material under the action of voltage, dependent on from Ion cluster passage inside sub- thin polymer film, cationic (or other anion) is moved in film and can be realized turns from anode-side Move and be transported to cathode side.Since cation is unable to individualism, it is necessary to reference to several hydrones under water environment, and then formed Hydrated cation, therefore when substantial amounts of hydrated cation moves to cathode side, will certainly cause cathode side covalent phase (i.e.- [C-C]-long-chain) it is swollen, stretches.Since the reduction anode-side of a large amount of cations is present with shrinkage phenomenon.

Ionic polymer metal composite material (ion-exchange polymer metal composite, abbreviation IPMC) It is the new transductive material of one kind based on the exploitation of above-mentioned principle, which mainly passes through object in ionic polymer membranes upper and lower surface Reason or chemical method deposit the metals such as one layer of gold, platinum, silver, copper and are prepared.The basic transduction principle of IPMC materials is：When to When IPMC material upper and lower surfaces electrode applies voltage signal, displacement occurs under the action of electric field for removable ion, so as to Form the uneven distribution of through-thickness ion concentration；Since removable ion pair solvent molecule has drag interaction, material The barometric gradient of internal solvent molecule changes therewith.Under the collective effect of both effects, IPMC material ions concentration Higher one side expands with solvent pressure gradient, and opposite side is shunk, and then results in the flexural deformation of material.Conversely, work as When applying external force load to IPMC materials, material occurs bending and deformation first, i.e., one side expands, and opposite side is shunk, and causes material Internal stress distribution is uneven, and ion and solvent molecule are forced to redistribute, cause expansion one side ion increase, shrink one side from Son is reduced, and electrical potential difference is generated so as to cause between upper/lower electrode layer.IPMC materials have huge due to its unique transduction principle Application potential, there are all various aspects such as underwater, aerospace and medical biotechnology in its main application field.

In fact, the quaternary composite material that IPMC materials are made of base film, electrode, driving ion and solvent.It is based on The structure composition of IPMC materials, conversion efficiency depend on material matrix film (including in matrix film type, solvent and film Drive ionic species), electrode layer (including electrode type, penetrating into region and thickness) etc..At present, the preparation in relation to IPMC materials The exploitation of technique is unfolded mainly around above-mentioned factor.Earlier US scholar M.Shahinpoor applies earliest using chemical deposition side Method prepares the patent (US6109852) of this material.In the preparation method of disclosure, IPMC materials mainly utilize ionomer Ion exchange principle and platinum ammonia metal ion oxidation characteristic, be prepared by chemical plating process.It is prepared by this technique IPMC materials, interface present layered distribution.The platinum salt that this method uses is fairly expensive, and preparation method take it is longer by (one As more than 72h).Japanese scholars Kazuo Onishi are using Au composite as oxidant, sodium sulfite and sodium borohydride difference As reducing agent, a kind of ionomer/gold metallic composite is developed, interface is presented dendritic distribution, effectively increases The contact area of ionomer/metal, the conversion efficiency of IPMC materials show excellent (Kazuo Onishi et al.Electrochimica Acta 46(2000)737–743).But used Au composite is prohibitively expensive, and preparation method It takes longer (general one week or more).Chinese Xi'an Communications University scholar Chen Hualing ions based on similar preparation scheme application The patent (ZL200810150783.6) of polymer/palladium metal composite material uses palladium ammonium ion conduct in their technique Graininess distribution is presented in oxidant, the polymer/metal interface of prepared IPMC materials.Although palladium metal is dropped as electrode material Low cost, but material prepared by this technique, there is also some defects, first, under DC voltage effect, material becomes to anode There is larger relaxation deformation after shape again, this is unfavorable for the application as DC actuation device；Second is that in the case where exchanging electro ultrafiltration, become Shape ability is still limited；Third, manufacturing cycle is longer, it is less efficient.Then this preparation process is optimized in they, system For the IPMC materials with graininess distribution interface of large scale, and patent (ZL 201110085960.9) is applied for, but has deposited The problem of be not fully solved.

During IPMC material transducings, there are two important function for metal electrode tool：First, as on-load voltage, conduction electricity The carrier of stream；Second is that the capacitor that can accommodate certain quantity of electric charge is formed with interlayer.By above-mentioned exploration, scholar recognizes The quality of ionomer/metallic interfacial layer directly influences the conversion efficiency of IPMC materials.Presently, there are three kinds of polymer/ Metal interface, dendritic interface make the contact area with bigger between polymer/metal, and the performance of transducing characteristic is optimal.It is but existing Have that the preparation process at the dendritic interface of polymer/metal is complicated for operation, time-consuming, and used metal composite is expensive. Therefore, in view of the above-mentioned problems, applicant proposes that a kind of quick preparation has the preparation side of dendritic ionomer/metal interface Method, this method is at low cost, it is short to take, and the IPMC material conversion efficiency prepared is excellent.

The content of the invention

In order to solve the problems in the prior art, the present invention provides a kind of preparation at the dendritic interface of ionomer/metal Technique, the preparation process use physics roughening, chemical deposition and electro-plating method, and ionic polymer membranes inner surface is made to generate dendritic gold Belong to electrode, outer surface forms the metal layer of one layer of low-resistivity, which is mainly used for expanding ionomer/metal interface Contact area, improves the preparation efficiency of ionomer/metallic composite, and obtains the excellent IPMC materials of conversion efficiency. Ionomer involved by the technology is suitable for the solid polymer dielectric films such as Nafion, Aciplex, involved metal It is suitable for platinum, palladium, silver, copper etc..

To achieve the above object, the technical solution adopted by the present invention is：

A kind of preparation process at the dendritic interface of ionomer/metal, comprises the following steps：

The pretreatment of S1, base film：Surface roughening processing is carried out to base film, then carries out matrix Membrane cleaning；

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：Preparing metal complex solution will be immersed in dress by the base film of step S1 pretreatments Have in the beaker of metal complex solution, and beaker is placed in water bath with thermostatic control and is shaken, then take out base film, and retain residue Metal complex solution；

S202, redox：The mixed liquor of reducing agent and ammonium hydroxide is prepared, by the matrix Jing Guo step S201 cation exchanges Film is placed in deionized water the metal composite for rinsing repeatedly and several times, removing its adsorption, then base film is placed in equipped with also In the beaker of former agent and ammonia water mixture, and beaker is placed in water bath with thermostatic control and is shaken, make metal composite in base film from Son is reduced into metal, is deposited on surface and the inner surface of base film；It adds in and first time equivalent isoconcentration at regular intervals Reducing agent, after redox, take out base film, rinsed repeatedly several times with deionized water；

S3, pre-electroplating treatment, plating and plating post processing, including following three steps：

S301, pre-electroplating treatment：Remaining metal composite in step S201 will be put by the base film of step S202 It is impregnated in object solution, and retains remaining metal complex solution, taken out base film, rinsed 2-3 times, treated repeatedly with deionized water With obtaining the precursor at the dendritic interface of ionomer/metallic composite at this time；

Why metal complex solution is reused, be because passing through 1 soaking and reducing or plating, can not inhale completely Metal composite ion is received, metal complex solution needs Reusability, until metal composite Ions Absorption is complete.

S302, plating：Precursor is fixed on to the cathode side of electroplanting device, electroplanting device makees anode with titanium net, and array can The spring probe of compression contains the golden water of plated metal ion as electroplate liquid as cathode；Visit cathode side array of springs Pin and one side surface close contact of precursor；After the completion of precursor one side is electroplated, 302 are repeated the above steps, carry out precursor another side Plating；

S303, plating post processing：After the completion of the step S302 plating, to obtained ionomer/Metals composite Material carries out trimming processing, is impregnated with the driving ion aqueous slkali or salting liquid that concentration is 0.1~1N；Then take out ionic polymerization Object/metallic composite is rinsed repeatedly with deionized water；

S4, detection：Electron microscopic observation and performance test are carried out to the ionomer/metallic composite being prepared.

In the step S1, base film refers to solid polymer electrolyte, solid polymer electrolyte is Nafion membrane, Flemion films or Aciplex films.

In the step S1, the surface roughening processing of base film comprises the following steps：

S101, diameter range is used to carry out matrix film surface for 0.01-0.5 microns of glass sand or other hard materials Sandblasting, blasting pressure 0.05-0.5MPa, base film single side polish the time as 5-60s, and sand-blasting machine is in base film in bruting process Zigzag uniform motion is done on surface, trimming processing after the completion of polishing；

In the step S1, matrix Membrane cleaning comprises the following steps：

S102, it is cleaned by ultrasonic the impurity that matrix film surface is remained in removal roughening processing procedure：It will be beaten in step S101 Base film after mill trimming is placed in ultrasonic cleaning agent and is cleaned, and aqueous temperature during ultrasonic cleaning is 30-80 DEG C, power For 100-400W, scavenging period 10min-2h；

S103, hydrochloric acid boil the foreign ion washed away inside except base film, while the cation in base film is purified, Cation ic-converted for H⁺, increase H in base film⁺Content：The hydrochloric acid 200ml of 0.1-0.2mol/L is taken to be placed in beaker, in perseverance 100 DEG C are heated in tepidarium, then the base film being cleaned by ultrasonic by step S102 is placed in beaker and keeps hydrochloric acid It is boiled for 100 DEG C and washes 10min-2h；

S104, deionization boiling wash the storage capacity of increase ionomer/metallic composite：Step S103 will be passed through Hydrochloric acid, which boils the base film washed and is placed in 100 DEG C of deionized water to boil, washes 30min.

In the step S201, metal composite is in four ammino palladium of dichloro, tetraammineplatinum chloride, silver nitrate and copper sulphate Any one.

It is 0.0001- by being immersed in by the base film of step S1 pretreatments equipped with concentration in the step S201 In the beaker of 0.2mol/L metal complex solutions, and beaker sealing is placed in thermostatic water bath vibrator, concussion frequency is 10-120r/min, temperature are 30-80 DEG C, keep at least 1h.

When metal composite is copper sulphate, silver nitrate, then directly using metal complex solution, when metal composite is two Four ammino palladium of chlorine, tetraammineplatinum chloride then need to be formulated as the mixed liquor of metal composite and ammonium hydroxide, and the mass fraction of ammonium hydroxide is 25-28%, the concentration of metal composite is 0.0001-0.2mol/L, wherein adding in the volume of ammonium hydroxide and metal complex solution Ratio is 100:1-100:5.

In the step S202, reducing agent NaBH₄, concentration 0.01-5g/L, the mass concentration of ammonium hydroxide is 25- 28%, wherein, the volume ratio of ammonium hydroxide and reducing agent is 100:1-100:5.

In the step S202, the base film Jing Guo step S201 cation exchanges is initially positioned in deionized water and is cleaned 1-3 times, then be immersed in the beaker equipped with reducing agent and ammonia water mixture, beaker is then placed in thermostatic water bath vibrator In, concussion frequency is 10-120r/min, and temperature is 30-80 DEG C, keeps at least 1h.

Step S201 and S202 are repeated, until obtained base film sheet resistance is less than 1 Ω/, enters back into step S3.

In the step S301, soaking time 10min-3h.

In the step S302, electroplating parameter is specially：Electroplating voltage 0.5-10V, electric current 0.001-0.5A, electroplating time 5s-2min；In the step S302, the electroplating parameter on precursor two sides is consistent；Repeat step S301 and S302,5-7 times, then Enter step S303.

In the step S303, ionomer/metallic composite is first put into the hydrochloric acid that concentration is 0.1-2mol/L In, at least 1h is impregnated, then impregnates 30min-12h with the driving ion aqueous slkali or salting liquid that concentration is 0.1~1N；Its In：Aqueous slkali can be to contain alkali metal ions or other active metal ions, the alkali of organic cation such as Li ﹑ Na ﹑ Jia ﹑ Ru ﹑ caesiums Metallic solution, the concentration of aqueous slkali is 0.1-2mol/L；Salting liquid can be containing alkali metal ions such as Li ﹑ Na ﹑ Jia ﹑ Ru ﹑ caesiums or The salting liquid of other active metal ions, organic cation, the concentration of salting liquid is 0.1-2mol/L.

Compared with prior art, the invention has the advantages that：

1st, take short, efficient.Electro-plating method is introduced into the preparation process of IPMC materials by the present invention, on the one hand, electricity Electroplating method forms dendritic electrode structure in ionomer/metal interface, effectively increases IPMC materials sandwich layer/metal contact Area improves the conversion efficiency of material；On the other hand, the preparation of IPMC materials 48h is shorten to by least 72h originally can be complete Into shortening preparation time.

2nd, it is inexpensive.Present invention process step understands that operating method is simple, and metal composite used in the present invention is Common compound, such as four ammino palladium of dichloro, silver nitrate, copper sulphate etc., price is all than less expensive, the IPMC materials that finally prepare Driveability is excellent, has very strong practicability.

3rd, repeatability is strong.Each operating procedure of the invention gives detailed description, and reagent dosage also has specific mark Standard, technique have operability and repeatability.By test, have by IPMC materials made of this method compared with same type of material Superior performance.

Description of the drawings

Fig. 1 is the structure diagram of electroplanting device in the present invention；

Fig. 2 is the Cross Section Morphology of ionomer/palladium metal composite material prepared by the present invention；

Fig. 3 is the Cross Section Morphology of ionomer/platinum composite material prepared by the present invention；

Fig. 4 is the Cross Section Morphology of ionomer/silver metal composite material prepared by the present invention；

Fig. 5 is the Cross Section Morphology of ionomer/copper metal composite material prepared by the present invention；

Wherein：1- power supplys, 2- anodes, 3- cathodes, 4- metal composites cation, 5- ionomers/Metals composite Expect precursor, 6- electroplate liquids, 7- surface electrodes, 8- base films, the dendritic interfaces of 9-.

Specific embodiment

The present invention is further described with reference to embodiment.

As illustrated in fig. 1 and 2, electroplanting device, including power supply 1, anode 2 and cathode 3, anode is titanium net, and cathode is array Compressible spring probe, precursor are fixed on the cathode side of electroplanting device, contain the golden water of plated metal ion as plating Liquid；There are metal composite cation 4, polymer/metal composite material precursors 5 in ionomer/metallic composite precursor 5 Centre for base film 8, the one side of base film 8 is surface electrode 7, and opposite side forms dendritic interface 9.

Embodiment 1

The present embodiment by prepare size for 6cm × 6cm there is dendritic electrode interface IPMC materials exemplified by illustrate this The preparation process of invention, wherein：Base film uses Nafion membrane, and metal composite uses four ammino palladium of dichloro, is prepared For ionomer/palladium metal composite material, prepared dendritic interface metal type is palladium metal；

The pretreatment of S1, base film：

The surface roughening processing of S101, base film：Using Nafion membrane as base film, surface preparation uses the present embodiment Grit-blasting treatment process.The base film of one piece of 6.5cm*6.5cm, fixing base film are cut first, and exposing size is 6cm* 6cm；Sandblasting is carried out using the glass sand of 150#, blasting pressure is set as 0.2MPa, and the polishing of base film single side is controlled in 30s, and And sand-blasting machine does zigzag uniform motion in bruting process.After the completion of polishing, trimming processing.

The cleaning step of base film：

S102, ultrasonic cleaning：The step cleans base film using supersonic cleaning machine, primarily to removal is rough The impurity of matrix film surface is remained in during changing.Aqueous solution is first heated to 60 DEG C during ultrasonic cleaning, then simultaneously to matrix Cation in film is purified, cation ic-converted for H⁺, increase hydrionic content in base film and base film be put into it In, it is cleaned by ultrasonic instrument and is arranged to 60 DEG C, power 250W, scavenging period 30min.The instrument of film is pressed from both sides using nonconductive tweezer, with gold Belong to tweezers to compare, nonconductive tweezer has an advantage in that, it will not leave the marking on base film.Base film is being put into ultrasonic cleaning After in machine, numerous air-bubble generation is had on the surface of base film, before cleaning is started, the bubble for being attached to film surface is rinsed Fall, otherwise can reduce the quality of ultrasonic cleaning.

S103, hydrochloric acid, which boil, to be washed：This step is primarily to foreign ion inside removal base film, while in base film Cation purified, it is cation ic-converted be H⁺, increase hydrionic content in base film, contribute to soaking and reducing plated Ion-exchange reactions in journey.Hydrochloric acid boils the HCl washed using 0.2mol/L, measures 200ml and is put in beaker, in thermostatted water It is heated in bath close to 100 DEG C, the base film for then crossing surface clean, which is put into boil in beaker, washes 30min.

S104, deionization boiling are washed：This step is to increase the storage capacity of IPMC materials.It is in salt that deionization, which is boiled and washed, Acid, which boils, washes into rear progress, is specifically put into be heated to boiling in 100 DEG C of deionized water and washes 30min.

S2, reduction is exchanged：

Reduction is exchanged primarily to being pre-formed a bed boundary electrode in base film, while also in matrix film surface shape Into one layer of metal electrode layer, the surface conductivity of base film, the activation before being electroplated to base film are improved with this.

S201, cation exchange：This step uses the amount of palladium metal compound as single side 2.048mg/cm², palladium metal is multiple It is 0.01mol/L to close object concentration.Again because the size of this embodiment base film is 6cm*6cm, the dichloro four of 340mg is taken Ammino palladium, and the deionized water of 138ml is taken in beaker, 18ml ammonium hydroxide is added in, then the four ammino palladium of dichloro of weighing is poured into In beaker, then the base film pre-processed is put into beaker, beaker is sealed, is put into thermostatic water bath vibrator.If Surely it is 90r/min to shake frequency, and temperature is 50 DEG C, keeps 1h.

S202, redox：This step uses NaBH₄As reducing agent, concentration 0.85g/L.According to base film Size takes the deionized water of 200ml to be positioned in beaker, adds the ammonium hydroxide of 1ml, takes the NaBH of 7.5mg afterwards₄Add in beaker In, being put by the base film of step S201 after deionized water rinsing in beaker, beaker is then positioned over water bath with thermostatic control In oscillator, setting frequency is 90r/min, and temperature 50 C keeps 1h.Step S201 and S202 are repeated, until obtained matrix Film surface resistance is less than 1 Ω/, enters back into step S3.

S301, pre-electroplating treatment：Trimming processing is carried out to base film made from step S2, to prevent the upper following table of base film Face electric pole short circuit.Remaining metal complex solution and ammonium hydroxide in step S201 will be put by the base film of step S202 It is impregnated in mixed liquor, a length of 1h during immersion.

S302, plating：Base film is taken out, after being cleaned 2-3 times with deionized water, is fixed in electroplanting device (such as Fig. 1 It is shown) cathode side, which makees anode with titanium net, and the compressible spring probe of array contains coated metal as cathode The golden water of ion is as electroplate liquid.Make cathode side array spring probe and one side surface close contact of base film.Electroplating voltage 5V is arranged to, electric current is arranged to 0.05A, and electroplating time is arranged to 30s.The S302 that repeats the above steps after the completion of plating carries out matrix The plating of another side surface of film, electroplating parameter set constant.Repeat S301 and S302,5-7 times.

S303, plating post processing：After plating is completed, trimming processing is carried out to material, then IPMC materials are put into Immersion treatment, time 2h are carried out in 0.2mol/L sodium hydroxide solutions.IPMC materials are taken out, are rinsed repeatedly with deionized water.

S4, detection：Progress electron microscopic observation (as shown in Figure 2) to ionomer/palladium metal composite material of preparation and property It can test.

Embodiment 2

The present embodiment by prepare size for 6cm × 6cm there is dendritic electrode interface IPMC materials exemplified by illustrate this The preparation process of invention, wherein：Base film uses Nafion membrane, and metal composite uses tetraammineplatinum chloride, is prepared For ionomer/platinum composite material, prepared dendritic interface metal type is platinum；

The pretreatment of S1, base film：

The cleaning step of base film：

S2, reduction is exchanged：

S201, cation exchange：This step uses the amount of platinum compound as single side 3.75mg/cm², platinum is compound Object concentration is 0.01mol/L.Again because the size of this embodiment base film is 6cm*6cm, four ammonia of dichloro of 320mg is taken Platinum is closed, and takes the deionized water of 150ml in beaker, 20ml ammonium hydroxide is added in, the tetraammineplatinum chloride of weighing is then poured into burning In cup, then the base film pre-processed is put into beaker, beaker is sealed, is put into thermostatic water bath vibrator.Setting Concussion frequency is 90r/min, and temperature is 50 DEG C, keeps 1h.

S4, detection：Progress electron microscopic observation (as shown in Figure 3) to ionomer/platinum composite material of preparation and property It can test.

Embodiment 3

The present embodiment by prepare size for 6cm × 6cm there is dendritic electrode interface IPMC materials exemplified by illustrate this The preparation process of invention, wherein：Base film uses Nafion membrane, and metal composite uses silver nitrate, and it is ion to be prepared Polymer/silver metallic composite, prepared dendritic interface metal type are silver metal；

The pretreatment of S1, base film：

The cleaning step of base film：

S2, reduction is exchanged：

S201, cation exchange：Silver metal compound (silver nitrate) solution that concentration is 0.01mol/L is placed in beaker In, then the base film pre-processed is put into beaker, beaker is sealed, is put into thermostatic water bath vibrator.Setting concussion Frequency is 90r/min, and temperature is 50 DEG C, keeps 1h.

S301, pre-electroplating treatment：Trimming processing is carried out to base film made from step S2, to prevent the upper following table of base film Face electric pole short circuit.It is impregnated being put by the base film of step S202 in step S201 in remaining metal complex solution, A length of 1h during immersion.

S4, detection：Progress electron microscopic observation (as shown in Figure 4) to ionomer/silver metal composite material of preparation and property It can test.

Embodiment 4

The present embodiment by prepare size for 6cm × 6cm there is dendritic electrode interface IPMC materials exemplified by illustrate this The preparation process of invention, wherein：Base film uses Nafion membrane, and metal composite uses copper sulphate, and it is ion to be prepared Polymer/copper metal composite material, prepared dendritic interface metal type are copper metal；

The pretreatment of S1, base film：

The cleaning step of base film：

S2, reduction is exchanged：

S201, cation exchange：Compound concentration is 0.01mol/L copper metals compound (copper sulphate) solution, and is filled Enter in beaker, then the base film pre-processed is put into beaker, beaker is sealed, is put into thermostatic water bath vibrator. Concussion frequency is set as 90r/min, temperature is 50 DEG C, keeps 1h.

S4, detection：Progress electron microscopic observation (as shown in Figure 5) to ionomer/copper metal composite material of preparation and property It can test.

Embodiment 5

In the step S1, base film refers to solid polymer electrolyte, and solid polymer electrolyte uses Flemion Film.

S101, diameter range is used to carry out base film surface sand-blasting for 0.01 micron of glass sand, blasting pressure is 0.05MPa, base film single side polish the time as 5s, and sand-blasting machine does zigzag uniform motion in matrix film surface in bruting process, beats Trimming is handled after the completion of mill；

In the step S1, matrix Membrane cleaning comprises the following steps：

S102, it is cleaned by ultrasonic the impurity that matrix film surface is remained in removal roughening processing procedure：It will be beaten in step S101 Base film after mill trimming is placed in ultrasonic cleaning agent and is cleaned, and aqueous temperature during ultrasonic cleaning is 30-80 DEG C, power For 100W, scavenging period 10min；

S103, hydrochloric acid boil the foreign ion washed away inside except base film, while the cation in base film is purified, Cation ic-converted for H⁺, increase H in base film⁺Content：The hydrochloric acid 200ml of 0.1mol/L is taken to be placed in beaker, in thermostatted water 100 DEG C are heated in bath, it is 100 that then the base film being cleaned by ultrasonic by step S102, which is placed in beaker, and keeps hydrochloric acid It DEG C boils and to wash 10min；

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：It is 0.0001mol/L by being immersed in by the base film of step S1 pretreatments equipped with concentration In the beaker of metal complex solution (silver nitrate solution), and beaker sealing is placed in thermostatic water bath vibrator, concussion frequency Rate is 10r/min, and temperature is 30 DEG C, keeps at least 1h, then takes out base film, and retain residual metallic complex solution；

S202, redox：Prepare reducing agent NaBH₄With the mixed liquor of ammonium hydroxide, reducing agent NaBH₄Concentration is 0.01g/L, The mass concentration of ammonium hydroxide is 25%, and the volume ratio of ammonium hydroxide and reducing agent is 100 in mixed liquor:1, step S201 cations will be passed through The base film of exchange is placed in deionized water to be rinsed 1 time repeatedly, removes the metal composite of its adsorption, then base film is put In the beaker equipped with reducing agent and ammonia water mixture, and beaker is placed in water bath with thermostatic control and is shaken, concussion frequency is 10r/ Min, temperature are 30 DEG C, keep at least 1h, the metal composite ion in base film is made to be reduced into metal, is deposited on base film Surface and inner surface；The reducing agent with first time equivalent isoconcentration is added at regular intervals, after redox, is taken out Base film is rinsed 2 times repeatedly with deionized water；

S301, pre-electroplating treatment：Remaining metal composite in step S201 will be put by the base film of step S202 It is impregnated in object solution, soaking time 10min, and retains remaining metal complex solution, taken out base film, use deionized water It rinses 2 times repeatedly, for use, obtains the precursor at the dendritic interface of ionomer/metallic composite at this time；

Why metal complex solution is reused, be because passing through 1 soaking and reducing or plating, can not inhale completely Metal composite ion is received, metal complex solution needs Reusability, until metal composite Ions Absorption is complete；

S302, plating：Precursor is fixed on to the cathode side of electroplanting device, electroplanting device makees anode with titanium net, and array can The spring probe of compression contains the golden water of plated metal ion as electroplate liquid as cathode；Visit cathode side array of springs Pin and one side surface close contact of precursor；After the completion of precursor one side is electroplated, 302 are repeated the above steps, carry out precursor another side Plating；Electroplating parameter is specially：Electroplating voltage 0.5V, electric current 0.001A, electroplating time 5s；In the step S302, precursor two The electroplating parameter in face is consistent；Step S301 and S302 are repeated, 5 times, enters back into step S303；

S303, plating post processing：It is compound to obtained ionomer/silver metal after the completion of step S302 plating Material carries out trimming processing, is first put into ionomer/silver metal composite material in the hydrochloric acid that concentration is 0.1mol/L, impregnates Then at least 1h impregnates 30min with the driving ion sodium hydroxide solution that concentration is 0.1N；Then take out ionomer/silver Metallic composite is rinsed repeatedly with deionized water；

Embodiment 6

In the step S1, base film refers to solid polymer electrolyte, and solid polymer electrolyte uses Aciplex Film.

S101, diameter range is used to carry out base film surface sand-blasting for 0.3 micron of glass sand, blasting pressure is 0.3MPa, base film single side polish the time as 45s, and sand-blasting machine does zigzag uniform motion in matrix film surface in bruting process, beats Trimming is handled after the completion of mill；

In the step S1, matrix Membrane cleaning comprises the following steps：

S102, it is cleaned by ultrasonic the impurity that matrix film surface is remained in removal roughening processing procedure：It will be beaten in step S101 Base film after mill trimming is placed in ultrasonic cleaning agent and is cleaned, and aqueous temperature during ultrasonic cleaning is 50 DEG C, power is 300W, scavenging period 1h；

S103, hydrochloric acid boil the foreign ion washed away inside except base film, while the cation in base film is purified, Cation ic-converted for H⁺, increase H in base film⁺Content：The hydrochloric acid 200ml of 0.15mol/L is taken to be placed in beaker, in constant temperature 100 DEG C are heated in water-bath, the base film being cleaned by ultrasonic by step S102 then is placed in holding hydrochloric acid in beaker is 100 DEG C are boiled and wash 1h；

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：It is 0.2mol/L gold by being immersed in by the base film of step S1 pretreatments equipped with concentration In the beaker for belonging to complex solution (copper-bath), and beaker sealing is placed in thermostatic water bath vibrator, shakes frequency For 90r/min, temperature is 50 DEG C, keeps 2h, then takes out base film, and retain residual metallic complex solution；

S202, redox：Prepare reducing agent NaBH₄With the mixed liquor of ammonium hydroxide, reducing agent NaBH₄Concentration is 3g/L, ammonium hydroxide Mass concentration for 26%, the volume ratio of ammonium hydroxide and reducing agent is 100 in mixed liquor:3, step S201 cation exchanges will be passed through Base film be placed in deionized water and rinse repeatedly 2 times, remove the metal composite of its adsorption, then base film be placed in dress In the beaker for having reducing agent and ammonia water mixture, and beaker is placed in water bath with thermostatic control and is shaken, concussion frequency is 90r/min, warm It spends for 5 DEG C, keeps 2h, the metal composite ion in base film is made to be reduced into metal, be deposited on the surface of base film and interior Surface；The reducing agent with first time equivalent isoconcentration is added at regular intervals, after redox, is taken out base film, is used Deionized water is rinsed 3 times repeatedly；

S301, pre-electroplating treatment：Remaining metal composite in step S201 will be put by the base film of step S202 It is impregnated in object solution, soaking time 2h, and retains remaining metal complex solution, take out base film, it is anti-with deionized water It rinses 3 times again, for use, obtains the precursor at the dendritic interface of ionomer/metallic composite at this time；

S302, plating：Precursor is fixed on to the cathode side of electroplanting device, electroplanting device makees anode with titanium net, and array can The spring probe of compression contains the golden water of plated metal ion as electroplate liquid as cathode；Visit cathode side array of springs Pin and one side surface close contact of precursor；After the completion of precursor one side is electroplated, 302 are repeated the above steps, carry out precursor another side Plating；Electroplating parameter is specially：Electroplating voltage 5V, electric current 0.3A, electroplating time 1min；In the step S302, precursor two sides Electroplating parameter it is consistent；Step S301 and S302 are repeated, 6 times, enters back into step S303；

S303, plating post processing：It is compound to obtained ionomer/copper metal after the completion of step S302 plating Material carries out trimming processing, is first put into ionomer/copper metal composite material in the hydrochloric acid that concentration is 1mol/L, is dipped to Then few 1h impregnates 2h with the driving ion potassium hydroxide solution that concentration is 5N；It is compound then to take out ionomer/copper metal Material is rinsed repeatedly with deionized water；

S4, detection：Electron microscopic observation and performance test are carried out to the ionomer/copper metal composite material being prepared.

Embodiment 7

In the step S1, base film refers to solid polymer electrolyte, and solid polymer electrolyte uses Nafion membrane.

S101, diameter range is used to carry out base film surface sand-blasting for 0.5 micron of glass sand, blasting pressure is 0.5MPa, base film single side polish the time as 60s, and sand-blasting machine does zigzag uniform motion in matrix film surface in bruting process, beats Trimming is handled after the completion of mill；

In the step S1, matrix Membrane cleaning comprises the following steps：

S102, it is cleaned by ultrasonic the impurity that matrix film surface is remained in removal roughening processing procedure：It will be beaten in step S101 Base film after mill trimming is placed in ultrasonic cleaning agent and is cleaned, and aqueous temperature during ultrasonic cleaning is 80 DEG C, power is 400W, scavenging period 2h；

S103, hydrochloric acid boil the foreign ion washed away inside except base film, while the cation in base film is purified, Cation ic-converted for H⁺, increase H in base film⁺Content：The hydrochloric acid 200ml of 0.2mol/L is taken to be placed in beaker, in thermostatted water 100 DEG C are heated in bath, it is 100 that then the base film being cleaned by ultrasonic by step S102, which is placed in beaker, and keeps hydrochloric acid It DEG C boils and to wash 2h；

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：Preparing metal complex solution and ammonia water mixture take the dichloro that concentration is 0.2mol/L Four ammino palladium solution, mass fraction are 28% ammonium hydroxide, wherein：The volume ratio of four ammino palladium solution of dichloro and ammonium hydroxide is 100:5, It will be immersed in the beaker equipped with metal complex solution and ammonia water mixture by the base film of step S1 pretreatments, then will Beaker seals, and is placed in thermostatic water bath vibrator, and concussion frequency is 120r/min, and temperature is 80 DEG C, keeps at least 1h, with After take out base film, and retain residual metallic complex solution；

S202, redox：Prepare reducing agent NaBH₄With the mixed liquor of ammonium hydroxide, reducing agent NaBH₄Concentration is 5g/L, ammonium hydroxide Mass concentration for 28%, the volume ratio of ammonium hydroxide and reducing agent is 100 in mixed liquor:5, step S201 cation exchanges will be passed through Base film be placed in deionized water and rinse repeatedly 3 times, remove the metal composite of its adsorption, then base film be placed in dress In the beaker for having reducing agent and ammonia water mixture, and beaker is placed in water bath with thermostatic control and is shaken, concussion frequency is 120r/min, warm It spends for 80 DEG C, keeps at least 1h, the metal composite ion in base film is made to be reduced into metal, is deposited on the surface of base film And inner surface；The reducing agent with first time equivalent isoconcentration is added at regular intervals, after redox, takes out matrix Film is rinsed 3 times repeatedly with deionized water；

S301, pre-electroplating treatment：Remaining metal composite in step S201 will be put by the base film of step S202 It is impregnated in the mixed liquor of object solution and ammonium hydroxide, soaking time 3h, and retains the mixed of remaining metal complex solution and ammonium hydroxide Liquid is closed, base film is taken out, is rinsed repeatedly with deionized water 3 times, for use, obtain ionomer/metallic composite branch at this time The precursor at shape interface；

S302, plating：Precursor is fixed on to the cathode side of electroplanting device, electroplanting device makees anode with titanium net, and array can The spring probe of compression contains the golden water of plated metal ion as electroplate liquid as cathode；Visit cathode side array of springs Pin and one side surface close contact of precursor；After the completion of precursor one side is electroplated, 302 are repeated the above steps, carry out precursor another side Plating；Electroplating parameter is specially：Electroplating voltage 10V, electric current 0.5A, electroplating time 2min；In the step S302, precursor two sides Electroplating parameter it is consistent；Step S301 and S302 are repeated, 7 times, enters back into step S303；

S303, plating post processing：It is compound to obtained ionomer/palladium metal after the completion of step S302 plating Material carries out trimming processing, impregnates 12h with the driving ion sodium chloride solution that concentration is 0.1~1N；Then take out ionic polymerization Object/palladium metal composite material is rinsed repeatedly with deionized water；

S4, detection：Electron microscopic observation and performance test are carried out to the ionomer/palladium metal composite material being prepared.

Embodiment 8

In the step S1, matrix Membrane cleaning comprises the following steps：

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：Preparing metal complex solution and ammonia water mixture, it is 0.0001mol/L's to take concentration Four ammino palladium solution of dichloro, mass fraction are 25% ammonium hydroxide, wherein：The volume ratio of four ammino palladium solution of dichloro and ammonium hydroxide is 100:1, it will be immersed in by the base film of step S1 pretreatments in the beaker equipped with metal complex solution and ammonia water mixture, Then beaker is sealed, be placed in thermostatic water bath vibrator, concussion frequency is 120r/min, and temperature is 80 DEG C, is kept extremely Few 1h, then takes out base film, and retains residual metallic compound and ammonia water mixture；

S301, pre-electroplating treatment：Remaining metal composite in step S201 will be put by the base film of step S202 It is impregnated in the mixed liquor of object and ammonium hydroxide, soaking time 3h, and retains the mixed liquor of remaining metal composite and ammonium hydroxide, taken out Base film is rinsed 3 times with deionized water, repeatedly for use, before obtaining the dendritic interface of ionomer/metallic composite at this time Body；

Embodiment 9

In the step S1, matrix Membrane cleaning comprises the following steps：

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：Preparing metal complex solution and ammonia water mixture take the dichloro that concentration is 0.1mol/L Four ammino platinum solution, mass fraction are 26% ammonium hydroxide, wherein：The volume ratio of tetraammineplatinum chloride solution and ammonium hydroxide is 100:3, It will be immersed in the beaker equipped with metal complex solution and ammonia water mixture by the base film of step S1 pretreatments, then will Beaker seals, and is placed in thermostatic water bath vibrator, and concussion frequency is 120r/min, and temperature is 80 DEG C, keeps at least 1h, with After take out base film, and retain residual metallic complex solution；

The dendritic interface of ionomer/metal prepared by above-mentioned technical proposal can be not only used for ion-drive/sensing Field can also be applied to electrochemical capacitor and fuel cell field, and the use for these fields also should be regarded as this hair The scope of bright protection.

The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims

1. a kind of preparation process at the dendritic interface of ionomer/metal, which is characterized in that comprise the following steps：

S2, reduction is exchanged：Including following two steps：

S201, cation exchange：Preparing metal complex solution will be immersed in by the base film of step S1 pretreatments equipped with gold In the beaker for belonging to complex solution, and beaker is placed in water bath with thermostatic control and is shaken, then taken out base film, and retain residual metallic Complex solution；

S202, redox：The mixed liquor of reducing agent and ammonium hydroxide is prepared, the base film Jing Guo step S201 cation exchanges is put It rinses the metal composite for several times, removing its adsorption repeatedly in deionized water, then base film is placed in equipped with reducing agent In the beaker of ammonia water mixture, and beaker is placed in water bath with thermostatic control and is shaken, make the metal composite ion quilt in base film Metal is reduced into, is deposited on surface and the inner surface of base film；Addition at regular intervals is gone back with first time equivalent isoconcentration Former agent after redox, is taken out base film, is rinsed repeatedly several times with deionized water；

S301, pre-electroplating treatment：It is molten by remaining metal composite in step S201 is put by the base film of step S202 It is impregnated in liquid, and retains remaining metal complex solution, taken out base film, rinsed 2-3 times repeatedly with deionized water, for use, The precursor at the dendritic interface of ionomer/metallic composite is obtained at this time；

S302, plating：Precursor is fixed on to the cathode side of electroplanting device, electroplanting device makees anode with titanium net, and array is compressible Spring probe as cathode, contain the golden water of plated metal ion as electroplate liquid；Make cathode side array spring probe with One side surface close contact of precursor；After the completion of precursor one side is electroplated, 302 are repeated the above steps, carry out the plating of precursor another side；

S303, plating post processing：After the completion of step S302 plating, to obtained ionomer/metallic composite into Row trimming is handled, and is impregnated with the driving ion aqueous slkali or salting liquid that concentration is 0.1~1N；Subsequent taking-up ionomer/ Metallic composite is rinsed repeatedly with deionized water；

2. the preparation process at the dendritic interface of ionomer/metal according to claim 1, which is characterized in that

S101, base film surface sand-blasting, blasting pressure 0.05-0.5MPa, when base film single side is polished are carried out using glass sand Between for 5-60s, sand-blasting machine does zigzag uniform motion in matrix film surface in bruting process, after the completion of polishing trimming handle；

In the step S1, matrix Membrane cleaning comprises the following steps：

S102, it is cleaned by ultrasonic the impurity that matrix film surface is remained in removal roughening processing procedure：Polishing in step S101 is cut Base film behind side, which is placed in ultrasonic cleaning agent, to be cleaned, and aqueous temperature during ultrasonic cleaning is 30-80 DEG C, power is 100-400W, scavenging period 10min-2h；

S103, hydrochloric acid boil the foreign ion washed away inside except base film, while the cation in base film is purified, sun Ion conversion is H⁺, increase H in base film⁺Content：The hydrochloric acid 200ml of 0.1-0.2mol/L is taken to be placed in beaker, in thermostatted water 100 DEG C are heated in bath, it is 100 that then the base film being cleaned by ultrasonic by step S102, which is placed in beaker, and keeps hydrochloric acid It DEG C boils and to wash 10min-2h；

S104, deionization boiling wash the storage capacity of increase ionomer/metallic composite：Step S103 hydrochloric acid will be passed through It boils the base film washed and is placed in 100 DEG C of deionized water to boil and wash 30min.

3. the preparation process at the dendritic interface of ionomer/metal according to claim 2, which is characterized in that the step In rapid S201, metal composite is any one in four ammino palladium of dichloro, tetraammineplatinum chloride, silver nitrate and copper sulphate.

4. the preparation process at the dendritic interface of ionomer/metal according to claim 2, which is characterized in that the step It is 0.0001-0.2mol/L metal composites by being immersed in by the base film of step S1 pretreatments equipped with concentration in rapid S201 In the beaker of solution, and beaker sealing is placed in thermostatic water bath vibrator, concussion frequency is 10-120r/min, and temperature is 30-80 DEG C, keep at least 1h.

5. the preparation process at the dendritic interface of ionomer/metal according to claim 2, which is characterized in that the step In rapid S202, reducing agent NaBH₄, concentration 0.01-5g/L, the mass concentration of ammonium hydroxide is 25-28%, wherein, ammonium hydroxide with The volume ratio of reducing agent is 100:1-100:5.

6. the preparation process at the dendritic interface of ionomer/metal according to claim 2, which is characterized in that the step In rapid S202, the base film Jing Guo step S201 cation exchanges is initially positioned in deionized water and is cleaned 1-3 times, then is soaked Then bubble is placed in beaker in thermostatic water bath vibrator in the beaker equipped with reducing agent and ammonia water mixture, concussion frequency is 10-120r/min, temperature are 30-80 DEG C, keep at least 1h.

7. the preparation process at the dendritic interface of ionomer/metal according to claim 2, which is characterized in that repeat to walk Rapid S201 and S202, until obtained base film sheet resistance is less than 1 Ω/, enters back into step S3.

8. the preparation process at the dendritic interface of ionomer/metal according to claim 1, which is characterized in that the step In rapid S301, soaking time 10min-3h.

9. the preparation process at the dendritic interface of ionomer/metal according to claim 1, which is characterized in that the step In rapid S302, electroplating parameter is specially：Electroplating voltage 0.5-10V, electric current 0.001-0.5A, electroplating time 5s-2min；The step In rapid S302, the electroplating parameter on precursor two sides is consistent；Step S301 and S302 are repeated, 5-7 times, enters back into step S303.

10. the preparation process at the dendritic interface of ionomer/metal according to claim 1, which is characterized in that the step In rapid S303, first ionomer/metallic composite is put into the hydrochloric acid that concentration is 0.1-2mol/L, impregnates at least 1h, Then 30min-12h is impregnated with the driving ion aqueous slkali or salting liquid that concentration is 0.1~1N.