CN104878433A - Preparation method of ionic conducting polymer film - Google Patents
Preparation method of ionic conducting polymer film Download PDFInfo
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- CN104878433A CN104878433A CN201510234183.8A CN201510234183A CN104878433A CN 104878433 A CN104878433 A CN 104878433A CN 201510234183 A CN201510234183 A CN 201510234183A CN 104878433 A CN104878433 A CN 104878433A
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Abstract
The invention discloses a preparation method of an ionic conducting polymer film. The preparation method comprises the following steps: firstly pretreating an electrode, and then dissolving an ionic polymer into a polar organic solvent to prepare an ionic polymer solution; adjusting a pH value of the ionic polymer solution by adding acid or alkali; then adjusting the deposition velocity of the ionic polymer by controlling the voltage and deposition time of a voltage-stabilized and current-stabilized power supply; removing the electrode, and drying to obtain the electrode with the ionic polymer deposited on the surface; and finally soaking the electrode into deionized water, then peeling an ionic conducting polymer film from the electrode surface, and soaking the ionic conducting polymer film into dilute H2SO4. The preparation method disclosed by the invention is low in cost, short in time consumption and simple in device, can be used for reducing the consumption of organic solvents, and is beneficial to environmental protection; and by adjusting the electrophoretic deposition time, the voltage and the concentration of the ionic polymer, the thickness and surface morphology of the film can be simply and effectively controlled, and the ionic conducting ability of the film in a vertical direction can be adjusted.
Description
Technical field
The present invention relates to technical field prepared by ionic conductive polymer membrane, particularly a kind of preparation method of ionic conductive polymer membrane.
Background technology
The general method preparing polymeric film comprises solution casting method, extrusion by melting.
Solution casting method masking required equipment is simple, easily operates, but needs to carry out strict control to each factor.Such as, for obtaining the uniform film of thickness, need the region to being separated to control, otherwise finally obtain be not film but powder or foam.In addition, Gu temperature, mold material and condition of surface can by affect liquid/, gas/liquid interfacial tension affects polymers soln and sprawls on-chip, the concentration of polymers soln, the molecular weight of superpolymer, solvent, system temperature also can affect polymers soln in on-chip mobility.
If there is no suitable solvent as organic polymer film-casting liquid, then extrusion by melting to be adopted to carry out film forming.Melt extruded membrane formation process is suitable for continuous prodution, does not use solvent in film process, but equipment, operation all more complicated.
In recent years, make charged colloidal particles generation displacement by electric field action and receive increasing concern at the electrophoretic deposition method of electrode surface discharge formation settled layer.Ionic conductive polymer to dissociate and charged at polar solvent, and under electric field action, charged ionic conductive polymer can move to charged contrary electrode surface, enrichment, completes sol-gel transition, and drying forms film.
Compared with preparing film with solution casting method, extrusion by melting, electrophoretic deposition required equipment and operating process are all simpler.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of preparation method of ionic conductive polymer membrane, overcoming in prior art and preparing polymeric film complex process, problem that cost is high.
Technical scheme of the present invention is: a kind of preparation method of ionic conductive polymer membrane, comprises the steps:
(1) pre-treatment of electrode: process electrode surface with polishing machine, makes electrode surface smooth, smooth; The electrode processed is put into successively dehydrated alcohol, deionized water for ultrasonic cleaning;
(2) preparation of ionomer solution: ionic polymer is dissolved in polar organic solvent, then adds deionized water, be made into ionomer solution; By solution magnetic agitation, and excessively filter residue, finally ultrasonic again; Add the pH of acid or alkali adjustment ionomer solution;
(3) ionic polymer is in the deposition of electrode surface: be connected on current regulator power supply by wire by the electrode of process in two panels (1); The ionomer solution of getting preparation in (2) is added in electrolyzer, inserts in electrolyzer by above-mentioned two electrodes; Switch on power, regulated the sedimentation velocity of ionic polymer by the voltage and depositing time controlling current regulator power supply; Take out electrode and drying, obtain the electrode that surface is deposited by ionic polymer;
(4) aftertreatment of ionic conductive polymer membrane: electrode is put into deionized water and soaks, then ionic conductive polymer membrane is peeled off from electrode surface, and put into rare H
2sO
4middle immersion, finally puts into deionized water and soaks stand-by.
Electrode described in step (1) is metal electrode, Graphite Electrodes or conductive glass.
Polar organic solvent described in step (2) is one or more in dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE.
Acid described in step (2) is the one in hydrochloric acid, formic acid, acetic acid, lactic acid, sulfuric acid, nitric acid.
Alkali described in step (2) is the one in sodium hydroxide, potassium hydroxide, triethylamine, thanomin, ammoniacal liquor, trolamine.
The mass percent of the effects of ion polymkeric substance described in step (2) is 1.5% ~ 5%.
Described in step (2), the pH of telomerized polymer solution is 1.2 ~ 9.0.
Electrode voltage described in step (3) is 10 ~ 25V, and the electrophoretic deposition time is 20 ~ 75min.
Beneficial effect of the present invention is:
(1) cost is low, and consuming time short, device is simple;
(2) reduce organic solvent usage quantity, be conducive to protection of the environment;
(3) by regulating the concentration of time of electrophoretic deposition, voltage and ionic polymer, can the thickness of simple and effective controlling diaphragm and surface topography, regulate the Vertical dimension ion conductivity of film.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail.
The ionic polymer adopted in the present invention to be sulfonation degree be 65% sulfonated polyether-ether-ketone and sulfonation degree be 70% sulfonation phenolic polyether sulphone.
Embodiment 1
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g dimethyl sulfoxide (DMSO), then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=2.4 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 75min under 15V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: the sulfonated polyether-ether-ketone of 0.45g is dissolved in 15.75g dimethyl sulfoxide (DMSO), then adds 1.80g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 107um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.143189S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 108um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.101473S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 41.1%.
Embodiment 2
The step that electrophoretic deposition prepares ionic conductive polymer membrane is as follows:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g N,N-DIMETHYLACETAMIDE, then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=2.9 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 25min under 25V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: the sulfonated polyether-ether-ketone of 0.45g is dissolved in 15.75g N,N-DIMETHYLACETAMIDE, then adds 1.80g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 107um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.123724S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 108um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.101473S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 21.9%.
Embodiment 3
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g N-Methyl pyrrolidone, then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=2.4 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 60min under 25V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: the sulfonated polyether-ether-ketone of 0.32g is dissolved in 11.20g N-Methyl pyrrolidone, then adds 1.28g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 78um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.113923S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 76um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.138564S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition reduces 17.8%.
Embodiment 4
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g dimethyl formamide, then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=3.0 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 30min under 20V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: the sulfonated polyether-ether-ketone of 0.35g is dissolved in 12.80g dimethyl formamide, then adds 1.40g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 87um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.096323S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 78um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.101233S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition reduces 4.8%.
Embodiment 5
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 1.2g sulfonated polyether-ether-ketone is dissolved in 70.8g dimethyl sulfoxide (DMSO), then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 1.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=2.6 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 60min under 20V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: the sulfonated polyether-ether-ketone of 0.45g is dissolved in 26.55g dimethyl sulfoxide (DMSO), then adds 3.00g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 105um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.105095S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 110um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.100132S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 4%.
Embodiment 6
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 4g sulfonated polyether-ether-ketone is dissolved in 70g dimethyl sulfoxide (DMSO), then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered, and sulfonated polyether-ether-ketone pH value of solution=2.3 obtained.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to join in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 20min under 20V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, and step is as follows: be dissolved in the dimethyl sulfoxide (DMSO) of 7.65g by the sulfonated polyether-ether-ketone of 0.45g, then adds 0.90g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 107um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.107847S.cm
-1.Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 109um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.100973S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 6.8%.
Embodiment 7
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g dimethyl sulfoxide (DMSO), then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation suspension 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered; Add massfraction be 36% glacial acetic acid regulate sulfonated polyether-ether-ketone solution to make its pH=1.2.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 30min under 20V voltage; Take out electrode drying at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, step is as follows: the sulfonated polyether-ether-ketone of 0.45g is dissolved in 15.75g dimethyl sulfoxide (DMSO), add 1.80g water, add massfraction be 36% glacial acetic acid regulate sulfonated polyether-ether-ketone solution to make its pH=1.2; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; By solution on a glass, dry at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 106um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.096201S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 108um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.095431S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 0.8%.
Embodiment 8
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) 2g sulfonated polyether-ether-ketone is dissolved in 70g dimethyl sulfoxide (DMSO), then adds the deionized water of 8g, be made into the solution that sulfonated polyether-ether-ketone mass percent is 2.5%; Magnetic agitation suspension 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonated polyether-ether-ketone solution filtered; Add massfraction be 25% ammoniacal liquor regulate sulfonated polyether-ether-ketone solution to make its pH=9.0.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonated polyether-ether-ketone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 40min under 20V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonated polyether-ether-ketone film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonated polyether-ether-ketone film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonated polyether-ether-ketone film prepared by solution casting method, step is as follows: the sulfonated polyether-ether-ketone of 0.45g is dissolved in 15.75g dimethyl sulfoxide (DMSO), add 1.80g water, add massfraction be 25% ammoniacal liquor regulate sulfonated polyether-ether-ketone solution to make its pH=9.0; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; By solution on a glass, dry at 100 DEG C; Sulfonated polyether-ether-ketone film is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonated polyether-ether-ketone film thickness prepared by electrophoretic deposition is 107um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.096201S.cm
-1; Sulfonated polyether-ether-ketone film thickness prepared by solution casting method is 105um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.089643S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 7.3%.
Embodiment 9
It is as follows that electrophoretic deposition prepares ionic conductive polymer membrane step:
(1) with polishing machine by long 6cm, the stainless steel substrates polishing of wide 4cm, thick 0.5mm, until smooth surface is as minute surface; Stainless steel substrates is put into successively dehydrated alcohol, deionized water ultrasonic cleaning 15min;
(2) be dissolved in 70g dimethyl formamide by 2g sulfonation phenolic polyether sulphone, then add the deionized water of 8g, being made into sulfonation phenolic polyether sulphone mass percent is the solution of 2.5%; Magnetic agitation solution 24h, crosses and filters non-dissolved residue, by the ultrasonic 15min of sulfonation phenolic polyether sulphone solution filtered, the pH=7.1 of gained solution.
(3) by wire, two panels stainless steel electrode is connected on current regulator power supply; Get 50g sulfonation phenolic polyether sulphone solution to be added in long 6.8cm, wide 2.5cm, high 5cm electrolyzer, stainless steel electrode is inserted in electrolyzer; Switch on power, control the voltage of current regulator power supply, electrophoretic deposition 30min under 20V voltage; Take out electrode to dry at 100 DEG C, obtain the electrode that surface is deposited by ionic polymer.
(4) aftertreatment of sulfonation phenolphthalein type poly (ether sulfone) film: stainless steel substrates is put into deionized water and soaks 30min, then peels off sulfonation phenolphthalein type poly (ether sulfone) film from electrode surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water soak stand-by.
Comparative example is sulfonation phenolphthalein type poly (ether sulfone) film prepared by solution casting method, and step is as follows: the sulfonation phenolic polyether sulphone of 0.45g is dissolved in 15.75g dimethyl formamide, then adds 1.80g water; By solution magnetic agitation 24h, and cross and filter residue, finally ultrasonic 15min again; Solution is dried on a glass at 100 DEG C; Sulfonation phenolic polyether sulphone is peeled off from glass surface, and puts into the H of 1mol/L
2sO
4soak 48h, then put into deionized water and soak stand-by.
Sulfonation phenolphthalein type poly (ether sulfone) film thickness prepared by electrophoretic deposition is 103um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.024902S.cm
-1; Sulfonation phenolphthalein type poly (ether sulfone) film thickness prepared by solution casting method is 110um; 70 DEG C, under RH=100% condition, the Vertical dimension proton conductivity of film is 0.024875S.cm
-1.Compared with solution casting method, the electric conductivity of film prepared by electrophoretic deposition improves 0.1%.
Claims (8)
1. a preparation method for ionic conductive polymer membrane, is characterized in that comprising the steps:
(1) pre-treatment of electrode: process electrode surface with polishing machine, makes electrode surface smooth, smooth; The electrode processed is put into successively dehydrated alcohol, deionized water for ultrasonic cleaning;
(2) preparation of ionomer solution: ionic polymer is dissolved in polar organic solvent, then adds deionized water, be made into ionomer solution; By solution magnetic agitation, and excessively filter residue, finally ultrasonic again; Add the pH of acid or alkali adjustment ionomer solution;
(3) ionic polymer is in the deposition of electrode surface: be connected on current regulator power supply by wire by the electrode of process in two panels (1); The ionomer solution of getting preparation in (2) is added in electrolyzer, inserts in electrolyzer by above-mentioned two electrodes; Switch on power, regulated the sedimentation velocity of ionic polymer by the voltage and depositing time controlling current regulator power supply; Take out electrode and drying, obtain the electrode that surface is deposited by ionic polymer;
(4) aftertreatment of ionic conductive polymer membrane: electrode is put into deionized water and soaks, then ionic conductive polymer membrane is peeled off from electrode surface, and put into rare H
2sO
4middle immersion, finally puts into deionized water and soaks stand-by.
2. the preparation method of ionic conductive polymer membrane according to claim 1, is characterized in that the electrode described in step (1) is metal electrode, Graphite Electrodes or conductive glass.
3. the preparation method of ionic conductive polymer membrane according to claim 1, the polar organic solvent that it is characterized in that described in step (2) is one or more in dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE.
4. the preparation method of ionic conductive polymer membrane according to claim 1, is characterized in that the acid described in step (2) is the one in hydrochloric acid, formic acid, acetic acid, lactic acid, sulfuric acid, nitric acid.
5. the preparation method of ionic conductive polymer membrane according to claim 1, is characterized in that the alkali described in step (2) is the one in sodium hydroxide, potassium hydroxide, triethylamine, thanomin, ammoniacal liquor, trolamine.
6. the preparation method of ionic conductive polymer membrane according to claim 1, is characterized in that the mass percent of the effects of ion polymkeric substance described in step (2) is 1.5% ~ 5%.
7. the preparation method of ionic conductive polymer membrane according to claim 1, is characterized in that the pH of telomerized polymer solution described in step (2) is 1.2 ~ 9.0.
8. the preparation method of ionic conductive polymer membrane according to claim 1, it is characterized in that the electrode voltage described in step (3) is 10 ~ 25V, the electrophoretic deposition time is 20 ~ 75min.
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