CN103871753B - The preparation method of hydrophilic graphene thin film - Google Patents
The preparation method of hydrophilic graphene thin film Download PDFInfo
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- CN103871753B CN103871753B CN201410065935.8A CN201410065935A CN103871753B CN 103871753 B CN103871753 B CN 103871753B CN 201410065935 A CN201410065935 A CN 201410065935A CN 103871753 B CN103871753 B CN 103871753B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses the preparation method of hydrophilic graphene thin film, it comprises the following steps: is added by graphene oxide powder in deionized water, ultrasonic disperse, obtains graphene oxide suspension；Iron powder, hydrochloric acid solution are added in graphene oxide suspension, stands after being stirred at room temperature；In mixed liquor, addition hydrochloric acid solution is until iron powder is removed completely, filters and separates, and cleans for several times with deionized water and ethanol solution, takes out product in baking oven after drying；In product, add sulfonating agent, clean up with deionized water, vacuum be collected by filtration after again ultrasonic disperse in water, add reducing agent, filtration washing, vacuum drying obtains hydrophilic graphene powder；In hydrophilic graphene powder, add graphite powder and politef, be mixed, by, in pressed disc method pressing graphene paper, obtaining hydrophilic graphene membrane electrode.The present invention increases the hydrophilic of graphene film by reducing the contact angle of Graphene, improves its ability in terms of capacitive deionization.
Description
Technical field
The present invention relates to the preparation method of graphene film, be specifically related to the preparation method of a kind of hydrophilic graphene thin film.
Background technology
Capacitive deionization is a kind of emerging desalination technology, and the charged ion in solution is removed in the electro-adsorption effect produced under DC electric field effect mainly by porous electrode material, the feature such as have that efficiency is high, pollution-free and energy consumption is low.According to its basic functional principle, ideal capacitance adsorption electrode high-specific surface area to be possessed, good electric conductivity, sizeable pore structure and excellent wettability (Oren Y. Capacitive
deionization (CDI) for desalination and water treatment—past, present and future
(a review) [J]. Desalination, 2008,228 (1): 10-29.).Current most of CDI is to include carbon silica aerogel electrode based on material with carbon element, activate carbon, ordered mesopore carbon, CNT and Graphene etc..
Graphene, be a kind of by carbon atom with sp2Hybrid orbital composition hexangle type is the flat film of honeycomb lattice, has up to 2630 m2The room-temperature conductivity of the Theoretical Area of/g, 7200 S/m and bigger mechanical strength (Novoselov K S, Geim
A K, Morozov S V, et al. Electric field effect in
Atomically thin carbon films [J]. science, 2004,306 (5696): 666-669.), Yang et al. is 92.5 through the water contact angle of experiment discovery single-layer graphene o, this character seriously limits its hydrophilic and the performance at capacitive deionization thereof.Koratkar et al. finds to use the roughness on control graphene film surface and surface chemistry can adjust the contact angle of Graphene by research thus increases its hydrophilic (Rafiee J, Rafiee
M A, Yu Z Z, et al. Superhydrophobic
to superhydrophilic wetting control in graphene films[J]. Advanced materials, 2010, 22(19):
2151-2154.).
Summary of the invention
It is an object of the invention to: the preparation method of a kind of hydrophilic graphene thin film is provided, increase the hydrophilic of graphene film by reducing the contact angle of Graphene, improve its ability in terms of capacitive deionization.
The technical solution of the present invention is that it comprises the following steps:
(1) graphene oxide powder is added in deionized water according to mass ratio 1:100 ~ 1000, ultrasonic disperse 0.5 ~ 2h, obtain finely dispersed graphene oxide suspension；
(2) 0.1 ~ 5g iron powder, 5 ~ 100 mL mass fraction 5% ~ 50% hydrochloric acid solutions being added in the graphene oxide suspension of steps 1, room temperature mechanical stirs and stands 1h after 60 min；
(3) in the mixed liquor of step 2, continuously add mass fraction 5% ~ 50% hydrochloric acid solution until iron powder therein is removed completely, filter and separate, and clean for several times with deionized water and ethanol solution, be placed in temperature 433K baking oven after being dried 6 h and take out；
(4) in the product of step 3, sulfonating agent is added according to mass ratio 1:1 ~ 10, and place it in taking-up after 2 h in ice bath, clean up with deionized water, vacuum be collected by filtration after again ultrasonic disperse in water, continuously stirred 12 h under the conditions of reducing agent is placed on 473K are added again according to mass ratio 1:1 ~ 10, filtration washing, vacuum drying obtains hydrophilic graphene powder；Described sulfonating agent is benzenesulfonic acid diazol or Sodium styrene sulfonate, and reducing agent is sodium borohydride or hydrazine hydrate；
(5) in hydrophilic graphene powder, add graphite powder and politef, be mixed, be pressed in graphene paper by pressed disc method, obtain hydrophilic graphene membrane electrode；Wherein, being 60% to the mass fraction of hydrophilic graphene powder, the mass fraction of graphite powder is 30%, and the mass fraction of politef is 10%.
The invention have the advantage that and reduce the contact angle of graphene film by controlling to introduce sour sulfur acidic group group, increase Graphene wettability and specific surface area, improve the hydrophilic of Graphene, capacitive deionization ability is strong and non-secondary pollution；By introducing sulfonic acid group, the water contact angle of the graphene film after sulfonation is by original 79.3oDrop to 39.5o, specific surface area also increases 55% than the thin film of the most sulfonated mistake；Being applied on ultracapacitor by graphene film, the efficiency of capacitive deionization has reached 83.4%, and capacitive adsorption amount increases to 8.6 mg/g, and is 40% without sulfonated capacitive deionization efficiency, and capacitive adsorption amount is 4.1 mg/g；The graphene film after the comparative illustration of these parameters is sulfonated capability improving on capacitive deionization 109%, the graphene film obtained by this method has preferable development potentiality in thin film ultracapacitor deionization field.
Accompanying drawing explanation
Graphene contact angle sulfonated for Fig. 1 and the comparison diagram without sulfonated contact angle.
Fig. 2 hydrophilic graphene membrane electrode and without sulfonated graphene membrane electrode to Na in solution+The comparison diagram of electro-adsorption.
Detailed description of the invention
Further illustrate the technical solution of the present invention below in conjunction with specific embodiment, these embodiments are not to be construed as the restriction to technical scheme.
Embodiment 1 :20g graphene oxide powder is joined in 2000 mL deionized waters, ultrasonic disperse 0.5h, obtain finely dispersed graphene oxide suspension；Take 0.1 g iron powder, the hydrochloric acid solution of 5mL mass fraction 15% adds in the beaker filling graphene oxide suspension, stands 1h under room temperature condition after mechanical agitation 60 min；Continue to add mass fraction be the hydrochloric acid solution of 15% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6 h, taking-up product be divided into two parts standby；A product adds 1g sulfonating agent benzenesulfonic acid diazol and places it in 2 h in ice bath, taking-up deionized water cleans up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 3g borane reducing agent sodium hydride is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 3g sodium borohydride is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；By 6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, it is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；By the graphene powder of 6g unsulfonated adds 3g graphite powder and 1g politef, it is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 2 :20g graphene oxide powder is joined in 10000mL deionized water, ultrasonic disperse 1h, obtain finely dispersed graphene oxide suspension；0.6g iron powder, the hydrochloric acid solution of 20ml mass fraction 25% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 25% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6 h, be divided into after taking-up product two parts standby；A product adds 3g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 24 h under the conditions of 1g reducing agent hydrazine hydrate is placed on 373K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 1g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 3 :20g graphene oxide powder is joined in 6000mL deionized water, ultrasonic disperse 2h, obtain finely dispersed graphene oxide suspension；1.5g iron powder, the hydrochloric acid solution of 10ml mass fraction 20% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 20% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6 h, be divided into after taking-up product two parts standby；A product adds 10g sulfonating agent benzenesulfonic acid diazol and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 5g borane reducing agent sodium hydride is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 5g borane reducing agent sodium hydride is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 4 :20g graphene oxide powder is joined in 4000mL deionized water, ultrasonic disperse 1.5 h, obtain finely dispersed graphene oxide suspension；5g iron powder, the hydrochloric acid solution of 100mL mass fraction 50% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 50% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 5g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 10g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 10g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 5 :20g graphene oxide powder is joined in 20000mL deionized water, ultrasonic disperse 1.5 h, obtain finely dispersed graphene oxide suspension；3.8g iron powder, the hydrochloric acid solution of 25ml mass fraction 5% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 5% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6 h, be divided into after taking-up product two parts standby；A product adds 3g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；By 6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, it is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；Unsulfonated by 6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, be pressed in graphene paper by pressed disc method, obtain the most sulfonated graphene membrane electrode.
Embodiment 6 :20g graphene oxide powder is joined in 8000mL deionized water, ultrasonic disperse 2 h, obtain finely dispersed graphene oxide suspension；4 g iron powder, the hydrochloric acid solution of 60mL mass fraction 30% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 30% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 5g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 6g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 7 :20g graphene oxide powder is joined in 12000mL deionized water, ultrasonic disperse 1.5 h, obtain finely dispersed graphene oxide suspension；4.8g iron powder, the hydrochloric acid solution of 75mL mass fraction 40% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 40% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 1g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 9g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 9g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 8 :20g graphene oxide powder is joined in 14000mL deionized water, ultrasonic disperse 1h, obtain finely dispersed graphene oxide suspension；0.5g iron powder, the hydrochloric acid solution of 15mL mass fraction 35% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 35% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 6g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 3g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 3g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 9 :20g graphene oxide powder is joined in 9000mL deionized water, ultrasonic disperse 0.5 h, obtain finely dispersed graphene oxide suspension；0.3g iron powder, the hydrochloric acid solution of 30mL mass fraction 10% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 10% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 2g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 10 :20g graphene oxide powder is joined in 11000mL deionized water, ultrasonic disperse 1 h, obtain finely dispersed graphene oxide suspension；2.5 g iron powder, the hydrochloric acid solution of 70mL mass fraction 35% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 35% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 4g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 9g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 9g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 11 :20g graphene oxide powder is joined in 8000mL deionized water, ultrasonic disperse 1.5 h, obtain finely dispersed graphene oxide suspension；2.6 g iron powder, the hydrochloric acid solution of 60mL mass fraction 30% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 30% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 5g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 6g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 12 :20g graphene oxide powder is joined in 16000mL deionized water, ultrasonic disperse 0.5 h, obtain finely dispersed graphene oxide suspension；0.6 g iron powder, the hydrochloric acid solution of 80mL mass fraction 45% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 45% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 7g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 8g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 13 :20g graphene oxide powder is joined in 18000mL deionized water, ultrasonic disperse 1 h, obtain finely dispersed graphene oxide suspension；3 g iron powder, the hydrochloric acid solution of 15mL mass fraction 40% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 40% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 2g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 14 :20g graphene oxide powder is joined in 6000mL deionized water, ultrasonic disperse 0.5 h, obtain finely dispersed graphene oxide suspension；1.6 g iron powder, the hydrochloric acid solution of 35mL mass fraction 15% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 15% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 6g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 6g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 6g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 15 :20g graphene oxide powder is joined in 20000mL deionized water, ultrasonic disperse 1.5 h, obtain finely dispersed graphene oxide suspension；2.5 g iron powder, the hydrochloric acid solution of 75mL mass fraction 25% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 25% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 2g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
Embodiment 16 :20g graphene oxide powder is joined in 3000mL deionized water, ultrasonic disperse 2 h, obtain finely dispersed graphene oxide suspension；3.5 g iron powder, the hydrochloric acid solution of 90mL mass fraction 45% add in the beaker filling scattered graphene oxide suspension, stand 1h under room temperature condition after mechanical agitation 60 min；Continue to add the hydrochloric acid solution of mass fraction 45% until the iron powder in beaker is removed completely, filter to separate and also clean for several times with deionized water and ethanol solution, be placed in the baking oven of 433K and be dried 6h, be divided into after taking-up product two parts standby；A product adds 9g sulfonating agent Sodium styrene sulfonate and places it in 2 h in ice bath, clean up with deionized water after taking-up, vacuum be collected by filtration after again ultrasonic disperse in water, add continuously stirred 12 h under the conditions of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing, vacuum drying obtains hydrophilic graphene powder；Adding continuously stirred 12 h under the conditions of the direct-reduction of 4g reducing agent hydrazine hydrate is placed on 473K, filtration washing in another part of product, vacuum drying obtains the graphene powder of unsulfonated；6g hydrophilic graphene powder adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains hydrophilic graphene membrane electrode；The 6g hydrophilic graphene powder of unsulfonated adds 3g graphite powder and 1g politef, is pressed in graphene paper by pressed disc method, obtains the most sulfonated graphene membrane electrode.
The hydrophilic graphene membrane electrode of embodiment 1-16 gained and the most sulfonated graphene membrane electrode are as shown in Figure 1, 2, Graphene contact angle sulfonated for Fig. 1 (a) and Fig. 1 (b) without the comparison diagram of sulfonated contact angle, Fig. 2 (a) hydrophilic graphene membrane electrode and Fig. 2 (b) without sulfonated graphene membrane electrode to Na in solution+The comparison diagram of electro-adsorption.
Claims (1)
1. the preparation method of hydrophilic graphene thin film, is characterized in that: it comprises the following steps:
(1) graphene oxide powder is added in deionized water according to mass ratio 1:100 ~ 1000, ultrasonic disperse 0.5 ~ 2h, obtain finely dispersed graphene oxide suspension；
(2) 0.1 ~ 5g iron powder, 5 ~ 100 mL mass fraction 5% ~ 50% hydrochloric acid solutions being added in the graphene oxide suspension of steps 1, room temperature mechanical stirs and stands 1h after 60 min；
(3) in the mixed liquor of step 2, continuously add mass fraction 5% ~ 50% hydrochloric acid solution until iron powder therein is removed completely, filter and separate, and clean for several times with deionized water and ethanol solution, be placed in temperature 433K baking oven after being dried 6 h and take out；
(4) in the product of step 3, sulfonating agent is added according to mass ratio 1:1 ~ 10, and place it in taking-up after 2 h in ice bath, clean up with deionized water, vacuum be collected by filtration after again ultrasonic disperse in water, continuously stirred 12 h under the conditions of reducing agent is placed on 473K are added again according to mass ratio 1:1 ~ 10, filtration washing, vacuum drying obtains hydrophilic graphene powder；Described sulfonating agent is benzenesulfonic acid diazol or Sodium styrene sulfonate, and reducing agent is sodium borohydride or hydrazine hydrate；
(5) in hydrophilic graphene powder, add graphite powder and politef, be mixed, be pressed in graphene paper by pressed disc method, obtain hydrophilic graphene membrane electrode；Wherein, the mass fraction of hydrophilic graphene powder is 60%, and the mass fraction of graphite powder is 30%, and the mass fraction of politef is 10%.
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