CN107687002B - A kind of activated cathode of doped graphene and preparation method thereof - Google Patents
A kind of activated cathode of doped graphene and preparation method thereof Download PDFInfo
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- CN107687002B CN107687002B CN201710708185.5A CN201710708185A CN107687002B CN 107687002 B CN107687002 B CN 107687002B CN 201710708185 A CN201710708185 A CN 201710708185A CN 107687002 B CN107687002 B CN 107687002B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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Abstract
The purpose of the present invention is to provide activated cathodes of a kind of doped graphene and preparation method thereof, it is characterized by: being cathode masking liquid by the graphene coated mixed solution with the one or more of ruthenium trichloride, cerous chloride, nickel chloride, chloroplatinic acid of pretreated nickel metal base surface, with salt acid for adjusting pH, the nickel metal after coating carries out thermal decomposition process until nickel metal surface metal oxide gain in weight reaches 5-30g/m2, obtain required activated cathode.The activated cathode can be applied in chlor-alkali ion-exchange membrane electrolyzer, and single machine energy consumption is further decreased, and improve single machine production capacity, and stability is good, have the longer industrial application service life.
Description
Technical field
The invention belongs to electrochemical technology fields, especially provide a kind of chlorine industry ion-exchange membrane electrolyzer activity yin
Pole and preparation method thereof.
Background technique
With (zero) film pole span close in the preparation process of dimensionally stable anode (DSA), chlor-alkali ion-exchange membrane electrolyzer
The continuous development and application of the technologies such as Flexible cathodes, the tank voltage of the analysis chlorine overpotential, ion-exchange membrane electrolyzer that make anode is not
It is disconnected to reduce, but the theoretical decomposition voltage 2.19V for forming chlorine and sodium hydroxide with water with chloride ion has a certain gap, current
Practical tank voltage is generally in 3.0V or more, and as electrolytic current density is by 4KA/m2It is increased to 8KA/m2, it is suitable for before low
The activated cathode of current density has been not fully appropriate in chlorine industry production, if wanting to obtain, energy-saving effect is more preferable, single machine
The higher ion-exchange membrane electrolyzer of production capacity, a kind of low overpotential of hydrogen evolution, high catalytic activity resist strong reverse current impact, iron-resistant
The development of the long-life activated cathode of the impurity such as ion poisoning will be the important channel for realizing above-mentioned target.
The common preparation method of existing activated cathode is usually to be electroplated or be coated with periodic table of elements VIII group on Ni substrate
Middle cobalt, nickel, ruthenium, rhodium, palladium, iridium, in one or several metal salt solution and the periodic table of elements in platinum in lanthanide series metal
Lanthanum, cerium, one or several metal salt in praseodymium mixed solution, the activity yin of corresponding active layer is prepared by thermal decomposition method
Pole.In order to improve activated cathode hydrogen evolution activity and it is anti-power-off and reverse current impact capacity, publication number: CN 101029405A
Patent, corresponding activated cathode has been prepared according to above-mentioned related process, but the binding force of source/drain and matrix is poor, sternly
Ghost image rings the service life of cathode；Publication number: the patent of CN 1265432A, by increasing between Ni substrate and active coating
Nickel oxide interlayer enhances the binding force of matrix and active layer, but the ability of its anti-reflective to rush of current is very weak.Prior art
Binding force is poor, the service life is short, anti-reflective is poor to rush of current ability, easily with formula lower activated cathode more or less all the existing prepared
The problems such as iron ion is poisoned.
Graphene is a kind of crystal structure of bi-dimensional cellular shape being made of carbon atom, there is the big pi bond of delocalization inside it,
And electronics can move freely inside it, and graphene is made to have good electric conductivity, and maximum conductivity is 10 at present6S/m；
Graphene is material most firm in current all material, and wear-resisting property is fabulous；At room temperature, graphene thermal conductivity with higher
Rate；Graphene also has very high specific surface area, is 2630m2g-1, the biggish specific surface area of graphene is conducive to the height of particle
Dispersion, excellent electric conductivity are conducive to transfer of the electronics from nanoparticle to graphene base body in electrochemical process, are conducive to press down
The active particle in electrochemical process is made to occur to reunite and form passivating film.The present invention is namely based on the above-mentioned characteristic of graphene,
It is entrained in activated cathode masking liquid, to prepare more resistant to iron ion and reverse current, high electric rate, the length of low hydrogen-evolution overpotential
Life activities cathode.
Summary of the invention
The purpose of the present invention is to provide activated cathodes of a kind of doped graphene and preparation method thereof, using party's legal system
Standby activated cathode can be applied in chlor-alkali ion-exchange membrane electrolyzer, and single machine energy consumption is further decreased, and improve single machine and produce
Can, especially suitable for chlor-alkali production activated cathode under high current density.
The present invention has the advantages that the present invention is good, chemical using high conductivity, high-specific surface area, the wearability of graphene
The features such as property is stablized, graphene dispersion is entrained in transition metal, the work of doped graphene is prepared for by thermal decomposition method
Property cathode, coating surface specific surface area with higher, good wearability, under high current density, have it is lower
Hydrogen-evolution overpotential resists strong reverse current, the poisoning of iron-resistant ion, the features such as stability is good, has the longer industrial application service life.
Technical solution of the present invention is as follows:
A kind of activated cathode of doped graphene, it is characterised in that: be coated with by pretreated nickel metal base surface
Cathode masking liquid, the cathode masking liquid are the one or more of graphene and ruthenium trichloride, cerous chloride, nickel chloride, chloroplatinic acid
Mixed solution adjusts its pH with hydrochloric acid；Nickel metal after coating is subjected to thermal decomposition process until nickel metal surface metal aoxidizes
Object gain in weight reaches 5-30g/m2, obtain required activated cathode.The nickel metallic matrix is preferably nickel mesh grid or nickel seine.
The present invention provides the preparation methods of the activated cathode of the doped graphene, it is characterised in that: the activity yin
The main process for preparing of pole includes metallic matrix pretreatment, the cathode masking liquid preparation of doped graphene, pre-treated metal surface painting
Cloth cathode masking liquid, thermal decomposition process.
Metallic matrix pretreatment: carrying out oil removal treatment for nickel metal lye and distilled water, then carry out blasting treatment,
At 50-90 DEG C, processing 1-15 minutes is carved with the Nacl sour of 10-25%, nickel metal weightlessness is made to reach 2-50g/m2, after taking-up
It is rinsed with lye, distilled water and is dried at 100 DEG C, it is stand-by after room temperature is cooling.
The cathode masking liquid of doped graphene is prepared: graphene is added to containing 50-180g/L ruthenium trichloride, 15-60g/L
In the mixed solution of the one or more of cerous chloride, 20-70g/L nickel chloride, 45-150g/L chloroplatinic acid, made with hydrochloric acid adjusting
Its pH < 0.5 keeps the concentration of graphene at 0.05-1.0g/L (preferably 0.3-0.6g/L)；By the cathode masking liquid of doped graphene
Room temperature ultrasound 0.5-3 hours, until until graphene is completely dispersed into mixed solution.By the doped graphene cathode of different component
Masking liquid is successively coated, and mixing cathode masking liquid will be ultrasonically treated before coating every time, and each coating process will be controlled 1
Within hour.
As a preferred option, the different doped graphene cathode masking liquid of three groups of components need to be prepared, and successively by each group yin
Pole masking liquid is coated on nickel metallic matrix: where the metal salt that must contain in first group of cathode masking liquid has nickel chloride and chlorine platinum
Acid, concentration are nickel chloride 20-70g/L, chloroplatinic acid 45-150g/L, and coated nickel metallic matrix is sintered 20 points at 450 DEG C
Clock；Second group of cathode masking liquid is without particular/special requirement；The metal salt that third group cathode masking liquid must contain has ruthenium trichloride, and concentration is
Coated nickel metallic matrix is sintered 30 minutes by 50-180g/L at 200 DEG C.
Thermal decomposition process: the cathode masking liquid of doped graphene is uniformly coated on by pretreated nickel metallic matrix,
Nickel metallic matrix after coating is dried into 10-30min at 100-150 DEG C, is sintered 20-60 minutes at 200-600 DEG C later,
Room temperature is cooling after taking-up, it is repeatedly above-mentioned coat, dry, sintering process, until nickel metal surface metal oxide gain in weight reaches
5-30g/m2, obtain required activated cathode.
Detailed description of the invention
Activated cathode apparent form of the Fig. 1 undoped with graphene.
The activated cathode apparent form of Fig. 2 doped graphene.
Specific embodiment
Embodiment 1
Nickel metal pretreatment: carrying out oil removal treatment for nickel mesh grid lye and distilled water, then carry out blasting treatment,
At 65-80 DEG C, with handling about 5 minutes at 15% Nacl sour quarter, nickel mesh grid weightlessness is made to reach 9g/m2, alkali is used after taking-up
Liquid, distilled water are rinsed and dry at 100 DEG C, stand-by after room temperature is cooling.
Masking liquid and activated cathode preparation: the cathode masking liquid of matched doped graphene is both needed to salt acid for adjusting pH < 0.5, room temperature
Ultrasound 1 hour, is dispersed in graphene uniform in mixed solution.
By graphene be added to containing 50g/L nickel chloride, 50g/L chloroplatinic acid mixed solution in, keep the dense of graphene
Degree is coated on the masking liquid as the first component by drying 10 points at 150 DEG C in pretreated nickel mesh grid in 0.35g/L
Clock, after taking-up 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 2-3 times；Then graphene is added to
Containing 110g/L ruthenium trichloride, 35g/L cerous chloride, 25g/L nickel chloride mixed solution in, keep the concentration of graphene to exist
0.55g/L, it is 10 minutes dry at 150 DEG C in the nickel mesh grid after which is coated on above-mentioned coating as the second component, it takes
After out 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 8-12 times；Graphene is finally entrained in 50g/
It in L ruthenium trichloride, keeps the concentration of graphene in 0.6/L, is coated on using the masking liquid as third component and is covered with above-mentioned two-wheeled painting
It is 10 minutes dry at 150 DEG C in the nickel mesh grid of the coating of cloth, it is sintered 30 minutes after taking-up at 200 DEG C, above-mentioned painting repeatedly
Cloth, drying, sintering process 2-3 times, until nickel metal on metal oxide gain in weight reaches 12.5-13.0g/m2, preparation completion.
Embodiment 2
Nickel metal pretreatment process is the same as embodiment 1.
Masking liquid and activated cathode preparation: matched solution is both needed to salt acid for adjusting pH < 0.5, the catholyte compartment of doped graphene
Warm ultrasound 1 hour, is dispersed in graphene uniform in mixed solution.
By graphene be added to containing 40g/L nickel chloride, 45g/L chloroplatinic acid mixed solution in, keep the dense of graphene
Degree is coated on the masking liquid as the first component by drying 10 points at 150 DEG C in pretreated nickel mesh grid in 0.3g/L
Clock, after taking-up 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 5-6 times；Then graphene is added to
Containing 80g/L ruthenium trichloride, 25g/L cerous chloride, 20g/L nickel chloride, 50g/L chloroplatinic acid mixed solution in, keep graphite
The concentration of alkene is in 0.55g/L, dry at 150 DEG C in the nickel mesh grid after which is coated on above-mentioned coating as the second component
Dry 10 minutes, after taking-up 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 8-12 times；Finally by graphite
Alkene is entrained in 55g/L ruthenium trichloride, keeps the concentration of graphene in 0.4g/L, which is coated on as third component and is covered
It is 10 minutes dry at 150 DEG C in the nickel mesh grid for having the coating of above-mentioned two-wheeled coating, 30 points are sintered at 200 DEG C after taking-up
Clock, it is repeatedly above-mentioned be coated and dried, sintering process 5-6 times.Cathode masking liquid is coated on nickel metallic matrix until its metal aoxidizes
Object gain in weight reaches 20.5-21.0g/m2, preparation completion.
Embodiment 3
For nickel metal pretreatment with embodiment 1, difference is not carry out the grouping masking liquid coating of three components, activated cathode preparation process
It is as follows:
Graphene be added to containing 110g/L ruthenium trichloride, 35g/L cerous chloride, 25g/L nickel chloride mixed solution in,
Keep the concentration of graphene in 0.55g/L, which be coated in nickel mesh grid, it is 10 minutes dry at 150 DEG C, after taking-up
450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 12-18 times, until nickel mesh grid on metal oxide increase
Weight reaches 12.5-13.0g/m2, preparation completion.
Embodiment 4
Nickel metal pretreatment process adjusts the content of graphene in each component in cathode masking liquid, remaining cathode with embodiment 1
Masking liquid component is the same as embodiment 2.
Masking liquid and activated cathode preparation: matched solution is both needed to salt acid for adjusting pH < 0.5, the catholyte compartment of doped graphene
Warm ultrasound 1 hour, is dispersed in graphene uniform in mixed solution.
By graphene be added to containing 40g/L nickel chloride, 45g/L chloroplatinic acid mixed solution in, keep the dense of graphene
Degree is coated on the masking liquid as the first component by drying 10 points at 150 DEG C in pretreated nickel mesh grid in 0.36g/L
Clock, after taking-up 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 2-3 times；Then graphene is added to
Containing 80g/L ruthenium trichloride, 25g/L cerous chloride, 20g/L nickel chloride, 50g/L chloroplatinic acid mixed solution in, keep graphite
The concentration of alkene is in 0.66g/L, dry at 150 DEG C in the nickel mesh grid after which is coated on above-mentioned coating as the second component
Dry 10 minutes, after taking-up 450 DEG C be sintered 20 minutes, it is repeatedly above-mentioned be coated and dried, sintering process 8-12 times；Finally by graphite
Alkene is entrained in 55g/L ruthenium trichloride, is kept the concentration of graphene in 0.48g/L, is coated on using the masking liquid as third component
It is covered in the nickel mesh grid of the coating of above-mentioned two-wheeled coating, it is 10 minutes dry at 150 DEG C, 30 are sintered at 200 DEG C after taking-up
Minute, it is repeatedly above-mentioned be coated and dried, sintering process 2-3 times.Cathode masking liquid is coated on nickel metal until its metal oxide
Gain in weight reaches 12.5-13.0g/m2, preparation completion.
Comparative example 1
Nickel metal pretreatment, cathode preparation process are the same as embodiment 1.Stone is free of in cathode masking liquid unlike the first embodiment
Black alkene, the composition and content of remaining component are the same as embodiment 1.Finally until nickel metal surface metal oxide gain in weight reaches
12.5-13.0g/m2, preparation completion.
Comparative example 2
Nickel metal pretreatment, cathode preparation process are the same as embodiment 2.Stone is free of in cathode masking liquid as different from Example 2
Black alkene, the composition and content of remaining component are the same as embodiment 2.Finally until nickel metal surface metal oxide gain in weight reaches
20.5-21.0g/m2, preparation completion.
The performance test of activated cathode:
1. hydrogen-evolution overpotential: in 11mol/L NaOH solution, 90 ± 2 DEG C, 3KA/m2、5KA/m2、8KA/m2Under current density,
After continuous electrolysis 720h, using activated cathode as working electrode, saturated calomel electrode is reference electrode, and nickel plate is to carry out electricity to electrode
Bit test；
2. powering off polarization test: in 11mol/L NaOH solution, 90 ± 2 DEG C, 5KA/m2It is sun with nickel plate under current density
Pole, activated cathode are that cathode carries out 720h polarization test, and wherein electrolytic process powers off 12 times altogether, every time pause 1 hour, test analysis
Hydrogen potential；
3. anti-reflective is tested to rush of current: in 11mol/L NaOH solution, 90 ± 2 DEG C, 200A/m2Under current density, electricity
Solution 0.5 hour adds up to carry out 12 times, and using activated cathode as anode, nickel plate is that cathode carries out polarization test, tests hydrogen-evolution overpotential；
4. the poisoning test of iron-resistant ion: in 11mol/L NaOH solution (wherein containing the Fe of 0.04mg/L3+), 90 ± 2 DEG C,
5KA/m2Under current density, using nickel plate as anode, activated cathode is that cathode is tested, and tests hydrogen-evolution overpotential.
The embodiment and comparative example of above-mentioned preparation is tested according to the above test method, obtains following result:
1 activated cathode hydrogen-evolution overpotential of table
In conjunction with 1 data of table, can be obtained by embodiment 1-2 and comparative example 1-2, under identical preparation condition, doped graphite
The activated cathode of alkene hydrogen-evolution overpotential more initial than the activated cathode of undoped graphene low 50-60mV under different current densities, and
After being electrolysed 720h, current potential elevation amplitude is also less than the activated cathode undoped with graphene；Pass through embodiment 1 and embodiment 3
It can be concluded that grouping point coating is lower than not being grouped point activated cathode hydrogen-evolution overpotential of coating preparation, it is coated with by third component
Activated cathode still there are part graphenes on surface after heat treatment, greatly improve the electric conductivity on surface, illustrate grouping apply
Cloth can be effectively improved the surface conductivity of activated cathode and the binding force of coating and matrix；It can by embodiment 2 and embodiment 4
To find out, hydrogen-evolution overpotential can not be effectively reduced in the content for increasing graphene in active masking liquid, be increased slightly instead, excessive to increase
The content of graphene can cause to cover to active layer surface instead, and then reduce hydrogen evolution activity, pass through embodiment 1-2 and comparative example
After 1-4 can be seen that doped graphene and grouping point coating, activated cathode has biggish electrode activation area and lesser electricity
Lotus transfer resistance greatly improves the conductivity and binding force of cathode surface, further illustrates doped graphite in the present embodiment
The activated cathode of alkene has better catalytic activity for hydrogen evolution and stability.
Table 2 is in 5KA/m2Under current density, add up electrolytic polarization after 720 hours, hydrogen-evolution overpotential situation of change, wherein electricity
Solution preocess powers off 12 times altogether, every time pause 1 hour.
The polarization of 2 different activities catholyte of table
In conjunction with 2 data of table, by power-off experiment as can be seen that the hydrogen-evolution overpotential of the activated cathode of doped graphene is not mixed than
The activated cathode of miscellaneous graphene wants low, and grouping coating further enhances the anti-cut-off capacity of activated cathode of doped graphene.
Amplify 5000 times by field emission electron flying-spot microscope, compared the activated cathode (Fig. 1) undoped with graphene
With the apparent form of the activated cathode (Fig. 2) of doped graphene.
By the comparison of Fig. 1 and Fig. 2, the active cathode surface degree of grain refinement of doped graphene is significantly better than undoped
The active cathode surface of graphene keeps the uniformity of cathode surface higher, can be effectively reduced actual current density, prevents part
Current density is excessive, causes the falling off from point to surface of coating, effectively extends the service life of electrode.
Anti-reflective is tested to rush of current: in 11mol NaOH solution, 90 ± 2 DEG C, and 200A/m2Under current density, electrolysis 0.5
Hour, add up to carry out 12 times, using activated cathode as anode, nickel plate is that cathode carries out polarization test, tests hydrogen-evolution overpotential；
3 reverse current impact experiment of table
By table 3 it is found that the ability of the anti-reverse current of the activated cathode of doped graphene than undoped graphene work
Property cathode hydrogen-evolution overpotential elevation amplitude after reverse electrolysis is small, is tested by reverse current, still further it can be seen that doped graphene
Activated cathode has very strong anti-reflective to current capacity, this is because metallic is in matrix surface by the doping of graphene
Be distributed it is more uniform, have better electrochemical stability, make electric current active layer surface be distributed it is more uniform, and then inhibit live
Property layer because caused by change in polarity Large area coatings fall off.
Iron-resistant ion poisoning test: in 11mol NaOH solution (wherein containing the Fe of 0.04mg/L3+), 90 ± 2 DEG C, 5KA/
m2Under current density, using nickel plate as anode, activated cathode is that cathode carries out polarization test, tests hydrogen-evolution overpotential, and statistics display is mixed
Equal conditions are free of Fe in the hydrogen-evolution overpotential contrast table 1 of the activated cathode of miscellaneous graphene3+Electrolyte electrolysis hydrogen-evolution overpotential, wave
Dynamic amplitude is 2% or so, and the activated cathode fluctuating range undoped with graphene is in 8-10% or so, due to the doping of graphene,
In matrix and active layer and active layer surface, refine the crystal grain of metallic more, surface tends to uniformly, and graphene has
Good chemical stability, and then inhibit Fe3+To the poisoning effect of activated cathode.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of activated cathode of doped graphene, it is characterised in that: by pretreated nickel metal base surface coating yin
Pole masking liquid, the cathode masking liquid are the mixed of the one or more of graphene and ruthenium trichloride, cerous chloride, nickel chloride, chloroplatinic acid
Solution is closed, adjusts its pH with hydrochloric acid；Nickel metal after coating is subjected to thermal decomposition process until nickel metal surface metal oxide
Gain in weight reaches 5-30g/m2, obtain required activated cathode；
The different doped graphene cathode masking liquid of three groups of components is prepared, and each group cathode masking liquid is successively coated on nickel metallic matrix
On, the metal salt that must contain in first group of cathode masking liquid has nickel chloride and chloroplatinic acid, and concentration is nickel chloride 20-70g/L, chlorine
Platinic acid 45-150g/L will apply the nickel metallic matrix made and be sintered 20 minutes at 450 DEG C；Third group cathode masking liquid must contain
Metal salt has ruthenium trichloride, and concentration 50-180g/L will apply the nickel metallic matrix made and be sintered 30 minutes at 200 DEG C；It will not
Doped graphene cathode masking liquid with component is successively coated, and mixing cathode masking liquid will carry out ultrasonic place before coating every time
Reason, each coating process will be controlled within an hour.
2. according to the activated cathode of doped graphene described in claim 1, it is characterised in that: the nickel metallic matrix is nickel braiding
Net or nickel seine.
3. a kind of preparation method of the activated cathode of doped graphene described in claim 1, it is characterised in that: the activated cathode
Preparation process include metallic matrix pretreatment, doped graphene cathode masking liquid prepare, pre-treated metal surface coated cathode
Masking liquid, thermal decomposition process.
4. the preparation method of the activated cathode according to doped graphene described in claim 3, it is characterised in that: metallic matrix is located in advance
Then reason carries out blasting treatment, at 50-90 DEG C, uses 10-25% for nickel metal lye and distilled water are carried out oil removal treatment
Nacl sour carve processing 1-15 minutes, so that nickel metal weightlessness is reached 2-50g/m2, rushed after taking-up with lye, distilled water
It washes and is dried at 100 DEG C, it is stand-by after room temperature is cooling.
5. the preparation method of the activated cathode according to doped graphene described in claim 3, it is characterised in that: doped graphene
The preparation of cathode masking liquid is: graphene is added to containing 50-180g/L ruthenium trichloride, 15-60g/L cerous chloride, 20-70g/L
In the mixed solution of the one or more of nickel chloride, 45-150g/L chloroplatinic acid, makes its pH < 0.5 with hydrochloric acid adjusting, keep graphite
The concentration of alkene is in 0.05-1.0g/L, by cathode masking liquid room temperature ultrasound 0.5-3 hours of doped graphene, until graphene divides completely
Until being scattered in mixed solution.
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