CN107687002A - 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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- CN107687002A CN107687002A CN201710708185.5A CN201710708185A CN107687002A CN 107687002 A CN107687002 A CN 107687002A CN 201710708185 A CN201710708185 A CN 201710708185A CN 107687002 A CN107687002 A CN 107687002A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
Abstract
It is an object of the invention to provide a kind of activated cathode of doped graphene and preparation method thereof, it is characterised in that：The nickel metal base surface by pretreatment it is graphene coated with ruthenium trichloride, the mixed solutions of the one or more of cerous chloride, nickel chloride, chloroplatinic acid be negative electrode masking liquid, 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, that is, required activated cathode is made.The activated cathode can be applied in chlor-alkali ion-exchange membrane electrolyzer, further reduce unit energy consumption, improve unit production capacity, and stability is good, has the longer industrial application life-span.
Description
Technical field
The invention belongs to electrochemical technology field, and it is cloudy especially to provide a kind of chlorine industry ion-exchange membrane electrolyzer activity
Pole and preparation method thereof.
Background technology
With nearly (zero) film pole span in dimensionally stable anode (DSA) preparation technology, chlor-alkali ion-exchange membrane electrolyzer
The continuous development and application of the technologies such as Flexible cathodes, make the analysis chlorine overpotential of anode, ion-exchange membrane electrolyzer tank voltage not
It is disconnected to reduce, but the theoretical decomposition voltage 2.19V for forming chlorine and sodium hydroxide with chlorion and water also has certain gap, current
Actual tank voltage is typically in more than 3.0V, and as electrolytic current density is by 4KA/m2Bring up to 8KA/m2, before suitable for low
The activated cathode of current density has been not fully appropriate in chlorine industry production, if thinking, obtain energy-conservation effect is more preferable, unit
The higher ion-exchange membrane electrolyzer of production capacity, a kind of low overpotential of hydrogen evolution, high catalytic activity, anti-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 of realizing above-mentioned target.
The conventional preparation method of existing activated cathode is typically to electroplate or be coated with periodic table of elements VIII on Ni substrate
One or the metal salt solution of several in middle cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, and in the periodic table of elements in lanthanide series metal
One or the mixed solution of the metal salt of several in lanthanum, cerium, praseodymium, the activity that corresponding active layer is prepared by thermal decomposition method are cloudy
Pole.In order to improve the hydrogen evolution activity of activated cathode and 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 adhesion of source/drain and matrix is poor, sternly
Ghost image rings the service life of negative electrode；Publication number：CN 1265432A patent, by increasing between Ni substrate and active coating
Nickel oxide interlayer, the adhesion of matrix and active layer is enhanced, but its anti-reflective is very weak to the ability of rush of current.Existing process
With the lower activated cathode prepared of formula it is more or less poor adhesion, short life, anti-reflective all be present to rush of current ability, easy
The problems such as iron ion is poisoned.
Graphene is a kind of crystal structure for the bi-dimensional cellular shape being made up of carbon atom, there is the big pi bond of delocalization inside it,
And electronics can move freely inside it, make graphene that there is good electric conductivity, maximum conductivity is 10 at present6S/m；
Graphene is material most firm in current all material, and anti-wear performance is fabulous；At room temperature, graphene has higher thermal conductivity
Rate；Graphene also has very high specific surface area, is 2630m2g-1, the larger specific surface area of graphene is advantageous to the height of particle
Scattered, excellent electric conductivity is advantageous to transfer of the electronics from nano-particle to graphene base body in electrochemical process, is advantageous 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, so as to prepare more resistant to iron ion and reverse current, high electric rate, the length of low hydrogen-evolution overpotential
Life activities negative electrode.
The content of the invention
It is an object of the invention to provide a kind of activated cathode 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, further reduce unit energy consumption, improve unit production
Can, especially suitable for chlor-alkali production activated cathode under high current density.
The advantage of the invention is that：The present invention is good, chemical using high conductivity, high-specific surface area, the wearability of graphene
The features such as property is stable, graphene dispersion is entrained in transition metal, the work of doped graphene is prepared for by thermal decomposition method
Property negative electrode, its coating surface has a higher specific surface area, good wearability, under high current density, has relatively low
Hydrogen-evolution overpotential, resist strong reverse current, the poisoning of iron-resistant ion, the features such as stability is good, there is the longer industrial application life-span.
Technical solution of the present invention is as follows：
A kind of activated cathode of doped graphene, it is characterised in that：In the nickel metal base surface coating by pretreatment
Negative electrode masking liquid, the negative electrode masking liquid are graphene and ruthenium trichloride, cerous chloride, nickel chloride, the one or more of chloroplatinic acid
Mixed solution, its pH is adjusted with hydrochloric acid；Nickel metal after coating is subjected to thermal decomposition process until the oxidation of nickel metal surface metal
Thing gain in weight reaches 5-30g/m2, that is, required activated cathode is made.The nickel metallic matrix is preferably that nickel mesh grid or nickel draw in the net.
The invention provides the preparation method of the activated cathode of the doped graphene, it is characterised in that：The activity is cloudy
The main process for preparing of pole includes metallic matrix pretreatment, the negative electrode masking liquid preparation of doped graphene, pre-treated metal surface painting
Cloth negative electrode masking liquid, thermal decomposition process.
Metallic matrix pre-processes：Nickel metal is subjected to oil removal treatment with alkali lye and distilled water, then carries out blasting treatment,
At 50-90 DEG C, processing 1-15 minutes are carved with 10-25% Nacl sour, nickel metal weightlessness is reached 2-50g/m2, after taking-up
It is rinsed with alkali lye, distilled water and is dried at 100 DEG C, it is stand-by after room temperature cooling.
The negative electrode masking liquid of doped graphene is prepared：Graphene is added to containing 50-180g/L ruthenium trichlorides, 15-60g/L
Cerous chloride, 20-70g/L nickel chlorides, 45-150g/L chloroplatinic acids one or more mixed solution in, with hydrochloric acid regulation make
Its pH<0.5, the concentration of graphene is kept at 0.05-1.0g/L (preferably 0.3-0.6g/L)；By the negative electrode masking liquid of doped graphene
Room temperature ultrasound 0.5-3 hours, untill being completely dispersed to graphene into mixed solution.By the doped graphene negative electrode of different component
Masking liquid is coated successively, and mixing negative electrode masking liquid will be ultrasonically treated before coating every time, and each coating process will be controlled 1
Within hour.
As preferable scheme, the different doped graphene negative electrode masking liquid of three groups of components need to be prepared, and it is successively that each group is cloudy
Pole masking liquid is coated on nickel metallic matrix：Wherein, the metal salt that must contain in first group of negative electrode masking liquid has nickel chloride and chlorine platinum
Acid, its concentration are nickel chloride 20-70g/L, chloroplatinic acid 45-150g/L, and coated nickel metallic matrix is sintered into 20 points at 450 DEG C
Clock；Second group of negative electrode masking liquid is without particular/special requirement；The metal salt that 3rd group of negative electrode masking liquid must contain has ruthenium trichloride, and its concentration is
50-180g/L, coated nickel metallic matrix is sintered 30 minutes at 200 DEG C.
Thermal decomposition process：The negative electrode masking liquid of doped graphene is uniformly coated on the nickel metallic matrix by pretreatment,
Nickel metallic matrix after coating is dried into 10-30min at 100-150 DEG C, sinters 20-60 minutes at 200-600 DEG C afterwards,
Room temperature cools down after taking-up, it is repeatedly above-mentioned coat, dry, sintering process, reach up to nickel metal surface metal oxide gain in weight
5-30g/m2, that is, required activated cathode is made.
Brief description of the drawings
Activated cathode apparent forms of the Fig. 1 undoped with graphene.
The activated cathode apparent form of Fig. 2 doped graphenes.
Embodiment
Embodiment 1
Nickel metal pretreatment：Nickel mesh grid is subjected to oil removal treatment with alkali lye and distilled water, then carries out blasting treatment,
At 65-80 DEG C, handled about 5 minutes with 15% Nacl sour quarter, nickel mesh grid weightlessness is reached 9g/m2, alkali is used after taking-up
Liquid, distilled water are rinsed and dried at 100 DEG C, stand-by after room temperature cooling.
It is prepared by masking liquid and activated cathode：The negative electrode masking liquid of matched somebody with somebody doped graphene is both needed to use salt acid for adjusting pH<0.5, room temperature
Ultrasound 1 hour, makes graphene uniform be dispersed in mixed solution.
By graphene be added to containing 50g/L nickel chlorides, 50g/L chloroplatinic acids mixed solution in, keep the dense of graphene
Spend in 0.35g/L, be coated on the masking liquid as the first component in the nickel mesh grid by pretreatment, 10 points are dried at 150 DEG C
Clock, sinters 20 minutes at 450 DEG C after taking-up, repeatedly above-mentioned coating, drying, sintering process 2-3 times；Then graphene is added to
Containing 110g/L ruthenium trichlorides, 35g/L cerous chlorides, 25g/L nickel chlorides mixed solution in, keep the concentration of graphene to exist
0.55g/L, in the nickel mesh grid after the masking liquid is coated on into above-mentioned coating as the second component, dry 10 minutes, take at 150 DEG C
Sinter 20 minutes after going out at 450 DEG C, repeatedly above-mentioned coating, drying, sintering process 8-12 times；Graphene is finally entrained in 50g/
In L ruthenium trichlorides, the concentration of graphene is kept in 0.6/L, is coated on using the masking liquid as third component and is covered with above-mentioned two-wheeled and applies
In the nickel mesh grid of the coating of cloth, dry 10 minutes, sintered 30 minutes at 200 DEG C after taking-up, above-mentioned painting repeatedly at 150 DEG C
Cloth, drying, sintering process 2-3 times, until nickel metal on metal oxide gain in weight reaches 12.5-13.0g/m2, prepare and complete.
Embodiment 2
Nickel metal pretreatment process is the same as embodiment 1.
It is prepared by masking liquid and activated cathode：Matched somebody with somebody solution is both needed to use salt acid for adjusting pH<0.5, the catholyte compartment of doped graphene
Warm ultrasound 1 hour, makes graphene uniform be dispersed in mixed solution.
By graphene be added to containing 40g/L nickel chlorides, 45g/L chloroplatinic acids mixed solution in, keep the dense of graphene
Spend in 0.3g/L, be coated on the masking liquid as the first component in the nickel mesh grid by pretreatment, 10 points are dried at 150 DEG C
Clock, sinters 20 minutes at 450 DEG C after taking-up, repeatedly above-mentioned coating, drying, sintering process 5-6 times；Then graphene is added to
Containing 80g/L ruthenium trichlorides, 25g/L cerous chlorides, 20g/L nickel chlorides, 50g/L chloroplatinic acids mixed solution in, keep graphite
The concentration of alkene is dry at 150 DEG C on 0.55g/L, the nickel mesh grid after the masking liquid is coated on into above-mentioned coating as the second component
Dry 10 minutes, sinter 20 minutes after taking-up at 450 DEG C, repeatedly above-mentioned coating, drying, sintering process 8-12 times；Finally by graphite
Alkene is entrained in 55g/L ruthenium trichlorides, keeps the concentration of graphene to be coated on the masking liquid as third component and cover in 0.4g/L
In the nickel mesh grid for having the coating of above-mentioned two-wheeled coating, dried 10 minutes at 150 DEG C, 30 points are sintered at 200 DEG C after taking-up
Clock, repeatedly above-mentioned coating, drying, sintering process 5-6 times.Negative electrode masking liquid is coated on nickel metallic matrix until its metal aoxidizes
Thing gain in weight reaches 20.5-21.0g/m2, prepare and complete.
Embodiment 3
For nickel metal pretreatment with embodiment 1, difference is not carry out the packet masking liquid coating of three components, activated cathode preparation process
It is as follows：
Graphene be added to containing 110g/L ruthenium trichlorides, 35g/L cerous chlorides, 25g/L nickel chlorides mixed solution in,
Keep the concentration of graphene the masking liquid to be coated in nickel mesh grid in 0.55g/L, dried 10 minutes at 150 DEG C, after taking-up
450 DEG C sinter 20 minutes, repeatedly above-mentioned coating, drying, sintering process 12-18 times, until metal oxide increases in nickel mesh grid
Weight reaches 12.5-13.0g/m2, prepare and complete.
Embodiment 4
Nickel metal pretreatment process adjusts the content of graphene in each component in negative electrode masking liquid, remaining negative electrode with embodiment 1
Masking liquid component is the same as embodiment 2.
It is prepared by masking liquid and activated cathode：Matched somebody with somebody solution is both needed to use salt acid for adjusting pH<0.5, the catholyte compartment of doped graphene
Warm ultrasound 1 hour, makes graphene uniform be dispersed in mixed solution.
By graphene be added to containing 40g/L nickel chlorides, 45g/L chloroplatinic acids mixed solution in, keep the dense of graphene
Spend in 0.36g/L, be coated on the masking liquid as the first component in the nickel mesh grid by pretreatment, 10 points are dried at 150 DEG C
Clock, sinters 20 minutes at 450 DEG C after taking-up, repeatedly above-mentioned coating, drying, sintering process 2-3 times；Then graphene is added to
Containing 80g/L ruthenium trichlorides, 25g/L cerous chlorides, 20g/L nickel chlorides, 50g/L chloroplatinic acids mixed solution in, keep graphite
The concentration of alkene is dry at 150 DEG C on 0.66g/L, the nickel mesh grid after the masking liquid is coated on into above-mentioned coating as the second component
Dry 10 minutes, sinter 20 minutes after taking-up at 450 DEG C, repeatedly above-mentioned coating, drying, sintering process 8-12 times；Finally by graphite
Alkene is entrained in 55g/L ruthenium trichlorides, keeps the concentration of graphene to be coated on using the masking liquid as third component in 0.48g/L
It is covered with the nickel mesh grid of the coating of above-mentioned two-wheeled coating, is dried 10 minutes at 150 DEG C, 30 are sintered at 200 DEG C after taking-up
Minute, above-mentioned coating, drying, sintering process 2-3 times repeatedly.Negative electrode masking liquid is coated on nickel metal until its metal oxide
Gain in weight reaches 12.5-13.0g/m2, prepare and complete.
Comparative example 1
Nickel metal pretreatment, negative electrode preparation process are the same as embodiment 1.Stone is free of in negative electrode masking liquid as different from Example 1
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, prepare and complete.
Comparative example 2
Nickel metal pretreatment, negative electrode preparation process are the same as embodiment 2.Stone is free of in negative electrode 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, prepare and complete.
The performance test of activated cathode：
1. hydrogen-evolution overpotential：In 11mol/L NaOH solutions, 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. power-off polarization test：In 11mol/L NaOH solutions, 90 ± 2 DEG C, 5KA/m2Under current density, using nickel plate as sun
Pole, activated cathode are that negative electrode carries out 720h polarization tests, 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 solutions, 90 ± 2 DEG C, 200A/m2Under current density, electricity
Solution 0.5 hour, add up to carry out 12 times, using activated cathode as anode, nickel plate is that negative electrode carries out polarization test, tests hydrogen-evolution overpotential；
4. iron-resistant ion poisoning test：In 11mol/L NaOH solutions (the wherein Fe containing 0.04mg/L3+), 90 ± 2 DEG C,
5KA/m2Under current density, using nickel plate as anode, activated cathode is that negative electrode is tested, and tests hydrogen-evolution overpotential.
The embodiment of above-mentioned preparation and comparative example are tested according to above method of testing, obtain following result：
The activated cathode hydrogen-evolution overpotential of table 1
With reference to the data of table 1, can be drawn by embodiment 1-2 and comparative example 1-2, under identical preparation condition, doped graphite
The activated cathode of alkene low 50-60mV under different current densities than the initial hydrogen-evolution overpotential of activated cathode undoped with graphene, and
After 720h is electrolysed, current potential elevation amplitude is also less than the activated cathode undoped with graphene；Pass through embodiment 1 and embodiment 3
It can draw, packet point coating is lower than not being grouped activated cathode hydrogen-evolution overpotential prepared by point coating, is coated with by third component
Activated cathode part graphene is still left on surface after heat treatment, greatly improve the electric conductivity on surface, illustrate packet apply
Cloth can be effectively improved the surface conductivity and the adhesion of coating and matrix of activated cathode；Can by embodiment 2 and embodiment 4
To find out, hydrogen-evolution overpotential can not effectively be reduced by increasing the content of graphene in active masking liquid, be increased slightly on the contrary, excessive increase
The content of graphene can cause to cover to active layer surface on the contrary, and then reduce hydrogen evolution activity, pass through embodiment 1-2 and comparative example
After 1-4 can be seen that doped graphene and packet point coating, activated cathode has larger electrode activation area and less electricity
Lotus transfer resistance, the electrical conductivity and adhesion of cathode surface are greatly improved, further illustrate doped graphite in the present embodiment
The activated cathode of alkene has more preferable 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 different activities catholyte of table 2 polarizes
With reference to the data of table 2, by powering 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 is low, and packet coating further enhancing the anti-cut-off capacity of activated cathode of doped graphene.
Amplify 5000 times by field emission electron flying-spot microscope, compared for the activated cathode (Fig. 1) undoped with graphene
With the apparent form of the activated cathode (Fig. 2) of doped graphene.
By Fig. 1 and Fig. 2 contrast, the active cathode surface degree of grain refinement of doped graphene be significantly better than undoped with
The active cathode surface of graphene, make the uniformity of cathode surface higher, can effectively reduce actual current density, prevent part
Current density is excessive, causes the coming 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 solutions, 90 ± 2 DEG C, 200A/m2Under current density, electrolysis 0.5
Hour, add up to carry out 12 times, using activated cathode as anode, nickel plate is that negative electrode carries out polarization test, tests hydrogen-evolution overpotential；
The reverse current impact experiment of table 3
By table 3, the ability of the anti-reverse current of the activated cathode of doped graphene is than the work undoped with graphene
Property negative electrode 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, and this is due to the doping by graphene, and metallic is in matrix surface
Distribution is more uniform, has more preferable electrochemical stability, makes electric current more uniform in active layer surface distributed, and then suppresses to live
Property layer Large area coatings caused by change in polarity come off.
The poisoning test of iron-resistant ion：In 11mol NaOH solutions (the wherein Fe containing 0.04mg/L3+), 90 ± 2 DEG C, 5KA/
m2Under current density, using nickel plate as anode, activated cathode is that negative electrode carries out polarization test, tests hydrogen-evolution overpotential, statistics display, mixes
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, ripple
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, the crystal grain of metallic is set more to refine, surface tends to be uniform, 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 can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.
Claims (7)
- A kind of 1. activated cathode of doped graphene, it is characterised in that：It is coated with the nickel metal base surface by pretreatment cloudy Pole masking liquid, the negative electrode masking liquid are that graphene and ruthenium trichloride, cerous chloride, nickel chloride, one or more of chloroplatinic acid are mixed Solution is closed, its pH is adjusted 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, that is, required activated cathode is made.
- 2. according to the activated cathode of doped graphene described in claim 1, it is characterised in that：The nickel metallic matrix weaves for nickel Net or nickel draw in the net.
- A kind of 3. 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 negative electrode 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 Manage as nickel metal is carried out into oil removal treatment with alkali lye and distilled water, then carry out blasting treatment, at 50-90 DEG C, use 10-25% Nacl sour carve processing 1-15 minutes, nickel metal weightlessness is reached 2-50g/m2, rushed after taking-up with alkali lye, distilled water Wash and dried at 100 DEG C, it is stand-by after room temperature cooling.
- 5. the preparation method of the activated cathode according to doped graphene described in claim 3, it is characterised in that：Doped graphene Negative electrode masking liquid is prepared：Graphene is added to containing 50-180g/L ruthenium trichlorides, 15-60g/L cerous chlorides, 20-70g/L Nickel chloride, 45-150g/L chloroplatinic acids one or more mixed solution in, with hydrochloric acid regulation make its pH<0.5, keep graphite The concentration of alkene by the negative electrode masking liquid room temperature ultrasound 0.5-3 hours of doped graphene, is divided in 0.05-1.0g/L completely to graphene Untill being scattered in mixed solution；The doped graphene negative electrode masking liquid of different component is coated successively, mixed every time before coating Negative electrode masking liquid will be ultrasonically treated, and each coating process will be controlled within an hour.
- 6. the preparation method of the activated cathode according to the doped graphene of claim 3 or 5, it is characterised in that：Prepare three groups The different doped graphene negative electrode masking liquid of component, and each group negative electrode masking liquid is coated on nickel metallic matrix successively, first group is cloudy The metal salt that must contain in the masking liquid of pole has nickel chloride and chloroplatinic acid, and its concentration is nickel chloride 20-70g/L, chloroplatinic acid 45- 150g/L, the nickel metallic matrix that painting makes is sintered 20 minutes at 450 DEG C；The metal salt that 3rd group of negative electrode masking liquid must contain has Ruthenium trichloride, its concentration are 50-180g/L, and the nickel metallic matrix that painting makes is sintered 30 minutes at 200 DEG C.
- 7. the preparation method of the activated cathode according to doped graphene described in claim 3, it is characterised in that：Thermal decomposition process is Nickel metallic matrix after coating is dried into 10-30min at 100-150 DEG C, then 20-60 minutes are sintered at 200-600 DEG C, is taken Go out the cooling of rear room temperature, it is repeatedly above-mentioned coat, dry, sintering process, up to nickel metallized metal oxide gain in weight reaches 5-30g/ m2, that is, required activated cathode is made.
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| CN108998807A (en) * | 2018-06-28 | 2018-12-14 | 江苏安凯特科技股份有限公司 | A kind of improved Ru-Ce coated electrode |
| WO2020110527A1 (en) * | 2018-11-27 | 2020-06-04 | 株式会社大阪ソーダ | Hydrogen generation electrode, method of producing same, and hydrogen production method |
| JP2022531603A (en) * | 2020-01-09 | 2022-07-07 | エルジー・ケム・リミテッド | Electrode for electrolysis |
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| CN113166958A (en) * | 2018-11-27 | 2021-07-23 | 株式会社大阪曹達 | Electrode for hydrogen generation, method for producing same, and method for producing hydrogen |
| JPWO2020110527A1 (en) * | 2018-11-27 | 2021-10-14 | 株式会社大阪ソーダ | Electrode for hydrogen generation, its manufacturing method, and hydrogen manufacturing method |
| JP2022531603A (en) * | 2020-01-09 | 2022-07-07 | エルジー・ケム・リミテッド | Electrode for electrolysis |
| JP7324310B2 (en) | 2020-01-09 | 2023-08-09 | エルジー・ケム・リミテッド | electrode for electrolysis |
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