CN104831335A - Graphene-nano nickel composite thermoelectric thin film - Google Patents
Graphene-nano nickel composite thermoelectric thin film Download PDFInfo
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Abstract
The invention discloses a graphene-nano nickel composite thermoelectric thin film which is prepared through a method comprising the steps of preparing and dispersing graphite oxide, successfully supporting nano nickel ions onto the surface of graphene layers through a solvothermal method and finally preparing the high-performance thermoelectric thin film through electro-deposition. The method is convenient and can be used for preparing the thin film being excellent in electro-conductivity.
Description
Technical field
The present invention relates to absorbing material field, in particular a kind of Graphene-nano nickel compound thermal conductive film.
Background technology
Along with science and technology and the development of electronic industry, increasing electromagenetic wave radiation is present in around us, show through research, excessive electromagenetic wave radiation occurs, except obstacle, even may bring out the serious disease comprising all kinds of cancer except causing neural system, immunity system, reproductive system and blood circulation etc.Be in for a long time in electromagnetic wave environment, damaged by hertzian wave in human body and the damage of the tissue of the self-regeneration that is not able to do in time and organ can become dynamic disease becomes because of long term accumulation, can threat to life time serious.
Graphene, the single layer structure due to its uniqueness makes it have the features such as ultralight density, large specific surface area, specific inductivity that conductivity is excellent and high, becomes a kind of novel wave-absorbing material.In addition, the chemical bond that oxidized graphenic surface exposes in a large number more easily produces the dielectric relaxor of out-shell electron and attenuates electromagnetic waves under the effect of electromagnetic field, for Graphene is inhaling the applications expanding prospect in ripple field, at graphenic surface loaded with nano nickel ion, not only can improve magnetism of material energy, the magnetic loss of reinforced composite, be conducive to the impedance matching of matrix material, and nano nickel ion particles is again stacking in three-dimensional graphite structure in drying process as spacer medium minimizing Graphene, considerable effect is played to stable graphene film Rotating fields.
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of Graphene-nano nickel compound thermal conductive film.
Technical scheme of the present invention is as follows:
A kind of Graphene-nano nickel compound thermal conductive film, it is characterized in that, its step is as follows:
Step one, made by graphite and be of a size of 50-200 order and obtain Graphite Powder 99, being added to massfraction is afterwards in the hydrochloric acid soln of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By Graphite Powder 99, Potassium Persulphate and P
2o
5add in the vitriol oil, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described Graphite Powder 99, Potassium Persulphate, P
2o
5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the vitriol oil;
Joined in concentrated nitric acid by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and concentrated nitric acid is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO
4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO
4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO
4, stir 20min, obtain the graphite mixture of preoxidation, described first time adds KMnO
4, second time adds KMnO
4kMnO is added with third time
4mass ratio be 1: 2: 3, described dried mixture and total KMnO
4ratio be 1-2: 10-15.
After the graphite mixture obtaining preoxidation is filtered also drying, be positioned in retort furnace and carry out heat treated, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into insulation can by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of preoxidation, then react 2.5h, by insulation can temperature to 40 DEG C, again add after-fractionating water and H
2o
2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H
2o
2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation after product hydrochloric acid soln washs, the volume of this hydrochloric acid soln is 10-50 times of centrifugation after product volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulphoxide ultrasonic dissolution and make surface treatment agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3, surface grafting, by step 3 obtain the mixed with polymers of surface-treated graphite oxide and required grafting, and be heated to 80-95 DEG C and pass into nitrogen, and the solution added containing quadrivalent cerium ion, stirring reaction 2-4h, after filtration, washing, dry, obtain described polymer graft graphite oxide, the mass ratio of the polymkeric substance of described graphite oxide and required grafting is 1-2: 1-3, the polymkeric substance of required grafting is by methyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate composition, described methyl methacrylate, glycidyl methacrylate, the mass ratio of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate is 1: 1: 2: 1,
Step 4, dispersion
The ethylene glycol ultrasonic disperse putting into 500ml after the graphite 1-2g of the surface grafting of step 3 gained is carried out frost drying at-10-30 DEG C with 1-10g polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50gNH
4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 9-11;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 130 DEG C, insulation 2h, 150 DEG C are warming up to afterwards with the temperature rise rate of 2-4 DEG C/min, insulation 4h, 200 DEG C are warming up to afterwards with the temperature rise rate of 3-6 DEG C/min, insulation 3h, then 180 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 200 DEG C with the temperature rise rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, dehydrated alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum-drying 24h, obtain the first product,
Be added in the solution of Witco 1298 Soft Acid by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and Witco 1298 Soft Acid is 1-1.5: 8-15;
Be dissolved in by 3g ammonium persulphate in 80-120ml distilled water, be slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum-drying 24 ~ 36h, obtain absorbing material.
Step 5, film forming, this absorbing material is added in deionized water, be configured to the aqueous solution that concentration is 5-25g/L, first mechanical stirring 10-15min is adopted, then be ultrasonic disperse 30-50min under the condition of 30Hz in ultrasonic frequency, form uniform solution, this solution is positioned in container stand-by;
Select Cu sheet as base material, this base material is adopted acetone, deionized water, methyl alcohol and deionized water successively, use ultrasonic cleaning 5-10min respectively, by base material complete for cleaning at 90-120 DEG C of vacuum-drying 10-30min, put into container afterwards as negative pole, adopt Fe sheet as positive pole, under electrophoresis apparatus being adjusted to the constant voltage mode of 30-120V, deposit 30-90min, both obtain thermal electric film.
The ratio of the g of graphite oxide described in step 2, methyl-sulphoxide ml, N-hydroxysuccinimide g and self-control surface treatment agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface treatment agent is made up of dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic acid, and described dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic mass ratio are 1: 1: 2: 3.
In described described step 2, the concentration of hydrochloric acid is the hydrochloric acid soln of volume ratio 1: 10.
This absorbing material is laminar nano composite wave-suction material, the growth of nano nickel uniform particle is in graphene sheet layer, on graphene sheet layer, load particle diameter is about the nano nickel particle of 20-100nm, and polyaniline-coated has the graphene sheet layer surface of nano nickel particle in load.
In absorbing material obtained by the present invention between Graphene and nano nickel ion with chemical bonds; in conjunction with very tight; can not make to depart from because of the stirring etc. in later stage, chemical property is also stablized, and polyaniline-coated has the graphene sheet layer surface protection nickel ion of nano nickel particle not oxidized in load.
Applicant prepares preoxidation graphite through large quantity research step one of the present invention and adopts different temperature rise rates to be warming up to required whipping temp, stirring stage by stage under different whipping temps, and adds KMnO at different temperature stage by stage
4contribute to the preparation of preoxidation graphite, make oxidation more thoroughly be higher than common disposable stirring and add KMnO
410-15%, and be conducive to the formation of later stage Graphene;
In step 2, further surface treatment is done for graphite oxide, adopt homemade surface treatment agent, the surperficial shortcoming low for metal ion affinity of graphite oxide enough can be made up after adding, increase the charge capacity of surface nickel ion, also make nickel ion below more even in the dispersion of graphite surface, the specific surface area of its graphite reaches 35-37m simultaneously
2/ g;
Graphite through grafting process just has fabulous solvability in the later stage, and be more easy to be added in high molecular polymer matrix, the associativity of the nano composite material formed is more outstanding.
During adopting different temperature rise rates to be warming up to required temperature, through insulation of once lowering the temperature, more contribute to the formation of graphene-supported nano nickel absorbing material, make the absorbing property of the final absorbing material formed stronger, be better than the performance 5-15% of the absorbing material that usual way is formed, and the tri compound absorbing material performance formed is more stable;
The present invention without the need to using nitrogen or oxygen protection, without the need to hot conditions, can effectively reduce synthesis cost, and effectively raising the dispersing uniformity of nano particle in graphite, improve the performance of product in preparation process;
The saturation magnetization of the graphene-supported nano nickel absorbing material of the present invention is the specific conductivity of 15.7-38.5emu/g, obtained film: 4.29 × 10
-3-8.56 × 10
-3s/cm, conductivity is excellent.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
A kind of Graphene-nano nickel compound thermal conductive film, it is characterized in that, its step is as follows:
Step one, made by graphite and be of a size of 50-200 order and obtain Graphite Powder 99, being added to massfraction is afterwards in the hydrochloric acid soln of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By Graphite Powder 99, Potassium Persulphate and P
2o
5add in the vitriol oil, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described Graphite Powder 99, Potassium Persulphate, P
2o
5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the vitriol oil;
Joined in concentrated nitric acid by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and concentrated nitric acid is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO
4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO
4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO
4, stir 20min, obtain the graphite mixture of preoxidation, described first time adds KMnO
4, second time adds KMnO
4kMnO is added with third time
4mass ratio be 1: 2: 3, described dried mixture and total KMnO
4ratio be 1-2: 10-15.
After the graphite mixture obtaining preoxidation is filtered also drying, be positioned in retort furnace and carry out heat treated, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into insulation can by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of preoxidation, then react 2.5h, by insulation can temperature to 40 DEG C, again add after-fractionating water and H
2o
2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H
2o
2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation after product hydrochloric acid soln washs, the volume of this hydrochloric acid soln is 10-50 times of centrifugation after product volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulphoxide ultrasonic dissolution and make surface treatment agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3, surface grafting, by step 3 obtain the mixed with polymers of surface-treated graphite oxide and required grafting, and be heated to 80-95 DEG C and pass into nitrogen, and the solution added containing quadrivalent cerium ion, stirring reaction 2-4h, after filtration, washing, dry, obtain described polymer graft graphite oxide, the mass ratio of the polymkeric substance of described graphite oxide and required grafting is 1-2: 1-3, the polymkeric substance of required grafting is by methyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate composition, described methyl methacrylate, glycidyl methacrylate, the mass ratio of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate is 1: 1: 2: 1,
Step 4, dispersion
The ethylene glycol ultrasonic disperse putting into 500ml after the graphite 1-2g of the surface grafting of step 3 gained is carried out frost drying at-10-30 DEG C with 1-10g polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50gNH
4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 9-11;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 130 DEG C, insulation 2h, 150 DEG C are warming up to afterwards with the temperature rise rate of 2-4 DEG C/min, insulation 4h, 200 DEG C are warming up to afterwards with the temperature rise rate of 3-6 DEG C/min, insulation 3h, then 180 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 200 DEG C with the temperature rise rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, dehydrated alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum-drying 24h, obtain the first product,
Be added in the solution of Witco 1298 Soft Acid by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and Witco 1298 Soft Acid is 1-1.5: 8-15;
Be dissolved in by 3g ammonium persulphate in 80-120ml distilled water, be slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum-drying 24 ~ 36h, obtain absorbing material.
Step 5, film forming, this absorbing material is added in deionized water, be configured to the aqueous solution that concentration is 5-25g/L, first mechanical stirring 10-15min is adopted, then be ultrasonic disperse 30-50min under the condition of 30Hz in ultrasonic frequency, form uniform solution, this solution is positioned in container stand-by;
Select Cu sheet as base material, this base material is adopted acetone, deionized water, methyl alcohol and deionized water successively, use ultrasonic cleaning 5-10min respectively, by base material complete for cleaning at 90-120 DEG C of vacuum-drying 10-30min, put into container afterwards as negative pole, adopt Fe sheet as positive pole, under electrophoresis apparatus being adjusted to the constant voltage mode of 30-120V, deposit 30-90min, both obtain thermal electric film.
The ratio of the g of graphite oxide described in step 2, methyl-sulphoxide ml, N-hydroxysuccinimide g and self-control surface treatment agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface treatment agent is made up of dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic acid, and described dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic mass ratio are 1: 1: 2: 3.
In described described step 2, the concentration of hydrochloric acid is the hydrochloric acid soln of volume ratio 1: 10.
This absorbing material is laminar nano composite wave-suction material, the growth of nano nickel uniform particle is in graphene sheet layer, on graphene sheet layer, load particle diameter is about the nano nickel particle of 20-100nm, and polyaniline-coated has the graphene sheet layer surface of nano nickel particle in load.
Obtained thickness to be the reflection loss peak of the sample of 2mm the be Absorber Bandwidth of 21.9dB, below reflection loss-10dB, up to 4.6GHz, effectively can absorb the hertzian wave of this frequency range.。The saturation magnetization of the graphene-supported nano nickel absorbing material of the present invention is the specific conductivity of 15.7-38.5emu/g, obtained film: 4.29 × 10
-3-8.56 × 10
-3s/cm, conductivity is excellent.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (4)
1. Graphene-nano nickel compound thermal conductive film, it is characterized in that, the preparation method of this film comprises the following steps:
Step one, made by graphite and be of a size of 50-200 order and obtain Graphite Powder 99, being added to massfraction is afterwards in the hydrochloric acid soln of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By Graphite Powder 99 stand-by for foregoing oven dry, Potassium Persulphate and P
2o
5add in the vitriol oil, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described Graphite Powder 99, Potassium Persulphate, P
2o
5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the vitriol oil;
Joined in concentrated nitric acid by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and concentrated nitric acid is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO
4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO
4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO
4, stir 20min, obtain the graphite mixture of preoxidation, described first time adds KMnO
4, second time adds KMnO
4kMnO is added with third time
4mass ratio be 1: 2: 3, described dried mixture and total KMnO
4ratio be 1-2: 10-15.
After the graphite mixture obtaining preoxidation is filtered also drying, be positioned in retort furnace and carry out heat treated, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into insulation can by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of preoxidation, then react 2.5h, by insulation can temperature to 40 DEG C, again add after-fractionating water and H
2o
2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H
2o
2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation after product hydrochloric acid soln washs, the volume of this hydrochloric acid soln is 10-50 times of centrifugation after product volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulphoxide ultrasonic dissolution and make surface treatment agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3, surface grafting, by step 3 obtain the mixed with polymers of surface-treated graphite oxide and required grafting, and be heated to 80-95 DEG C and pass into nitrogen, and the solution added containing quadrivalent cerium ion, stirring reaction 2-4h, after filtration, washing, dry, obtain described polymer graft graphite oxide, the mass ratio of the polymkeric substance of described graphite oxide and required grafting is 1-2: 1-3, the polymkeric substance of required grafting is by methyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate composition, described methyl methacrylate, glycidyl methacrylate, the mass ratio of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate is 1: 1: 2: 1,
Step 4, dispersion
The ethylene glycol ultrasonic disperse putting into 500ml after the graphite 1-2g of the surface grafting of step 3 gained is carried out frost drying at-10-30 DEG C with 1-10g polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50gNH
4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 9-11;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 130 DEG C, insulation 2h, 150 DEG C are warming up to afterwards with the temperature rise rate of 2-4 DEG C/min, insulation 4h, 200 DEG C are warming up to afterwards with the temperature rise rate of 3-6 DEG C/min, insulation 3h, then 180 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 200 DEG C with the temperature rise rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, dehydrated alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum-drying 24h, obtain the first product,
Be added in the solution of Witco 1298 Soft Acid by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and Witco 1298 Soft Acid is 1-1.5: 8-15;
Be dissolved in by 3g ammonium persulphate in 80-120ml distilled water, be slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum-drying 24 ~ 36h, obtain absorbing material.
Step 5, film forming, this absorbing material is added in deionized water, be configured to the aqueous solution that concentration is 5-25g/L, first mechanical stirring 10-15min is adopted, then be ultrasonic disperse 30-50min under the condition of 30Hz in ultrasonic frequency, form uniform solution, this solution is positioned in container stand-by;
Select Cu sheet as base material, this base material is adopted acetone, deionized water, methyl alcohol and deionized water successively, use ultrasonic cleaning 5-10min respectively, by base material complete for cleaning at 90-120 DEG C of vacuum-drying 10-30min, put into container afterwards as negative pole, adopt Fe sheet as positive pole, under electrophoresis apparatus being adjusted to the constant voltage mode of 30-120V, deposit 30-90min, both obtain thermal electric film.
2. preparation method according to claim 1, it is characterized in that, the ratio of the g of graphite oxide described in step 2, methyl-sulphoxide ml, N-hydroxysuccinimide g and self-control surface treatment agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface treatment agent is made up of dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic acid, and described dicyclohexylcarbodiimide, sodium laurylsulfonate, sodium polystyrene sulfonate and polyacrylic mass ratio are 1: 1: 2: 3.
3. preparation method according to claim 1, is characterized in that, in described described step 2, the concentration of hydrochloric acid is the hydrochloric acid soln of volume ratio 1: 10.
4. nano combined absorbing material according to claim 1, it is characterized in that, this absorbing material is laminar nano composite wave-suction material, the growth of nano nickel uniform particle is in graphene sheet layer, on graphene sheet layer, load particle diameter is about the nano nickel particle of 20-100nm, and polyaniline-coated has the graphene sheet layer surface of nano nickel particle in load.
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