CN105887168A - Preparation method for composite thermoelectrical thin film with nano nickel loaded on graphene - Google Patents

Abstract

The invention discloses a preparation method for a composite thermoelectrical thin film with nano nickel loaded on graphene. The preparation method comprises the steps that graphite oxide is prepared and scattered, nano-nickel ions are successfully loaded on the surface of a graphene slice layer through a solvothermal method, and finally the thermoelectrical thin film with the good performance is prepared through an electro-deposition method. The preparation method for the composite thermoelectrical thin film with the nano nickel loaded on the graphene is convenient and efficient and can prepare the thin film material which is excellent in conductive performance.

Description

A kind of preparation method of graphene-supported nano nickel compound thermal conductive film

Technical field

The present invention relates to absorbing material field, the preparation side of a kind of graphene-supported nano nickel compound thermal conductive film Method.

Background technology

Along with the development of science and technology with electronics industry, increasing electromagenetic wave radiation is present in around us, through research Showing, excess electromagenetic wave radiation is except causing the generation obstacles such as nervous system, immune system, reproductive system and blood circulation Outward, in some instances it may even be possible to induction serious disease including all kinds of cancers.It is chronically in electromagnetic wave environment, by electromagnetic wave in human body The damage of the tissue and organ that damage and have not enough time to self-regeneration can become dynamic disease and become because of long term accumulation, can time serious Threat to life.

Graphene, due to the single layer structure of its uniqueness make it have ultralight density, big specific surface area, electric conductivity excellent and The features such as high dielectric constant so that it is become a kind of novel wave-absorbing material.It addition, what oxidized graphenic surface exposed in a large number Chemical bond is more prone to the dielectric relaxor of outer-shell electron and electromagnetic wave of decaying under the effect of electromagnetic field, is inhaling ripple neck for Graphene The applications expanding in territory prospect, loads nano nickel ion at graphenic surface, is possible not only to improve magnetism of material energy, strengthens compound The impedance matching of the magnetic loss of material, beneficially composite, and nano nickel ion particles reduces Graphene as spacer medium Dry run stacks again in three-dimensional graphite structure, stable graphene film Rotating fields is played considerable effect.

The technical problem to be solved is for the deficiencies in the prior art, it is provided that a kind of graphene-supported nano nickel is combined The preparation method of thermal electric film.

Technical scheme is as follows:

The preparation method of a kind of graphene-supported nano nickel compound thermal conductive film, it is characterised in that its step is as follows:

Step one, the preparation of pre-oxidation graphite

By graphite powder, potassium peroxydisulfate and P₂O₅Adding in concentrated sulphuric acid, form mixture, the pH value of the mixture formed is 1.5, This mixture is stirred at 60 DEG C 1-2h, then at 80 DEG C, stirs 2-4h, finally with 2 with the ramp of 5 DEG C/min DEG C/min be warming up to 87 DEG C stirring 1-2h, then use this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, place and use after 36h distilled water to filter so that mixture pH value is 6-7, after carry out drying at room temperature, described graphite powder, Potassium peroxydisulfate, P₂O₅It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；

Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time₄, stir 30min, At being cooled to-12 DEG C afterwards, second time adds KMnO₄, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO₄, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO₄, second time adds KMnO₄ KMnO is added with third time₄Mass ratio be 1: 2: 3, described dried mixture and total KMnO₄Ratio be 1-2∶10-15。

Step 2, the preparation of the graphite oxide that surface processes

The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 2.5h, by couveuse temperature to 40 DEG C, again add after-fractionating water and H₂O₂Reaction 10-60min, the amount of described after-fractionating water is the 1-1.5 of the first distilled water Times, after-fractionating water and H₂O₂Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min, Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, Rear dialysis obtains graphite oxide in 7-8 days,

Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify, Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H₂O₂Composition, concentrated sulphuric acid and H₂O₂Mass ratio be 1-2: 2-5,；

Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution 2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；

Step 3, dispersion

The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic Dispersion, then radiates 36h under ultraviolet irradiation and forms uniform first dispersion liquid；

Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g NH₄Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；

Step 4, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C, Insulation 2h, is warming up to 150 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min Rate is warming up to 200 DEG C, is incubated 3h, is then cooled to 180 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6 DEG C/heating rate of min is warming up to 200 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room Temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts Respectively wash three times with dehydrated alcohol and deionized water, be vacuum dried 24h at 50～70 DEG C, obtain the first product；

5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min, Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；

3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h, To absorbing material.

Step 5, film forming, this absorbing material is added to deionized water, is configured to the aqueous solution that concentration is 5-25g/L, first First use mechanical agitation 10-15min, then ultrasonic disperse 30-50min under conditions of ultrasonic frequency is 30Hz, formed all Even solution, is positioned in container stand-by by this solution；

Select Cu sheet as base material, this base material used acetone, deionized water, methanol and deionized water successively, Use ultrasonic waves for cleaning 5-10min respectively, be vacuum dried 10-30min by cleaning complete base material at 90-120 DEG C, put afterwards Enter as negative pole in container, use Fe sheet as positive pole, electrophresis apparatus is adjusted under the constant voltage mode of 30-120V deposition 30-90min, had both obtained thermal electric film.

The particle diameter of described graphite powder is 15-30um.

Graphite oxide g described in step 2, dimethyl sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g's Ratio is 0.2-0.5: 20-25: 2-5: 0.1-05, and described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl Sodium sulfonate, kayexalate and polyacrylic acid composition, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, polyphenyl Vinyl sulfonic acid sodium and polyacrylic mass ratio are 1: 1: 2: 3.

The hydrochloric acid solution that concentration is volume ratio 1: 10 of hydrochloric acid in described described step 2.

This absorbing material is laminar nano composite wave-suction material, and nano nickel uniform particle is grown in graphene sheet layer, at Graphene Load the nano nickel particle that particle diameter is about 20-100nm on lamella, and polyaniline-coated is in the Graphene being loaded with nano nickel particle Sheet surfaces.

With chemical bonds between Graphene and nano nickel ion in absorbing material obtained by the present invention, in conjunction with very tight, will not Because the stirring in later stage etc. make to depart from, chemical property is also stable, and polyaniline-coated is in the graphene film being loaded with nano nickel particle Layer surface protection nickel ion is not oxidized.

It is required that applicant uses different heating rates to be warming up to through numerous studies step one of the present invention preparation pre-oxidation graphite The whipping temp wanted, stirring stage by stage under different whipping temps, and add KMnO the most at different temperature₄ Contribute to pre-oxidizing the preparation of graphite so that oxidation is more thoroughly higher than common disposable stirring and adds KMnO₄'s 10-15%, and the formation of beneficially later stage Graphene；

Step 2 does further surface for graphite oxide process, used homemade surface conditioning agent, by energy after adding Enough graphite oxide surfaces that enough makes up, for the low shortcoming of metal ion affinity, increase the load capacity of surface nickel ion, also simultaneously Making nickel ion below more uniform in the dispersion of graphite surface, the specific surface area of its graphite reaches 35-37m²/g；

Dispersion effect in step 3 is good, and stability is high, be conducive to next step operation and with the combination of nickel ion；

During step 4 of the present invention using different heating rates be warming up to required temperature, through the guarantor that once lowers the temperature Temperature, more contributes to the formation of graphene-supported nano nickel absorbing material so that the absorbing property of the absorbing material ultimately formed is more By force, it is better than performance 5-15% of the absorbing material that commonsense method is formed, and the tri compound absorbing material performance formed is more Stable；

The present invention in preparation process without use nitrogen or oxygen protection, it is not necessary to hot conditions, it is possible to effectively reduce synthesis Cost, and effectively raise nano-particle dispersing uniformity in graphite, improve the performance of product；

.The saturation magnetization of the present invention graphene-supported nano nickel absorbing material is 15.7-38.5emu/g, and obtained is thin The electrical conductivity of film: 4.29*10^-3-8.56*10^-3S/cm, electric conductivity is excellent.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described in detail.

The preparation method of a kind of graphene-supported nano nickel compound thermal conductive film, it is characterised in that its step is as follows:

Step one, the preparation of pre-oxidation graphite

By graphite powder, potassium peroxydisulfate and P₂O₅Adding in concentrated sulphuric acid, form mixture, the pH value of the mixture formed is 1.5, This mixture is stirred at 60 DEG C 1-2h, then at 80 DEG C, stirs 2-4h, finally with 2 with the ramp of 5 DEG C/min DEG C/min be warming up to 87 DEG C stirring 1-2h, then use this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, place and use after 36h distilled water to filter so that mixture pH value is 6-7, after carry out drying at room temperature, described graphite powder, Potassium peroxydisulfate, P₂O₅It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；

Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time₄, stir 30min, At being cooled to-12 DEG C afterwards, second time adds KMnO₄, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO₄, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO₄, second time adds KMnO₄ KMnO is added with third time₄Mass ratio be 1: 2: 3, described dried mixture and total KMnO₄Ratio be 1-2∶10-15。

Step 2, the preparation of the graphite oxide that surface processes

The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 2.5h, by couveuse temperature to 40 DEG C, again add after-fractionating water and H₂O₂Reaction 10-60min, the amount of described after-fractionating water is the 1-1.5 of the first distilled water Times, after-fractionating water and H₂O₂Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min, Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, Rear dialysis obtains graphite oxide in 7-8 days,

Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify, Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H₂O₂Composition, concentrated sulphuric acid and H₂O₂Mass ratio be 1-2: 2-5,；

Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution 2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；

Step 3, dispersion

The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic Dispersion, then radiates 36h under ultraviolet irradiation and forms uniform first dispersion liquid；

Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g NH₄Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；

Step 4, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C, Insulation 2h, is warming up to 150 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min Rate is warming up to 200 DEG C, is incubated 3h, is then cooled to 180 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6 DEG C/heating rate of min is warming up to 200 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room Temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts Respectively wash three times with dehydrated alcohol and deionized water, be vacuum dried 24h at 50～70 DEG C, obtain the first product；

5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min, Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；

3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h, To absorbing material.

Step 5, film forming, this absorbing material is added to deionized water, is configured to the aqueous solution that concentration is 5-25g/L, first First use mechanical agitation 10-15min, then ultrasonic disperse 30-50min under conditions of ultrasonic frequency is 30Hz, formed all Even solution, is positioned in container stand-by by this solution；

Select Cu sheet as base material, this base material used acetone, deionized water, methanol and deionized water successively, Use ultrasonic waves for cleaning 5-10min respectively, be vacuum dried 10-30min by cleaning complete base material at 90-120 DEG C, put afterwards Enter as negative pole in container, use Fe sheet as positive pole, electrophresis apparatus is adjusted under the constant voltage mode of 30-120V deposition 30-90min, had both obtained thermal electric film.

The particle diameter of described graphite powder is 15-30um.

Graphite oxide g described in step 2, dimethyl sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g's Ratio is 0.2-0.5: 20-25: 2-5: 0.1-05, and described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl Sodium sulfonate, kayexalate and polyacrylic acid composition, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, polyphenyl Vinyl sulfonic acid sodium and polyacrylic mass ratio are 1: 1: 2: 3.

The hydrochloric acid solution that concentration is volume ratio 1: 10 of hydrochloric acid in described described step 2.

This absorbing material is laminar nano composite wave-suction material, and nano nickel uniform particle is grown in graphene sheet layer, at Graphene Load the nano nickel particle that particle diameter is about 20-100nm on lamella, and polyaniline-coated is in the Graphene being loaded with nano nickel particle Sheet surfaces.

Prepared thickness be the reflection loss peak of the sample of 2mm be that the Absorber Bandwidth of 21.9dB, below reflection loss-10dB is high Reach 4.6GHz, it is possible to effectively absorb the electromagnetic wave of this frequency range..The saturated magnetization of the present invention graphene-supported nano nickel absorbing material Intensity is 15.7-38.5emu/g, the electrical conductivity of obtained thin film: 4.29*10^-3-8.56*10^-3S/cm, electric conductivity is excellent Different.

It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted, and institute There are these modifications and variations all should belong to the protection domain of claims of the present invention.

Claims (5)

1. the preparation method of a graphene-supported nano nickel compound thermal conductive film, it is characterised in that its step is as follows:

Step one, the preparation of pre-oxidation graphite

By graphite powder, potassium peroxydisulfate and P₂O₅Adding in concentrated sulphuric acid, form mixture, the pH value of the mixture formed is 1.5, This mixture is stirred at 60 DEG C 1-2h, then at 80 DEG C, stirs 2-4h, finally with 2 with the ramp of 5 DEG C/min DEG C/min be warming up to 87 DEG C stirring 1-2h, then use this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, place and use after 36h distilled water to filter so that mixture pH value is 6-7, after carry out drying at room temperature, described graphite powder, Potassium peroxydisulfate, P₂O₅It is 1-3: 1-2: 1-2: 5-10 with the mass ratio of concentrated sulphuric acid；

Dried mixture is joined stirring 45-60min in concentrated nitric acid so that pH value is 2-4, described dried mixed Compound is 1-4: 50-100 with the mass ratio of concentrated nitric acid, adds KMnO after stirring at-8 DEG C for the first time₄, stir 30min, At being cooled to-12 DEG C afterwards, second time adds KMnO₄, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO₄, to stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO₄, second time adds KMnO₄ KMnO is added with third time₄Mass ratio be 1: 2: 3, described dried mixture and total KMnO₄Ratio be 1-2∶10-15。

Step 2, the preparation of the graphite oxide that surface processes

The graphite mixture of pre-oxidation made for step one is put into couveuse is warmed up to 40 DEG C, react 3h, subsequently, add With consistent amount of first distilled water of graphite mixture volume of pre-oxidation, then react 2.5h, by couveuse temperature to 40 DEG C, again add after-fractionating water and H₂O₂Reaction 10-60min, the amount of described after-fractionating water is the 1-1.5 of the first distilled water Times, after-fractionating water and H₂O₂Volume ratio be 4-20: 1, reaction terminate after carry out centrifugation 10min, rotating speed 9500r/min, Centrifugation afterproduct hydrochloric acid solution washs, and the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, Rear dialysis obtains graphite oxide in 7-8 days,

Graphite oxide is put into purification liquid and prepares mixing liquid, the graphite oxide after carrying out concussion dispersion and being filtrated to get to purify, Described purification liquid is due to the concentrated sulphuric acid of 1.72g/ml and H₂O₂Composition, concentrated sulphuric acid and H₂O₂Mass ratio be 1-2: 2-5,；

Graphite oxide after purifying adds N-hydroxysuccinimide and self-control surface after using dimethyl sulfoxide ultrasonic dissolution 2h stir in reason agent at 35 DEG C, and product carries out sucking filtration, washs, dries, and i.e. obtains the graphite oxide of surface process；

Step 3, dispersion

The graphite oxide 1-2g that surface obtained by step 2 processes is carried out at-10-30 DEG C after lyophilization with 1-10g polycyclic Oxidative ethane-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and 1g are made up of polymethylacrylic acid and polyacrylamide Mixture (mass ratio of polymethylacrylic acid and polyacrylamide is 1: 1) put in the lump the ethylene glycol of 500ml is carried out ultrasonic Dispersion, then radiates 36h under ultraviolet irradiation and forms uniform first dispersion liquid；

Simultaneously by 20-40ml protochloride nickel ethylene glycol solution (0.1mol/ml), 6～25g polyvinylpyrrolidones and 10～50g NH₄Ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, the first dispersion liquid and the second dispersion liquid is mixed and stirs Mix, and regulate with ammonia, make the settled solution that pH value is 9-11；

Step 4, puts in reactor by the settled solution obtained by 100ml step 3, after sealing, is heated to 130 DEG C, Insulation 2h, is warming up to 150 DEG C with the heating rate of 2-4 DEG C/min afterwards, is incubated 4h, afterwards with the intensification speed of 3-6 DEG C/min Rate is warming up to 200 DEG C, is incubated 3h, is then cooled to 180 DEG C of insulation 2h with the cooling rate of 5-7 DEG C/min, the most again with 3-6 DEG C/heating rate of min is warming up to 200 DEG C, it is incubated 7h, after question response completes, reactor is taken out, is allowed to be cooled to room Temperature, described cooling rate is 3-6 DEG C/min, by the powder centrifugation 10min of gained, rotating speed 8000～10000r/min, adopts Respectively wash three times with dehydrated alcohol and deionized water, be vacuum dried 24h at 50～70 DEG C, obtain the first product；

5g the first product and 5-10g aniline monomer are added to the solution of DBSA, ultrasonic disperse 65min, Forming the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15；

3g Ammonium persulfate. is dissolved in 80-120ml distilled water, is slowly dropped in the second product, stirring reaction 15h, instead After should terminating, sucking filtration, use distilled water, washing with alcohol product colourless to filtrate respectively, 50～70 DEG C of vacuum drying 24～36h, To absorbing material.

Step 5, film forming, this absorbing material is added to deionized water, is configured to the aqueous solution that concentration is 5-25g/L, first First use mechanical agitation 10-15min, then ultrasonic disperse 30-50min under conditions of ultrasonic frequency is 30Hz, formed all Even solution, is positioned in container stand-by by this solution；

Select Cu sheet as base material, this base material used acetone, deionized water, methanol and deionized water successively, Use ultrasonic waves for cleaning 5-10min respectively, be vacuum dried 10-30min by cleaning complete base material at 90-120 DEG C, put afterwards Enter as negative pole in container, use Fe sheet as positive pole, electrophresis apparatus is adjusted under the constant voltage mode of 30-120V deposition 30-90min, had both obtained thermal electric film.

Preparation method the most according to claim 1, it is characterised in that the particle diameter of described graphite powder is 15-30um.

Preparation method the most according to claim 1, it is characterised in that graphite oxide g described in step 2, diformazan are sub- The ratio of sulfone ml, N-hydroxysuccinimide g and self-control surface conditioning agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, Described self-control surface conditioning agent is by dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic acid group Becoming, described dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic mass ratio are 1∶1∶2∶3。

Preparation method the most according to claim 1, it is characterised in that in described described step 2, the concentration of hydrochloric acid is The hydrochloric acid solution of volume ratio 1: 10.

Nano combined absorbing material the most according to claim 1, it is characterised in that this absorbing material is that laminar nano is multiple Closing absorbing material, nano nickel uniform particle is grown in graphene sheet layer, loads particle diameter and be about 20-100nm on graphene sheet layer Nano nickel particle, and polyaniline-coated is in the graphene sheet layer surface being loaded with nano nickel particle.