CN108521683A - Nano-cellulose graphene oxide thermo electric material and preparation method thereof - Google Patents
Nano-cellulose graphene oxide thermo electric material and preparation method thereof Download PDFInfo
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- CN108521683A CN108521683A CN201810462147.0A CN201810462147A CN108521683A CN 108521683 A CN108521683 A CN 108521683A CN 201810462147 A CN201810462147 A CN 201810462147A CN 108521683 A CN108521683 A CN 108521683A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
Abstract
The present invention provides a kind of nano-cellulose graphene oxide thermo electric materials and preparation method thereof, including：Substrate；The heating layer being formed in substrate, wherein heating layer contains graphene, graphene oxide, nano-cellulose；And it is connected to the electrode of heating layer.Preparation method includes choosing substrate；It selects coating spraying or brushes and form the first insulating layer on the type face of substrate；Mixed system is obtained after nano-cellulose and graphene oxide are carried out mixing dispersion；It will be mixed with mixed system after graphene ultrasonic disperse, obtain compound dispersing agent after continuing ultrasonic disperse, compound dispersing agent is coated on by inkjet printing or spraying or brushing film build method on the first insulating coating and forms heating layer；Setting electrode is connect with heating layer；It selects coating spraying or brushes and obtain nano-cellulose graphene oxide thermo electric material after formation second insulating layer on heating layer.
Description
Technical field
The present invention relates to nano-cellulose electric heating function Material Fields.It is more particularly related to a kind of with thin
Aqueous, operating temperature is stable and the nano-cellulose graphene oxide thermo electric material and preparation method thereof of uniformity of temperature profile.
Background technology
Graphene thermo electric material has higher electric conversion efficiency, and heating response is fast, can be used for snow melt deicing, demisting is removed
The fields such as frost, heating service, microelectronic component heating and thermal insulation and film micro area thermal analysis are an important sides of graphene application
To.Currently, correlative study using carbon fiber and slurry carry out it is compound obtain basis material, then graphene is mixed with other auxiliary agents
It is attached on basis material according to predetermined process at slurry, by a series of solidifications, is dried to obtain graphene thermo electric material.It should
The graphene that kind of technique obtains has many advantages, such as preferable flexibility and not oxidizable；In addition, correlative study is utilized in high score
The particle preparations such as carbon fiber, graphite powder and carbon nanotube are added in sub- material goes out a kind of high molecular electrothermal material.Such electric heating
Conductive resistance value is unstable to influence its guarantor caused by conductive particle mixing is uneven in material improvement high molecular electrothermal material
The problem of temp effect.Such thermo electric material has larger resistance value, is relatively suitable for low-temperature heat, with adding for human body intimate contact
Hot attemperator；In addition, correlative study is also warming up to centainly with certain rate using graphene aerogel in an inert atmosphere
Cooling is handled after temperature, obtains certain density and the graphene Electric radiant Heating Film of bore hole size.This kind of preparation method obtains one kind and is based on
The pressure-sensitive Electric radiant Heating Film of graphene.The pressure-sensitive Electric radiant Heating Film includes graphene Electric radiant Heating Film and coated in efficiently pressure-sensitive graphene electricity
The insulating protective layer of both sides above and below hotting mask.The pressure-sensitive Electric radiant Heating Film can make fast electric heating response under different ess-strains, answer
Power is bigger, and electro-thermal response saturation temperature is higher.This kind of technology preparation process is relatively simple, the graphene-based pressure-sensitive electric heating material of preparation
Material is had excellent performance, and has faster electro-thermal response.Relatively it is suitble to large-scale production in production.In absorbent regeneration and catalysis bone
Frame etc. has a wide range of applications.
Inventor also applied before in a kind of nano-cellulose graphene complex electrocaloric film and its green preparation process
State's patent, the patent application No. is 2017104727432, mix system which disclose graphene and nano-cellulose is used
At composite membrane, which can serve as Electric radiant Heating Film use after being bonded with electrode and insulating layer.In the technical solution, Nanowire
When dimension element is blended with graphene, under crosslinked action, nano-cellulose is equivalent to skeleton organization and holds graphene, but makes merely
Nano-cellulose is used to be had the following problems as skeleton organization：The spatial network skeleton organization unobvious that nano-cellulose is formed,
It is not high to result in degree of scatter of the graphene in nano-cellulose skeleton organization, also results in nano-cellulose and graphene is handed over
It is not high to join the film uniformity being mixed to form, so that manufactured Electric radiant Heating Film heat conductivility and stability are not good enough.
Same above-mentioned correlative study is not there is also graphene dispersion degree is high, non-uniform temperature, and hygroscopic infiltration is unfavorable
In the stability of the course of work.In addition, the prior art seldom can be suitably used for the preparation of special-shaped substrate surface thermo electric material.
Invention content
It is an object of the invention to solve at least the above defect, and provide the advantages of at least will be described later.
In order to realize these purposes and other advantages according to the present invention, a kind of nano-cellulose graphene oxide is provided
Thermo electric material, wherein including：
Substrate；Different materials can be selected as substrate, such as plank, iron plate, plastics etc. as needed
The heating layer being formed in substrate, wherein the heating layer contains graphene, graphene oxide and nanofiber
Element；After graphene oxide mixes dispersion with nano-cellulose, it can be cross-linked to form solid netted skeleton structure, it is solid netted
On the one hand skeleton structure increases skeleton structure compared with directly utilizing the skeleton structure that nano-cellulose generates in conventional method
Stability, on the other hand the gap more regular uniform in solid netted skeleton structure, helps to improve graphene in bone
Dispersed homogeneous degree in frame structure so that thermo electric material fever uniformity higher obtained, and then improve the power of thermo electric material
Learn performance and thermal stability.
It is connected to the electrode of the heating layer, electrode is used for heating power.
Preferably, in the nano-cellulose graphene oxide thermo electric material, the substrate has certain type face,
The type face is curved surface, arc surface or plane.Substrate for adapting to different shaped face.
Preferably, in the nano-cellulose graphene oxide thermo electric material, further include be formed in the substrate with
The first insulating layer between heating layer, and it is formed in the second insulating layer of the heating layer another side, avoid heating layer from leaking electricity.
Preferably, in the nano-cellulose graphene oxide thermo electric material, first insulating layer and second is absolutely
Edge layer is epoxy resin, polyurethane, heterocycle polymer, organic polymer paint, and thickness is 0.02~0.3mm.
Preferably, in the nano-cellulose graphene oxide thermo electric material, the electrode is longer than second insulating layer,
Shorter than the first insulating layer makes the electrode section expose, and is powered on convenient for connecing electricity.
Preferably, the mass ratio of graphene is 25%~65% in the heating layer, graphene oxide and nanofiber
Both plain quality accounting is 35%~75%；Wherein, the graphene oxide accounts for both graphene oxide and nano-cellulose
The 10%~60% of gross mass.
Preferably, in the nano-cellulose graphene oxide thermo electric material, the heating layer further includes hydrophobing agent,
The hydrophobing agent is fluoropolymer, fluorine containing silane, fluorination double-phobia polyurethane, nano silicon dioxide and perfluoroalkyl methyl-prop
Any one in the emulsion mixture of the mixed solution of olefin(e) acid copolymer, beeswax and palm wax, hydrophobing agent additive amount are heating layer
The 0.08%~4.2% of material weight.
A kind of preparation method of nano-cellulose graphene oxide thermo electric material, including：
Choose substrate；
It selects coating spraying or brushes and form the first insulating layer on the type face of the substrate；
Nano-cellulose and graphene oxide obtain after mixing dispersion mixed system or by nano-cellulose, oxidation
Graphene and hydrophobing agent obtain mixed system after carrying out mixing dispersion；It will be mixed with the mixed system after graphene ultrasonic disperse
It closes, obtains compound dispersing agent after continuing ultrasonic disperse, the compound dispersing agent is passed through into inkjet printing or spraying or brushing
Film build method is coated on first insulating coating and forms heating layer；It makes full use of between graphene oxide and nano-cellulose
Being cross-linked with each other, it is solid netted to be formed, and utilizes the surface both in aqueous phase system that negative potential characteristic is presented, and improves graphite
Dispersed homogeneous degree and electric heating temperature uniformity of the alkene in system, enhance the mechanical property and thermal stability of thermo electric material, especially
It is the adhesive force enhanced to substrate.
Setting electrode is connect with the heating layer；
It selects coating spraying or brushes and obtain the nanofiber after formation second insulating layer on the heating layer
Plain graphene oxide thermo electric material.
Preferably, it in the preparation method of the nano-cellulose graphene oxide thermo electric material, specifically includes following
Step：
Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprays or brush in substrate surface
Coating forms the first insulating layer, and coating weight is 50~200g/m2, it is placed in 70~90 DEG C of 3~6h of drying in vacuum drying chamber；
Electrode is made Step 2: copper foil or copper sheet are adhered on substrate insulation coating, or by conductive coating or conduction
Colloid is by printing or coated on forming electrode after drying on the first insulating layer；
Step 3: by both graphene oxide, nano-cellulose mixed liquor or by graphene oxide, nano-cellulose and
Hydrophobing agent three's mixed liquor is configured to the aqueous dispersions of a concentration of 0.1~2mg/ml, the ultrasonic disperse under 300~1000W power
Mixed system is obtained after 10~70min；
Step 4: the graphene aqueous dispersions of a concentration of 0.1~3mg/ml are prepared, the ultrasound point under 500~1000W power
It dissipates 10~70min and obtains graphene aqueous dispersions, graphene accounts for the 25%~65% of heating layer material weight；
Step 5: the mixed system is mixed with the graphene aqueous dispersions, it is ultrasonic under 300~1200W power
20~100min obtains compound dispersing agent；
Step 6: by the compound dispersing agent inkjet printing or spraying or being painted on first insulating layer, Tu Yin
Amount is 4~26g/m2, then 50~80 DEG C of dryings 6 in vacuum drying chamber~for 24 hours are placed in, form heating layer；
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer；
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight is 50~200g/m2, juxtaposition
70~90 DEG C of 3~6h of drying, obtain thermo electric material in vacuum drying chamber；
Step 9: gained thermo electric material is carried out quenching treatment, with 1.5~2.5 times of its rated power 2~12h that are powered
Afterwards, part removal graphene and graphene oxide thin slice on defect group, improve electric conductivity, formed structure it is relatively stable,
The relatively stable nano-cellulose graphene oxide thermo electric material of power.
Preferably, in the preparation method of the nano-cellulose graphene oxide thermo electric material, the graphite oxide
The ratio that alkene accounts for both nano-cellulose and graphene oxide gross weight is 10%~60%, the nano-cellulose and graphite oxide
Both alkene accounts for the 35%~75% of the heating layer quality；Hydrophobing agent is such as used, then the hydrophobing agent additive amount is heating layer material
Expect the 0.08%~4.2% of quality.
The present invention includes at least following advantageous effect：
First, the present invention uses graphene oxide and nano-cellulose with preferable film forming ability, use a certain amount of
Hydrophobing agent is mixed with graphene, is improved the consistency on thermo electric material surface and resistance to wet stability, is enhanced the operation is stable performance.
The present invention first uses graphene oxide dispersion and nano-cellulose to be mixed with dispersion, and individually disperses stone
After black alkene aqueous dispersions, redisperse is blended in the two, makes full use of and is cross-linked with each other to be formed between graphene oxide and nano-cellulose
It is solid netted, and utilize the surface both in aqueous phase system that negative potential characteristic is presented, graphene is improved in system
Dispersed homogeneous degree and electric heating temperature uniformity enhance the mechanical property and thermal stability of thermo electric material, especially enhance pair
The adhesive force of substrate.
The present invention is suitable for more using coating as insulating layer by the method that inkjet printing or spraying or brushing prepare electrothermal layer
Kind type face substrate surface.
The present invention is applicable to the surface of various type faces substrate using the technique of spraying, using with certain hydrophobic performance
Graphene oxide and hydrophobing agent improve the resistance to wet stability of thermo electric material, improve attachment of the thermo electric material to base coating
Power；Using with good filming performance graphene oxide and nano-cellulose effectively increase graphene point as dispersion
Uniformity is dissipated, operating temperature distribution consistency degree is improved, is beneficial to improve its applicability using coating as waterproof layer.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings
Fig. 1 is nano-cellulose graphene oxide thermo electric material amplification factor made from embodiment 1 of the present invention
1000 times of scanning electron microscopic picture；
Fig. 2 is the scanning electron microscopic picture of 1000 times of 1 amplification factor of contrast material made from comparative example 1 of the present invention；
Fig. 3 is that nano-cellulose graphene oxide thermo electric material made from embodiment 1 of the present invention and comparative example 1 are made
The energization situation comparison diagram of the contrast material 1 obtained；
Fig. 4 is that nano-cellulose graphene oxide thermo electric material made from embodiment 2 of the present invention and comparative example 2 are made
The energization situation comparison diagram of the contrast material 2 obtained；
Fig. 5 is that nano-cellulose graphene oxide thermo electric material made from embodiment 3 of the present invention and comparative example 3 are made
The energization situation comparison diagram of the contrast material 3 obtained；
Fig. 6 is that nano-cellulose graphene oxide thermo electric material made from embodiment 1 of the present invention and comparative example 1 are made
The thermogravimetric situation comparison diagram of the contrast material 1 obtained.
Specific implementation mode
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
The present invention primary raw material be：
Embodiment 1
Step 1: substrate is chosen, in substrate after the drying of paint surfaces activating agent, in substrate surface sprayed coating shape
At the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: weighing 0.5:0.25:Graphene, graphene oxide, the nano-cellulose of 0.25 mass ratio, i.e. graphene
The graphene oxide weighed, nano-cellulose are mixedly configured into concentration by 5g, graphene oxide 2.5g, nano-cellulose 2.5g
The aqueous dispersions of 0.5 mg/ml obtain mixed system under 800W power after 50 min of ultrasonic disperse.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, 50 min of ultrasound under 900W power
Obtain compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Dry matter weight gauge), then 70 DEG C of 15 h of drying in vacuum drying chamber are placed in, form heating layer；The size of heating layer is across both ends
Electrode 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length 15mm (power connection end), and the other end is less than electricity
Pole length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain thermo electric material in empty drying box.
Step 9: gained thermo electric material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity, formed structure compared with
For the relatively stable nano-cellulose graphene oxide Electric radiant Heating Film of stabilization, power.
Embodiment 2
Step 1: substrate is chosen, in substrate after the drying of paint surfaces activating agent, in substrate surface sprayed coating shape
At the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: weighing 0.35:0.325:Graphene, graphene oxide, the nano-cellulose of 0.325 mass ratio, i.e. stone
The graphene oxide weighed, nano-cellulose are mixed and are matched by black alkene 3.5g, graphene oxide 3.25g, nano-cellulose 3.25g
The aqueous dispersions of concentration 0.5mg/ml are set to, mixed system is obtained after ultrasonic disperse 50min under 800W power.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasound 50min is obtained under 900W power
To compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Dry matter weight gauge), then 70 DEG C of dry 15h in vacuum drying chamber are placed in, form heating layer；The size of heating layer is electric across both ends
Pole 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length 15mm (power connection end), and the other end is less than electrode
Length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain thermo electric material in empty drying box.
Step 9: gained thermo electric material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity, formed structure compared with
For the relatively stable nano-cellulose graphene oxide Electric radiant Heating Film of stabilization, power.
Embodiment 3
Step 1: substrate is chosen, in substrate after the drying of paint surfaces activating agent, in substrate surface sprayed coating shape
At the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: weighing 0.55:0.225:Graphene, graphene oxide, the nano-cellulose of 0.225 mass ratio, i.e. stone
The graphene oxide weighed, nano-cellulose are mixed and are matched by black alkene 5.5g, graphene oxide 2.25g, nano-cellulose 2.25g
The aqueous dispersions of concentration 0.5mg/ml are set to, mixed system is obtained after ultrasonic disperse 50min under 800W power.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasound 50min is obtained under 900W power
To compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Dry matter weight gauge), then 70 DEG C of dry 15h in vacuum drying chamber are placed in, form heating layer；The size of heating layer is electric across both ends
Pole 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length 15mm (power connection end), and the other end is less than electrode
Length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain thermo electric material in empty drying box.
Step 9: gained thermo electric material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity, formed structure compared with
For the relatively stable nano-cellulose graphene oxide Electric radiant Heating Film of stabilization, power.
Embodiment 4
Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprays or brush in substrate surface
Coating forms the first insulating layer, coating weight 50g/m2, it is placed in 70 DEG C of drying 6h in vacuum drying chamber；
Electrode is made Step 2: copper foil or copper sheet are adhered on substrate insulation coating, or by conductive coating or conduction
Colloid is by printing or coated on forming electrode after drying on the first insulating layer；
Step 3: weighing 0.5:0.25:Graphene, graphene oxide, the nano-cellulose of 0.25 mass ratio, i.e. graphene
5g, graphene oxide 2.5g, nano-cellulose 2.5g are weighed and are accounted for graphene, graphene oxide and nano-cellulose three's gross weight
The graphene oxide weighed, nano-cellulose and hydrophobing agent are mixedly configured into dense by 0.8% hydrophobing agent, i.e. hydrophobing agent 0.08g
The aqueous dispersions for spending 0.35mg/ml, mixed system is obtained under 300W power after ultrasonic disperse 70min；
Step 4: the graphene aqueous dispersions of a concentration of 0.25mg/ml are prepared with the graphene weighed, under 500W power
Ultrasonic disperse 70min obtains graphene aqueous dispersions；
Step 5: the mixed system is mixed with the graphene aqueous dispersions, the ultrasound 100min under 300W power
Obtain compound dispersing agent；
Step 6: by the compound dispersing agent inkjet printing or spraying or being painted on first insulating layer, Tu Yin
Amount is 4g/m2, then be placed in 50 DEG C of dryings in vacuum drying chamber and for 24 hours, form heating layer；
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer；
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 50g/m2, it is placed in vacuum
70 DEG C of drying 6h, obtain thermo electric material in drying box；
Step 9: gained thermo electric material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity, formed structure compared with
For the relatively stable nano-cellulose graphene oxide thermo electric material of stabilization, power.
Embodiment 5
Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprays or brush in substrate surface
Coating forms the first insulating layer, coating weight 200g/m2, it is placed in 90 DEG C of drying 3h in vacuum drying chamber；
Electrode is made Step 2: copper foil or copper sheet are adhered on substrate insulation coating, or by conductive coating or conduction
Colloid is by printing or coated on forming electrode after drying on the first insulating layer；
Step 3: weighing 0.5:0.25:Graphene, graphene oxide, the nano-cellulose of 0.25 mass ratio, i.e. graphene
5g, graphene oxide 2.5g, nano-cellulose 2.5g are weighed and are accounted for graphene, graphene oxide and nano-cellulose three's gross weight
The graphene oxide weighed, nano-cellulose and hydrophobing agent are mixedly configured into dense by 4.2% hydrophobing agent, i.e. hydrophobing agent 0.42g
The aqueous dispersions for spending 0.75mg/ml, mixed system is obtained under 1000W power after ultrasonic disperse 10min；
Step 4: the graphene aqueous dispersions of a concentration of 0.65mg/ml are prepared, the ultrasonic disperse 10min under 1000W power
Obtain graphene aqueous dispersions；
Step 5: the mixed system is mixed with the graphene aqueous dispersions, the ultrasound 20min under 1200W power
Obtain compound dispersing agent；
Step 6: by the compound dispersing agent inkjet printing or spraying or being painted on first insulating layer, Tu Yin
Amount is 26g/m2, then be placed in 80 DEG C of dryings in vacuum drying chamber and for 24 hours, form heating layer；
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer；
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 200g/m2, it is placed in true
90 DEG C of drying 3h, obtain thermo electric material in empty drying box；
Step 9: gained thermo electric material progress quenching treatment is partly gone after 2.5 times of energization 2h of its rated power
Except the defect group on graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity, formed structure compared with
For the relatively stable nano-cellulose graphene oxide thermo electric material of stabilization, power.
Embodiment 6
A kind of nano-cellulose graphene oxide thermo electric material, wherein including：Substrate；The heating layer being formed in substrate,
Wherein, the heating layer contains graphene, graphene oxide and nano-cellulose；And it is connected to the electrode of the heating layer.
The mass ratio of graphene is 50% in the heating layer, and the mass ratio of graphene oxide and nano-cellulose is 50%；Wherein, institute
State graphene oxide accounts for both graphene oxide and nano-cellulose gross mass 50%.
Embodiment 7
A kind of nano-cellulose graphene oxide thermo electric material, wherein including：Substrate；The heating layer being formed in substrate,
Wherein, the heating layer contains graphene, graphene oxide, nano-cellulose and hydrophobing agent；And it is connected to the heating layer
Electrode.Further include the first insulating layer being formed between the substrate and heating layer, and to be formed in the heating layer another
The second insulating layer in face.First insulating layer and second insulating layer are epoxy resin, polyurethane, heterocycle polymer, You Jiju
Object coating is closed, thickness is 0.02~0.3mm.The mass ratio of graphene is 50% in the heating layer, graphene oxide and nanometer
The mass ratio of cellulose is 49%, and the mass ratio of hydrophobing agent is 1%；Wherein, the graphene oxide accounts for graphene oxide and receives
The 50% of both rice celluloses gross mass.
Comparative example 1
Comparative example 1 and embodiment 1 difference lies in：It is added without graphene oxide, nano-cellulose and graphene is used only
Contrast material 1 is made, and the content of graphene is 50%, i.e., the mass ratio of nano-cellulose and graphene is 1:1.
Specially：Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprayed in substrate surface
It applies coating and forms the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: weighing 1:The graphene and nano-cellulose of 1 mass ratio, i.e. graphene 5g, nano-cellulose 5g, will claim
The nano-cellulose taken is mixedly configured into the aqueous dispersions of concentration 0.5mg/ml, under 800W power after ultrasonic disperse 50min
To mixed system.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasound 50min is obtained under 900W power
To compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Graphene, graphene oxide and nano-cellulose dry weight meter), then 70 DEG C of dry 15h in vacuum drying chamber are placed in, form fever
Layer；The size of heating layer is across two end electrodes 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length
15mm (power connection end), the other end are less than electrode length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain drying material in empty drying box；
Step 9: gained drying material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, contrast material 1 is obtained.
Comparative example 2
Comparative example 2 the difference from example 2 is that：It is added without graphene oxide, nano-cellulose and graphene is used only
Contrast material 2 is made, and the content of graphene is 35%, i.e., the mass ratio of nano-cellulose and graphene is 0.65:0.35.
Specially：Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprayed in substrate surface
It applies coating and forms the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: in mass ratio 0.35：0.65 weighs graphene and nano-cellulose, i.e. graphene 3.5g, nanofiber
The nano-cellulose weighed is mixedly configured into concentration 0.5mg/ml aqueous dispersions, the ultrasonic disperse under 800W power by plain 6.5g
Mixed system is obtained after 50min.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasound 50min is obtained under 900W power
To compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Graphene, graphene oxide and nano-cellulose dry weight meter), then 70 DEG C of dry 15h in vacuum drying chamber are placed in, form fever
Layer；The size of heating layer is across two end electrodes 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length
15mm (power connection end), the other end are less than electrode length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain drying material in empty drying box.
Step 9: gained drying material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, contrast material 2 is obtained.
Comparative example 3
Comparative example 3 and embodiment 3 difference lies in：It is added without graphene oxide, nano-cellulose and graphene is used only
Contrast material 3 is made, and the content of graphene is 55%, i.e., the mass ratio of nano-cellulose and graphene is 0.45:0.55.
Specially：Step 1: choosing substrate, in substrate after the drying of paint surfaces activating agent, sprayed in substrate surface
It applies coating and forms the first insulating layer, coating weight 100g/m2, it is placed in 80 DEG C of drying 5h in vacuum drying chamber.
Electrode is made Step 2: copper foil is adhered on substrate insulation coating；Two interelectrode distances and orientation root
Depending on required efficient heat generation breadth and base type face.
Step 3: in mass ratio 0.55：0.45 weighs graphene and nano-cellulose, i.e. graphene 5.5g, nanofiber
The nano-cellulose weighed is mixedly configured into the aqueous dispersions of concentration 0.5mg/ml by plain 4.5g, the ultrasound point under 800W power
Mixed system is obtained after dissipating 50min.
Step 4: the graphene aqueous dispersions of a concentration of 0.5mg/ml are prepared using the graphene weighed, in 800W power
Lower ultrasonic disperse 50min obtains graphene aqueous dispersions.
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasound 50min is obtained under 900W power
To compound dispersing agent.
Step 6: by the compound dispersing agent inkjet printing on first insulating layer, Tu Yinliang 15g/m2It (presses
Graphene, graphene oxide and nano-cellulose dry weight meter), then 70 DEG C of dry 15h in vacuum drying chamber are placed in, form fever
Layer；The size of heating layer is across two end electrodes 5mm or more；It is parallel to electrode length direction, one end size is less than electrode length
15mm (power connection end), the other end are less than electrode length 3mm.
Step 7: according to preset efficient heat generation face shape and size, either manually or mechanically being polished using sand paper, it is extra to remove
Heating layer.
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight 100g/m2, it is placed in true
80 DEG C of drying 5h, obtain drying material in empty drying box.
Step 9: gained drying material progress quenching treatment is partly gone after 1.5 times of energization 12h of its rated power
Except the defect group on graphene and graphene oxide thin slice, contrast material 3 is obtained.
Date comprision
(1)
Fig. 1 is the scanning electron microscope (SEM) photograph that nano-cellulose graphene oxide thermo electric material made from embodiment amplifies 1000 times
Piece.The Dispersion on surface degree of material is relatively uniform as seen from Figure 1, and mixability is high, this is because graphene well into
Graphene oxide forms the structure of dispersion degree uniformly, stable with the skeleton organization of nano-cellulose mixed system composition.
Fig. 2 is the scanning electron microscopic picture of 1000 times of 1 amplification factor of contrast material made from comparative example 1.Fig. 2 can see very
Material surface is clearly visible there are the same structure of cobweb, these spider web frames are that nano-cellulose fails to fill with graphene
Point mixing and float on material surface formation, basic reason is that the cross-linked structure that is formed due to nano-cellulose itself is not bright enough
Aobvious, graphene fails to evenly spread in nano-cellulose, therefore stability of material obtained is poor.
(2) material made from Examples 1 to 3 and comparative example 1~3 is subjected to energizing test and thermogravimetric analysis, record is logical
Electric situation and thermogravimetric situation.
Fig. 3 is that nano-cellulose graphene oxide thermo electric material made from embodiment 1 of the present invention and comparative example 1 are made
The energization situation comparison diagram of the contrast material 1 obtained；Wherein ,-graphene content 50%, the thick line pair of graphene oxide is not added
What is answered is the energization situation of the material of embodiment 1 ,-content of graphite 50%, be not added graphene oxide filament it is corresponding be pair
Than the energization situation of material 1, from figure 3, it can be seen that with the increase of conduction time, 1 corresponding material temperature of embodiment increases
Faster and higher, illustrate nano-cellulose graphene oxide thermo electric material made from the present embodiment 1 have better thermal conductivity
Can, there is a degree of promotion compared to contrast material 1.
Fig. 4 is that nano-cellulose graphene oxide thermo electric material made from embodiment 2 of the present invention and comparative example 2 are made
The energization situation comparison diagram of the contrast material 2 obtained；Wherein ,-graphene content 35%, the thick line pair of graphene oxide is not added
What is answered is the energization situation of the material of embodiment 2 ,-content of graphite 35%, be not added graphene oxide filament it is corresponding be pair
Than the energization situation of material 2, from fig. 4, it can be seen that with the increase of conduction time, 2 corresponding material temperature of embodiment increases
Faster and higher, illustrate nano-cellulose graphene oxide thermo electric material made from the present embodiment 2 have better thermal conductivity
Can, there is a degree of promotion compared to contrast material 2.
Fig. 5 is that nano-cellulose graphene oxide thermo electric material made from embodiment 3 of the present invention and comparative example 3 are made
The energization situation comparison diagram of the contrast material 3 obtained；Wherein ,-graphene content 55%, the thick line pair of graphene oxide is not added
What is answered is the energization situation of the material of embodiment 3 ,-content of graphite 55, be not added graphene oxide filament it is corresponding be comparison
The energization situation of material 3, from fig. 5, it can be seen that with the increase of conduction time, 3 corresponding material temperature of embodiment is raised
Faster and higher, illustrate that nano-cellulose graphene oxide thermo electric material made from the present embodiment 3 has better heat conductivility,
There is a degree of promotion compared to contrast material 3.
Fig. 6 is that nano-cellulose graphene oxide thermo electric material made from embodiment 1 of the present invention and comparative example 1 are made
The thermogravimetric situation comparison diagram of the contrast material 1 obtained.Wherein, the corresponding lines expression of graphene oxide is added is embodiment 1
The thermogravimetric situation of material；The thermogravimetric situation for the contrast material 1 that the corresponding lines of graphene oxide indicate is not added, it can be with from Fig. 6
Find out, with the raising of temperature, the membrane material mass loss of graphene oxide is added compared with being added without graphene oxide membrane material
Mass loss is small.Thus nano-cellulose graphene oxide thermo electric material made from implementing 1, which can be explained, has more excellent heat
Stability.
In conclusion compared with traditional thermo electric material, nano-cellulose graphene oxide thermo electric material of the invention exists
Promotion with matter on heat conductivility and thermal stability.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily
Realize other modification.The present invention is not limited to specific details.
Claims (10)
1. a kind of nano-cellulose graphene oxide thermo electric material, wherein including：
Substrate；
The heating layer being formed in substrate, wherein the heating layer contains graphene, graphene oxide and nano-cellulose；
It is connected to the electrode of the heating layer.
2. nano-cellulose graphene oxide thermo electric material as described in claim 1, wherein the substrate has certain type
Face, the type face are curved surface, arc surface or plane.
3. nano-cellulose graphene oxide thermo electric material as claimed in claim 2, wherein further include being formed in the substrate
The first insulating layer between heating layer, and it is formed in the second insulating layer of the heating layer another side.
4. nano-cellulose graphene oxide thermo electric material as claimed in claim 3, wherein first insulating layer and second
Insulating layer is epoxy resin, polyurethane, heterocycle polymer, organic polymer paint, and thickness is 0.02~0.3mm.
5. nano-cellulose graphene oxide thermo electric material as claimed in claim 4, wherein the electrode is longer than the second insulation
Layer, shorter than the first insulating layer makes the electrode section expose, convenient for connecing electric energization.
6. nano-cellulose graphene oxide thermo electric material as described in claim 1, wherein graphene in the heating layer
Quality accounting is 25%~65%, and the quality accounting of graphene oxide and nano-cellulose is 35%~75%；Wherein, the oxygen
Graphite alkene accounts for the 10%~60% of both graphene oxide and nano-cellulose gross mass.
7. nano-cellulose graphene oxide thermo electric material as described in claim 1, wherein the heating layer further includes hydrophobic
Agent, the hydrophobing agent are fluoropolymer, fluorine containing silane, fluorination double-phobia polyurethane, nano silicon dioxide and perfluoroalkyl first
Any one in the emulsion mixture of the mixed solution of base acrylic copolymer, beeswax and palm wax；The hydrophobing agent additive amount
It is the 0.08%~4.2% of fever layer weight.
8. a kind of preparation method of nano-cellulose graphene oxide thermo electric material, wherein including：
Choose substrate；
It selects coating spraying or brushes and form the first insulating layer on the type face of the substrate；
Nano-cellulose and graphene oxide obtain after mixing dispersion mixed system or by graphene oxide, Nanowire
Dimension element and hydrophobing agent obtain mixed system after carrying out mixing dispersion；It will be mixed with the mixed system after graphene ultrasonic disperse,
Compound dispersing agent is obtained after continuing ultrasonic disperse, the compound dispersing agent by inkjet printing or spraying or is brushed into film forming
Method is coated on first insulating coating and forms heating layer；
Setting electrode is connect with the heating layer；
It selects coating spraying or brushes and obtain the nano-cellulose oxygen after formation second insulating layer on the heating layer
Graphite alkene thermo electric material.
9. the preparation method of nano-cellulose graphene oxide thermo electric material as claimed in claim 8, wherein specifically include with
Lower step：
Step 1: substrate is chosen, in substrate after the drying of paint surfaces activating agent, in substrate surface spraying or brushing paint
The first insulating layer is formed, coating weight is 50~200g/m2, it is placed in 70~90 DEG C of 3~6h of drying in vacuum drying chamber；
Electrode is made Step 2: copper foil or copper sheet are adhered on substrate insulation coating, or by conductive coating or conductive rubber
By printing or coated on forming electrode after drying on the first insulating layer；
Step 3: both graphene oxide, nano-cellulose are mixed or by graphene oxide, nano-cellulose and hydrophobing agent
Three is mixedly configured into the aqueous dispersions of a concentration of 0.1~2mg/ml, 10~70min of ultrasonic disperse under 300~1000W power
After obtain mixed system；
Step 4: the graphene aqueous dispersions of a concentration of 0.1~3mg/ml are prepared, the ultrasonic disperse 10 under 500~1000W power
~70min obtains graphene aqueous dispersions；
Step 5: the mixed system is mixed with the graphene aqueous dispersions, ultrasonic 20 under 300~1200W power~
100min obtains compound dispersing agent；
Step 6: by the compound dispersing agent inkjet printing or spraying or being painted on first insulating layer, Tu Yinliang 4
~26g/m2, then 50~80 DEG C of dryings 6 in vacuum drying chamber~for 24 hours are placed in, form heating layer；
Step 7: according to preset efficient heat generation face shape and size, is either manually or mechanically polished using sand paper and remove extra hair
Thermosphere；
Step 8: in the heating layer surface spraying or brushing second insulating layer, coating weight is 50~200g/m2, it is placed in vacuum
70~90 DEG C of 3~6h of drying, obtain thermo electric material in drying box；
Step 9: gained thermo electric material is subjected to quenching treatment, and after 1.5~2.5 times of its rated power 2~12h that are powered, portion
Defect group on point removal graphene and graphene oxide thin slice, improve electric conductivity and phase structure regularity to get to
The nano-cellulose graphene oxide thermo electric material that structure is relatively stable, power is relatively stable.
10. the preparation method of nano-cellulose graphene oxide thermo electric material as claimed in claim 9, wherein the oxidation
The ratio that graphene accounts for both the graphene oxide and nano-celluloses gross weight is 10%~60%, graphene oxide and nanometer
Both celluloses account for the 35%~75% of the heating layer quality；Hydrophobing agent is such as used, then the hydrophobing agent additive amount is fever
The 0.08%~4.2% of layer quality.
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