A kind of graphene-based flexible conducting membrane material and preparation method thereof
Technical field
The invention belongs to conductive material field, and in particular to a kind of graphene-based flexible conducting membrane material and its preparation side
Method.
Background technology
Conducting film is a kind of important photoelectric material, be widely used in touch-screen, liquid crystal display, Organic Light Emitting Diode show
Show, the photoelectric field such as solar cell.With the continuous progress of technology and product, it is desirable to conducting film towards flexibility, stably
Property well etc. develop by direction.The main material of traditional conducting film is ITO, copper, zinc oxide etc., wherein with ITO combination property most
Good, usage amount is also most, but ITO material resources are limited, inflexibility and easy moisture absorption are turned to be yellow, it is impossible to meet high-tech development
Demand.
Graphene be one kind by carbon atom with sp2Hybridized orbit composition hexangle type is in the flat film of honeycomb lattice, only
The two-dimensional material of one carbon atom thickness.Graphene has excellent theoretical electric conductivity, and intensity is high, while having excellent flexible
Property, heat endurance and chemical stability, electronic device, gas sensor, composite, photoelectric device, field emmision material and
The fields such as energy stores obtain extensive use.However, the resistance of prepared graphene membrane material is higher at present, actual electric conductivity is simultaneously
It is not good.Accordingly, it would be desirable to prepare a kind of good electric conductivity and flexible graphene-based conducting membrane material and preparation method thereof.
The content of the invention
The present invention to be solved at least one of prior art problem there is provided a kind of graphene-based flexible conducting membrane material and
Its preparation method.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions:
The invention discloses a kind of graphene-based flexible conducting membrane material, including flexible substrates and it is overlying on the flexible substrates
On conductive material, the conductive material is prepared by the component of following parts by weight:30-60 parts of graphene oxide, nanometer
7-18 parts of tantalum powder, 10-23 parts of polyaniline, 5-12 parts of polyvinyl alcohol, modified 7-15 parts of alum, 6-13 parts of formaldehyde modified lignin,
2-11 parts of sulfamic acid, 4-10 parts of Trimethylamine borine, 2-7 parts of nm-class active calcium carbonate, 2-8 parts of methylcellulose, poly- second two
25-36 parts of alcohol, 7-15 parts of ammonium poly-vanadate, 2-9 parts of lithium chlorate, 3-16 parts of dimethylformamide, 0.5mol/L salpeter solutions 65-
130 parts, 200-400 parts of water.
It is preferred that, the flexible substrates are PET, PBT or PVC.
It is further preferred that the conductive material is prepared by the component of following parts by weight:Graphene oxide 34-55
Part, 10-16 parts of nano-tantalum, 13-20 parts of polyaniline, 6-10 parts of polyvinyl alcohol, modified 8-13 parts of alum, formaldehyde modified lignin
7-11 parts, it is 3-9 parts of sulfamic acid, 5-9 parts of Trimethylamine borine, 3-6 parts of nm-class active calcium carbonate, 3-6 parts of methylcellulose, poly-
28-32 parts of ethylene glycol, 8-13 parts of ammonium poly-vanadate, 4-8 parts of lithium chlorate, 7-14 parts of dimethylformamide, 0.5mol/L salpeter solutions
73-125 parts, 250-380 parts of water.
A kind of preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 50-65
DEG C, suction filtration after stirring reaction 6-12h, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 150-400W, and ultrasonic time is 30-60min, and ultrasonic temperature is 25-40 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 200-300W, and ultrasonic time is 3-6h, and ultrasonic temperature is 60-80 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 100-400W, and ultrasonic time is 5-10 hours, and ultrasonic temperature is 25-40 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
Step 1 described above)In be heated to 58 DEG C, stirring reaction 10h.
Step 2 described above)Middle ultrasonic power is 320W, and ultrasonic time is 50min, and ultrasonic temperature is 35 DEG C.
Step 3 described above)Middle ultrasonic disperse power is 250W, and ultrasonic time is 5h, and ultrasonic temperature is 70 DEG C.
Step 4 described above)Middle ultrasonic power is 350W, and ultrasonic time is 7 hours, and ultrasonic temperature is 30 DEG C.
The present invention has the advantages that compared with prior art:
Graphene-based conductive membrane material prepared by the present invention improves the deficiencies in the prior art, prepared conducting membrane material
Square resistance is relatively low, respectively less than 10 Ω/, electrical conductivity up to 525.4 more than S/cm, and by 200 times bend after, conductive membrane material
Electrical conductivity conservation rate be more than 90.2%, display satisfactory electrical conductivity, resistance to bend(ing) is good, can meet the application in flexible electronic field
Demand.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.Following examples are used to illustrate the present invention,
But it is not limited to the scope of the present invention.
Embodiment 1
A kind of graphene-based flexible conducting membrane material, including flexible substrates and the conduction material being overlying in the flexible substrates
Material, the conductive material is prepared by the component of following parts by weight:30 parts of graphene oxide, 7 parts of nano-tantalum, polyaniline
10 parts, 5 parts of polyvinyl alcohol, modified 7 parts of alum, 6 parts of formaldehyde modified lignin, 2 parts of sulfamic acid, 4 parts of Trimethylamine borine, receive
2 parts of activated Calcium carbonate of rice, 2 parts of methylcellulose, 25 parts of polyethylene glycol, 7 parts of ammonium poly-vanadate, 2 parts of lithium chlorate, dimethylformamide
3 parts, 65 parts of 0.5mol/L salpeter solutions, 200 parts of water.
The flexible substrates are PET, PBT or PVC.
The preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 50 DEG C, stir
Suction filtration after reaction 6h is mixed, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 150W, and ultrasonic time is 30min, and ultrasonic temperature is 25 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 200W, and ultrasonic time is 3h, and ultrasonic temperature is 60 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 100W, and ultrasonic time is 5 hours, and ultrasonic temperature is 25 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
After tested, the square resistance of the conductive membrane material of preparation is 8.9 Ω/, and electrical conductivity is 525.4S/cm, by 200 times
After bending, its electrical conductivity conservation rate is 90.2%, stable electrical properties.
Embodiment 2
A kind of graphene-based flexible conducting membrane material, including flexible substrates and the conduction material being overlying in the flexible substrates
Material, the conductive material is prepared by the component of following parts by weight:60 parts of graphene oxide, 18 parts of nano-tantalum, polyphenyl
23 parts of amine, 12 parts of polyvinyl alcohol, modified 15 parts of alum, 13 parts of formaldehyde modified lignin, 11 parts of sulfamic acid, Trimethylamine borine
10 parts, 7 parts of nm-class active calcium carbonate, 8 parts of methylcellulose, 36 parts of polyethylene glycol, 15 parts of ammonium poly-vanadate, 9 parts of lithium chlorate, diformazan
16 parts of base formamide, 130 parts of 0.5mol/L salpeter solutions, 400 parts of water.
The flexible substrates are PET, PBT or PVC.
The preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 65 DEG C, stir
Suction filtration after reaction 12h is mixed, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 400W, and ultrasonic time is 60min, and ultrasonic temperature is 40 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 300W, and ultrasonic time is 6h, and ultrasonic temperature is 80 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 400W, and ultrasonic time is 10 hours, and ultrasonic temperature is 40 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
After tested, the square resistance of the conductive membrane material of preparation is 7.5 Ω/, and electrical conductivity is 583.7S/cm, by 200 times
After bending, its electrical conductivity conservation rate is 91.3%, stable electrical properties.
Embodiment 3
A kind of graphene-based flexible conducting membrane material, including flexible substrates and the conduction material being overlying in the flexible substrates
Material, the conductive material is prepared by the component of following parts by weight:45 parts of graphene oxide, 12 parts of nano-tantalum, polyphenyl
16 parts of amine, 8 parts of polyvinyl alcohol, modified 11 parts of alum, 10 parts of formaldehyde modified lignin, 6 parts of sulfamic acid, Trimethylamine borine 7
Part, 4.5 parts of nm-class active calcium carbonate, 5 parts of methylcellulose, 30 parts of polyethylene glycol, 11 parts of ammonium poly-vanadate, 5 parts of lithium chlorate, diformazan
10 parts of base formamide, 97 parts of 0.5mol/L salpeter solutions, 300 parts of water.
The flexible substrates are PET, PBT or PVC.
The preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 57 DEG C, stir
Suction filtration after reaction 9h is mixed, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 270W, and ultrasonic time is 45min, and ultrasonic temperature is 32 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 250W, and ultrasonic time is 3-6h, and ultrasonic temperature is 75 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 250W, and ultrasonic time is 7 hours, and ultrasonic temperature is 32 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
After tested, the square resistance of the conductive membrane material of preparation is 8.4 Ω/, and electrical conductivity is 564.2S/cm, by 200 times
After bending, its electrical conductivity conservation rate is 90.9%, stable electrical properties.
Embodiment 4
A kind of graphene-based flexible conducting membrane material, including flexible substrates and the conduction material being overlying in the flexible substrates
Material, the conductive material is prepared by the component of following parts by weight:34 parts of graphene oxide, 10 parts of nano-tantalum, polyphenyl
13 parts of amine, 6 parts of polyvinyl alcohol, modified 8 parts of alum, 7 parts of formaldehyde modified lignin, 3 parts of sulfamic acid, 5 parts of Trimethylamine borine,
3 parts of nm-class active calcium carbonate, 3 parts of methylcellulose, 28 parts of polyethylene glycol, 8 parts of ammonium poly-vanadate, 4 parts of lithium chlorate, dimethyl formyl
7 parts of amine, 73 parts of 0.5mol/L salpeter solutions, 250 parts of water.
The flexible substrates are PET, PBT or PVC.
The preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 58 DEG C, stir
Suction filtration after reaction 10h is mixed, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 320W, and ultrasonic time is 50min, and ultrasonic temperature is 35 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 250W, and ultrasonic time is 5h, and ultrasonic temperature is 70 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 350W, and ultrasonic time is 7 hours, and ultrasonic temperature is 3 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
After tested, the square resistance of the conductive membrane material of preparation is 6.5 Ω/, and electrical conductivity is 603.6S/cm, by 200 times
After bending, its electrical conductivity conservation rate is 91.5%, stable electrical properties.
Embodiment 5
A kind of graphene-based flexible conducting membrane material, including flexible substrates and the conduction material being overlying in the flexible substrates
Material, the conductive material is prepared by the component of following parts by weight:55 parts of graphene oxide, 16 parts of nano-tantalum, polyphenyl
20 parts of amine, 10 parts of polyvinyl alcohol, modified 13 parts of alum, 11 parts of formaldehyde modified lignin, 9 parts of sulfamic acid, Trimethylamine borine 9
Part, 6 parts of nm-class active calcium carbonate, 6 parts of methylcellulose, 32 parts of polyethylene glycol, 13 parts of ammonium poly-vanadate, 8 parts of lithium chlorate, dimethyl
14 parts of formamide, 125 parts of 0.5mol/L salpeter solutions, 380 parts of water.
The flexible substrates are PET, PBT or PVC.
The preparation method of above-mentioned graphene-based flexible conducting membrane material, preparation process is as follows:
1)Add graphene oxide into 0.5mol/L salpeter solutions, add Trimethylamine borine, be heated to 58 DEG C, stir
Suction filtration after reaction 10h is mixed, and alternately washing is to neutrality with water and alcohol, freeze-drying obtains graphene, standby;
2)By above-mentioned graphene ultrasonic disperse in 1/2 water, dimethylformamide is added, graphene solution is made into, its
Middle ultrasonic power is 320W, and ultrasonic time is 50min, and ultrasonic temperature is 35 DEG C;
3)By nano-tantalum, polyaniline, polyvinyl alcohol, modified alum, formaldehyde modified lignin, sulfamic acid, trimethyl
Amine borine, nm-class active calcium carbonate, methylcellulose, polyethylene glycol, ammonium poly-vanadate, lithium chlorate are added in remaining 1/2 water, are surpassed
Sound is scattered to obtain mixed liquor A, and its ultrasonic disperse power is 250W, and ultrasonic time is 5h, and ultrasonic temperature is 70 DEG C;
4)By step 2)In graphene solution add to step 3)In mixed liquor A in, continue ultrasonic disperse mixed
Liquid B is closed, its ultrasonic power is 350W, and ultrasonic time is 7 hours, and ultrasonic temperature is 3 DEG C;
5)By mixed liquid B coating on a flexible substrate, through ultraviolet drying and burin-in process, that is, obtain graphene-based flexible and lead
Film material.
After tested, the square resistance of the conductive membrane material of preparation is 6.1 Ω/, and electrical conductivity is 615.8S/cm, by 200 times
After bending, its electrical conductivity conservation rate is 90.8%, stable electrical properties.
Comparative example 1
This comparative example the difference is that only with embodiment 2:Without nano-tantalum, formaldehyde modified lignin and lithium chlorate
And its correlation step.
After tested, the square resistance of the conductive membrane material of preparation is 14.5 Ω/, and electrical conductivity is 426.9S/cm, by 200
After secondary bending, its electrical conductivity conservation rate is 87.6%, stable electrical properties.
Comparative example 2
This comparative example the difference is that only with embodiment 2:Without nm-class active calcium carbonate and nano-tantalum and its phase
Close step.
After tested, the square resistance of the conductive membrane material of preparation is 17.7 Ω/, and electrical conductivity is 447.2S/cm, by 200
After secondary bending, its electrical conductivity conservation rate is 86.2%, stable electrical properties.
The square resistance of conductive membrane material prepared by the present invention is relatively low, respectively less than 10 Ω/, electrical conductivity up to 525.4 S/cm with
On, and after 200 times bend, the electrical conductivity conservation rate of conductive membrane material is more than 90.2%, display satisfactory electrical conductivity, resist bending
Property is good, can meet the application demand in flexible electronic field.