CN108584939A - A kind of titanium carbide of high dielectric/graphene composite thin film material preparation method - Google Patents
A kind of titanium carbide of high dielectric/graphene composite thin film material preparation method Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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Abstract
A kind of titanium carbide of high dielectric/graphene composite thin film material preparation method, it is related to a kind of preparation method of graphene composite thin film material.The invention aims to solve the problems, such as that the dielectric properties of existing graphene oxide film are low.Method：One, graphene oxide is prepared；Two, mixed solution is prepared；Three, TiC nanometer sheet solution is prepared；Four, it mixes, vacuum filtration obtains titanium carbide/graphene composite thin film material of high dielectric.The heat resistance of the titanium carbide of high dielectric prepared by the present invention/graphene composite thin film material is good, while improving dielectric constant, and dielectric constant is 20~160.The present invention can get a kind of titanium carbide of high dielectric/graphene composite thin film material.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene composite thin film material.
Background technology
Graphene is the laminated structure that carbon atom is constituted, because it is with high mechanical strength, excellent conduction and heat conduction
Property and abundant source (graphite), make its in recent years always be research hot topic.The physics that many mysteries are presented in graphene is special
Property, wherein it is exactly electric property to study most commonly used.It is that raw material prepares the one of graphene that graphene oxide, which is using graphene,
Kind presoma, itself is insulator, is a kind of potential dielectric material.
But the dielectric constant of the dielectric properties of graphene oxide film is not high at present, generally below 50, therefore limit
The extensive use in conventional energy storage device of graphene film.
Invention content
The invention aims to solve the problems, such as that the dielectric properties of existing graphene oxide film are low, and provide a kind of high
The titanium carbide of dielectric-graphene composite thin film material preparation method.
A kind of titanium carbide of high dielectric-graphene composite thin film material preparation method, is completed according to the following steps：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is that 1h~2h is stirred under 300r/min~400r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：60mL
~100mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 90 DEG C~95 DEG C, then heat preservation 30min at being 90 DEG C~95 DEG C in temperature~
35min obtains mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 100r/min~300r/min at room temperature, obtains graphene oxide water solution；By oxygen
Graphite aqueous solution is centrifuged under the centrifugal speed of 3000r/min~3500r/min, takes the upper layer after centrifugation clear
Liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 8000r/min~8500r/min again
Separation takes the deposit after centrifuging, then carries out freeze-drying 20h~for 24 hours at being -80 DEG C in temperature, obtains oxidation stone
Black alkene powder；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:(5mL~6mL)；
Two, mixed solution is prepared：
1., 3. graphene oxide powder that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 5g/L~15g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min~5000r/min, take
Supernatant liquor after centrifugation；Centrifugation again by the supernatant liquor obtained after centrifugation in 9000r/min~10000r/min is fast
Centrifuged again under degree, obtain lower sediment, to centrifugation after deionized water is added again in obtained lower sediment, then stirring
It is that 10min~30min is stirred under 100r/min~500r/min to mix speed, and the graphene oxide for obtaining even size distribution is molten
Liquid；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 5g/L~10g/L, size
The size of graphene oxide is 1 μm~50 μm in the graphene oxide solution being evenly distributed；
Three, TiC nanometer sheet solution is prepared：
1., by Ti3AlC2Be added to mass fraction be 98% the concentrated sulfuric acid in, then low whipping speed be 100r/min~
It is stirred to react 0.5h~2h under 300r/min, adds fluorination lithium powder, then reaction 10h at being 35 DEG C~50 DEG C in temperature~
14h obtains reaction solution；
Step 3 1. described in Ti3AlC2Quality and mass fraction be 98% the concentrated sulfuric acid volume ratio be (2g~
4g):30mL；
Step 3 1. described in fluorination lithium powder quality be 98% with mass fraction the volume ratio of the concentrated sulfuric acid be
(0.5g~2g):30mL；
2., reaction solution is cooled to room temperature, then in the case where centrifugal speed is 6000r/min~8000r/min centrifugation 10min~
20min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 2 times~4 times first, reuses nothing
It is neutrality, the solid matter after being cleaned that water-ethanol, which is cleaned to the pH value of cleaning solution,；
3., be added n,N-dimethylacetamide into the solid matter after cleaning, then under protection of argon gas and ultrasonic power
For ultrasound 3h~5h under 100W~500W, then in the case where centrifugal speed is 3000r/min~4000r/min centrifugation 10min~
20min, then take supernatant, then 10min, then taking precipitate matter are centrifuged in the case where centrifugal speed is 10000r/min, then to sediment
Deionized water is added in matter, then low whipping speed is to be stirred to react 10min~30min under 300r/min~500r/min, is obtained
The TiC nanometer sheet solution of size uniform distribution；
Step 3 1. described in Ti3AlC2Quality and step 3 3. in the volume ratio of DMAC N,N' dimethyl acetamide be (2g
~4g):100mL；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 1g/L~
2g/L, size are 0.3 μm~2 μm；
Four, it 1., by the graphene oxide solution of the TiC nanometer sheets solution of size uniform distribution and even size distribution mixes
It closes, then it is to be stirred to react 10h~14h under 300r/min~500r/min, then be in ultrasonic power that speed, which is stirred at room temperature,
Ultrasound 20min~40min, obtains the mixed solution of titanium carbide and graphene oxide under 500W~1000W；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide
The volume ratio of solution is (1~7):(14~20)；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then in room
It is filtered using Vacuum filtration device under temperature, filters 10h~20h in the case where vacuum degree is 0.2MPa~0.5MPa, then at room temperature certainly
It so dries, obtains titanium carbide/graphene composite thin film material of high dielectric.
The principle of the present invention：
The present invention uses oxidation-reduction method to obtain graphene oxide solution first, then is prepared into size by gradient centrifugation
Then the graphene oxide solution being evenly distributed prepares TiC nanometer sheet solution by chemical etching method, then prepares titanium carbide and oxygen
The mixed solution of graphite alkene obtains titanium carbide/graphene composite thin film material of high dielectric finally by vacuum filtration；
The present invention utilizes micro conductive carbonized titanium and the compound titanium carbide/graphene oxide THIN COMPOSITE that high dielectric is made of graphene oxide
Membrane material builds micro conductive network using it, the dielectric properties of graphene, titanium carbide/oxidation of high dielectric is greatly improved
Graphene composite thin film material is expected to a kind of following novel dielectric material for becoming flexible heat resistant.
Advantages of the present invention：
One, titanium carbide is typical transition metal carbide, and the structure of crystal determines that titanium carbide has high intensity, resistance to height
The excellent properties such as temperature, thermal conductivity, therefore, titanium carbide/graphene composite thin film material of high dielectric prepared by the present invention
Heat resistance it is good, while improving dielectric constant, dielectric constant is 20~160；
Two, titanium carbide/graphene composite thin film material flexibility stretch-proof of high dielectric prepared by the present invention, and resistance to height
Temperature is a kind of potential Inorganic Dielectric Material, and future is expected to be utilized on a large scale.
The present invention can get a kind of titanium carbide of high dielectric/graphene composite thin film material.
Description of the drawings
Fig. 1 is dielectric constant figure, in Fig. 11 be pure graphene film dielectric constant curve, 2 prepare for embodiment one
The dielectric constant curve of the titanium carbide of high dielectric/graphene composite thin film material, 3 be high dielectric prepared by embodiment two
The dielectric constant curve of titanium carbide/graphene composite thin film material, 4 for embodiment three prepare high dielectric titanium carbide/
The dielectric constant curve of graphene composite thin film material；
Fig. 2 is raman spectrum, in Fig. 21 be pure graphene film Raman curve, the 2 high dielectrics prepared for embodiment one
Titanium carbide/graphene composite thin film material Raman curve；Titanium carbide/oxygen of the 3 high dielectrics prepared for embodiment two
The Raman curve of graphite alkene composite film material；
Fig. 3 is XRD spectra, in Fig. 31 be pure graphene film XRD curves, the 2 high dielectrics prepared for embodiment one
The XRD curves of titanium carbide/graphene composite thin film material；Titanium carbide/oxidation stone of the 3 high dielectrics prepared for embodiment two
The XRD curves of black alkene composite film material.
Specific implementation mode
Specific implementation mode one：Present embodiment is a kind of titanium carbide of high dielectric-graphene composite thin film material,
Preparation method is completed according to the following steps：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is that 1h~2h is stirred under 300r/min~400r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：60mL
~100mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 90 DEG C~95 DEG C, then heat preservation 30min at being 90 DEG C~95 DEG C in temperature~
35min obtains mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 100r/min~300r/min at room temperature, obtains graphene oxide water solution；By oxygen
Graphite aqueous solution is centrifuged under the centrifugal speed of 3000r/min~3500r/min, takes the upper layer after centrifugation clear
Liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 8000r/min~8500r/min again
Separation takes the deposit after centrifuging, then carries out freeze-drying 20h~for 24 hours at being -80 DEG C in temperature, obtains oxidation stone
Black alkene powder；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:(5mL~6mL)；
Two, mixed solution is prepared：
1., 3. graphene oxide powder that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 5g/L~15g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min~5000r/min, take
Supernatant liquor after centrifugation；Centrifugation again by the supernatant liquor obtained after centrifugation in 9000r/min~10000r/min is fast
Centrifuged again under degree, obtain lower sediment, to centrifugation after deionized water is added again in obtained lower sediment, then stirring
It is that 10min~30min is stirred under 100r/min~500r/min to mix speed, and the graphene oxide for obtaining even size distribution is molten
Liquid；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 5g/L~10g/L, size
The size of graphene oxide is 1 μm~50 μm in the graphene oxide solution being evenly distributed；
Three, TiC nanometer sheet solution is prepared：
1., by Ti3AlC2Be added to mass fraction be 98% the concentrated sulfuric acid in, then low whipping speed be 100r/min~
It is stirred to react 0.5h~2h under 300r/min, adds fluorination lithium powder, then reaction 10h at being 35 DEG C~50 DEG C in temperature~
14h obtains reaction solution；
Step 3 1. described in Ti3AlC2Quality and mass fraction be 98% the concentrated sulfuric acid volume ratio be (2g~
4g):30mL；
Step 3 1. described in fluorination lithium powder quality be 98% with mass fraction the volume ratio of the concentrated sulfuric acid be
(0.5g~2g):30mL；
2., reaction solution is cooled to room temperature, then in the case where centrifugal speed is 6000r/min~8000r/min centrifugation 10min~
20min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 2 times~4 times first, reuses nothing
It is neutrality, the solid matter after being cleaned that water-ethanol, which is cleaned to the pH value of cleaning solution,；
3., be added n,N-dimethylacetamide into the solid matter after cleaning, then under protection of argon gas and ultrasonic power
For ultrasound 3h~5h under 100W~500W, then in the case where centrifugal speed is 3000r/min~4000r/min centrifugation 10min~
20min, then take supernatant, then 10min, then taking precipitate matter are centrifuged in the case where centrifugal speed is 10000r/min, then to sediment
Deionized water is added in matter, then low whipping speed is to be stirred to react 10min~30min under 300r/min~500r/min, is obtained
The TiC nanometer sheet solution of size uniform distribution；
Step 3 1. described in Ti3AlC2Quality and step 3 3. in the volume ratio of DMAC N,N' dimethyl acetamide be (2g
~4g):100mL；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 1g/L~
2g/L, size are 0.3 μm~2 μm；
Four, it 1., by the graphene oxide solution of the TiC nanometer sheets solution of size uniform distribution and even size distribution mixes
It closes, then it is to be stirred to react 10h~14h under 300r/min~500r/min, then be in ultrasonic power that speed, which is stirred at room temperature,
Ultrasound 20min~40min, obtains the mixed solution of titanium carbide and graphene oxide under 500W~1000W；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide
The volume ratio of solution is (1~7):(14~20)；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then in room
It is filtered using Vacuum filtration device under temperature, filters 10h~20h in the case where vacuum degree is 0.2MPa~0.5MPa, then at room temperature certainly
It so dries, obtains titanium carbide/graphene composite thin film material of high dielectric.
The principle of present embodiment：
Present embodiment uses oxidation-reduction method to obtain graphene oxide solution first, then is prepared by gradient centrifugation
Then the graphene oxide solution of even size distribution prepares TiC nanometer sheet solution by chemical etching method, then prepares titanium carbide
With the mixed solution of graphene oxide, titanium carbide/graphene composite thin film of high dielectric is obtained finally by vacuum filtration
Material；Present embodiment utilizes micro conductive carbonized titanium and the compound titanium carbide/oxidation stone that high dielectric is made of graphene oxide
Black alkene composite film material builds micro conductive network using it, the dielectric properties of graphene, the carbon of high dielectric is greatly improved
Change titanium/graphene composite thin film material and is expected to a kind of following novel dielectric material for becoming flexible heat resistant.
The advantages of present embodiment：
One, titanium carbide is typical transition metal carbide, and the structure of crystal determines that titanium carbide has high intensity, resistance to height
The excellent properties such as temperature, thermal conductivity, therefore, titanium carbide/graphene composite thin film of high dielectric prepared by present embodiment
The heat resistance of material is good, while improving dielectric constant, and dielectric constant is 20~160；
Two, titanium carbide/graphene composite thin film material flexibility stretch-proof of high dielectric prepared by present embodiment, and
High temperature resistant is a kind of potential Inorganic Dielectric Material, and future is expected to be utilized on a large scale.
Present embodiment can get a kind of titanium carbide of high dielectric/graphene composite thin film material.
Specific implementation mode two：Present embodiment is with one difference of specific implementation mode：Step 2 1. in by step 1
3. obtained graphene oxide powder is dissolved into water, graphene oxide solution is obtained；Step 2 1. described in graphite oxide
A concentration of 5g/L~10g/L of alkene solution；Step 2 2. in by graphene oxide solution 4000r/min~4500r/min's
It is centrifuged under centrifugal speed, takes the supernatant liquor after centrifugation；The supernatant liquor obtained after centrifugation is existed again
Centrifuged again under the centrifugal speed of 9500r/min~10000r/min, obtain lower sediment, to centrifugation after obtained lower layer
Deionized water is added in precipitation again, then low whipping speed is that 10min~20min is stirred under 100r/min~300r/min, is obtained
To the graphene oxide solution of even size distribution；Step 2 2. described in even size distribution graphene oxide solution
A concentration of 5g/L~6g/L, the size of graphene oxide is 1 μm~50 μm in the graphene oxide solution of even size distribution.Its
Its step is same as the specific embodiment one.
Specific implementation mode three：One of present embodiment and specific implementation mode one or two difference are：Step 2 1. in
3. graphene oxide powder that step 1 obtains is dissolved into water, graphene oxide solution is obtained；Step 2 1. described in
A concentration of 10g/L~15g/L of graphene oxide solution；Step 2 2. in by graphene oxide solution 4000r/min~
It is centrifuged under the centrifugal speed of 5000r/min, takes the supernatant liquor after centrifugation；The upper layer that will be obtained after centrifugation again
Clear liquid is centrifuged again under the centrifugal speed of 9000r/min~9500r/min, obtains lower sediment, to centrifugation after obtain
Lower sediment in be added deionized water again, then low whipping speed be stirring 20min under 300r/min~500r/min~
30min obtains the graphene oxide solution of even size distribution；Step 2 2. described in even size distribution graphite oxide
A concentration of 7g/L~8g/L of alkene solution, the size of graphene oxide is 1 μm in the graphene oxide solution of even size distribution
~50 μm.Other steps are the same as one or two specific embodiments.
Specific implementation mode four：One of present embodiment and specific implementation mode one to three difference are：Step 3 1. in
By Ti3AlC2It is added in the concentrated sulfuric acid that mass fraction is 98%, then low whipping speed is to be stirred under 200r/min~300r/min
0.5h~1h is reacted, fluorination lithium powder is added, then 10h~12h is reacted at being 35 DEG C~40 DEG C in temperature, obtains reaction solution.
Other steps are identical as specific implementation mode one to three.
Specific implementation mode five：One of present embodiment and specific implementation mode one to four difference are：Step 3 1. in
The Ti3AlC2Quality and mass fraction be 98% the volume ratio of the concentrated sulfuric acid be (2g~3g):30mL.Other steps with
Specific implementation mode one to four is identical.
Specific implementation mode six：One of present embodiment and specific implementation mode one to five difference are：Step 3 1. in
The volume ratio for the concentrated sulfuric acid that the quality of the fluorination lithium powder is 98% with mass fraction is (0.5g~1g):30mL.It is other
Step is identical as specific implementation mode one to five.
Specific implementation mode seven：One of present embodiment and specific implementation mode one to six difference are：Step 4 1. in
The volume ratio of the TiC nanometer sheets solution of the size uniform distribution and the graphene oxide solution of even size distribution is 7:
14.6.Other steps are identical as specific implementation mode one to six.
Specific implementation mode eight：One of present embodiment and specific implementation mode one to seven difference are：Step 4 1. in
The volume ratio of the TiC nanometer sheets solution of the size uniform distribution and the graphene oxide solution of even size distribution is 1:
(14~19).Other steps are identical as specific implementation mode one to seven.
Specific implementation mode nine：One of present embodiment and specific implementation mode one to eight difference are：Step 4 1. in
The volume ratio of the TiC nanometer sheets solution of the described size uniform distribution and the graphene oxide solution of even size distribution be (1~
7):19.8.Other steps are identical as specific implementation mode one to eight.
Specific implementation mode ten：One of present embodiment and specific implementation mode one to nine difference are：Step 4 2. in
The mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then utilizes vacuum at room temperature
Suction filtration device filters, and filters 10h~15h, then naturally dry at room temperature in the case where vacuum degree is 0.2MPa~0.3MPa, obtains height
The titanium carbide of dielectric/graphene composite thin film material.Other steps are identical as specific implementation mode one to nine.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：A kind of titanium carbide of high dielectric-graphene composite thin film material preparation method, is by following step
Suddenly it completes：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is to stir 1.5h under 300r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：
60mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 95 DEG C, then 30min is kept the temperature at being 95 DEG C in temperature, obtain mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 200r/min at room temperature, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant liquor after centrifugation；It will be obtained after centrifugation again
Supernatant liquor be centrifuged again under the centrifugal speed of 8000r/min, take centrifuge after deposit, then
Temperature is to carry out freeze-drying 20h at -80 DEG C, obtains graphene oxide powder；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:5mL；
Two, mixed solution is prepared：
1., 3. graphene oxide powder that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 10g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min, take the upper layer after centrifugation
Clear liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 10000r/min again, is obtained down
Layer precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is to be stirred under 300r/min
20min obtains the graphene oxide solution of even size distribution；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 5g/L, even size distribution
Graphene oxide solution in graphene oxide size be 1 μm~50 μm；
Three, TiC nanometer sheet solution is prepared：
1., by 3g Ti3AlC2It is added in the concentrated sulfuric acid that 30mL mass fractions are 98%, then low whipping speed is 100r/
It is stirred to react 1h under min, 1g fluorination lithium powders is added, then 12h is reacted at being 40 DEG C in temperature, obtains reaction solution；
2., by step 3 1. in obtained reaction solution be cooled to room temperature, then centrifuged in the case where centrifugal speed is 8000r/min
10min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 3 times first, reuses anhydrous second
It is neutrality, the solid matter after being cleaned that alcohol, which is cleaned to the pH value of cleaning solution,；
3., to step 3 2. in 100mL n,N-dimethylacetamide is added in solid matter after obtained cleaning, then
It is under protection of argon gas ultrasound 4h under 500W with ultrasonic power, then 10min is centrifuged in the case where centrifugal speed is 3000r/min, then takes
Supernatant, then 10min, then taking precipitate matter are centrifuged in the case where centrifugal speed is 10000r/min, then be added and go into deposit
Ionized water, then low whipping speed are to be stirred to react 20min under 300r/min, obtain the TiC nanometer sheet solution of size uniform distribution；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 1g/L, ruler
Very little is 0.3 μm~2 μm；
Four, it 1., by the graphene oxide solution of the TiC nanometer sheets solution of size uniform distribution and even size distribution mixes
It closes, then is stirred to react 12h under being 300r/min in room temperature and mixing speed, then the ultrasound 30min in the case where ultrasonic power is 1000W,
Obtain the mixed solution of titanium carbide and graphene oxide；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide
The volume ratio of solution is 1:19.8；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then in room
Temperature is lower to be filtered using Vacuum filtration device, is filtered 15h, then naturally dry at room temperature in the case where vacuum degree is 0.2MPa, is obtained height
The titanium carbide of dielectric/graphene composite thin film material.
Embodiment two：A kind of titanium carbide of high dielectric-graphene composite thin film material preparation method, is by following step
Suddenly it completes：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is to stir 1.5h under 300r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：
60mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 95 DEG C, then 30min is kept the temperature at being 95 DEG C in temperature, obtain mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 200r/min at room temperature, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant liquor after centrifugation；It will be obtained after centrifugation again
Supernatant liquor be centrifuged again under the centrifugal speed of 8000r/min, take centrifuge after deposit, then
Temperature is that freeze-drying 20h~for 24 hours is carried out at -80 DEG C, obtains graphene oxide powder；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:5mL；
Two, mixed solution is prepared：
1., 3. graphene oxide powder that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 10g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min, take the upper layer after centrifugation
Clear liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 10000r/min again, is obtained down
Layer precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is to be stirred under 300r/min
30min obtains the graphene oxide solution of even size distribution；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 10g/L, Size Distribution is equal
The size of graphene oxide is 1 μm~50 μm in even graphene oxide solution；
Three, TiC nanometer sheet solution is prepared：
1., by 3g Ti3AlC2It is added in the concentrated sulfuric acid that 30mL mass fractions are 98%, then low whipping speed is 100r/
It is stirred to react 1h under min, 1g fluorination lithium powders is added, then 12h is reacted at being 40 DEG C in temperature, obtains reaction solution；
2., by step 3 1. in obtained reaction solution be cooled to room temperature, then centrifuged in the case where centrifugal speed is 8000r/min
10min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 3 times first, reuses anhydrous second
It is neutrality, the solid matter after being cleaned that alcohol, which is cleaned to the pH value of cleaning solution,；
3., to step 3 2. in 100mL n,N-dimethylacetamide is added in solid matter after obtained cleaning, then
It is under protection of argon gas ultrasound 4h under 500W with ultrasonic power, then 10min is centrifuged in the case where centrifugal speed is 3000r/min, then takes
Supernatant, then 10min, then taking precipitate matter are centrifuged in the case where centrifugal speed is 10000r/min, then be added and go into deposit
Ionized water, then low whipping speed are to be stirred to react 20min under 300r/min, obtain the TiC nanometer sheet solution of size uniform distribution；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 2g/L, ruler
Very little is 0.3 μm~2 μm；
Four, it 1., by the graphene oxide solution of the TiC nanometer sheets solution of size uniform distribution and even size distribution mixes
It closes, then is stirred to react 12h under being 300r/min in room temperature and mixing speed, then the ultrasound 30min in the case where ultrasonic power is 1000W,
Obtain the mixed solution of titanium carbide and graphene oxide；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide
The volume ratio of solution is 1:19；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then in room
Temperature is lower to be filtered using Vacuum filtration device, is filtered 15h, then naturally dry at room temperature in the case where vacuum degree is 0.3MPa, is obtained height
The titanium carbide of dielectric/graphene composite thin film material.
Embodiment three：A kind of titanium carbide of high dielectric-graphene composite thin film material preparation method, is by following step
Suddenly it completes：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is to stir 1.5h under 300r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：
60mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 95 DEG C, then 30min is kept the temperature at being 95 DEG C in temperature, obtain mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 200r/min at room temperature, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant liquor after centrifugation；It will be obtained after centrifugation again
Supernatant liquor be centrifuged again under the centrifugal speed of 8000r/min, take centrifuge after deposit, then
Temperature is that 3h is dried at 70 DEG C, obtains graphene oxide；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:5mL；
Two, mixed solution is prepared：
1., 3. graphene oxide that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 10g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min, take the upper layer after centrifugation
Clear liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 10000r/min again, is obtained down
Layer precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is to be stirred under 300r/min
20min obtains the graphene oxide solution of even size distribution；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 10g/L, Size Distribution is equal
The size of graphene oxide is 1 μm~50 μm in even graphene oxide solution；
Three, TiC nanometer sheet solution is prepared：
1., by 3g Ti3AlC2It is added in the concentrated sulfuric acid that 30mL mass fractions are 98%, then low whipping speed is 100r/
It is stirred to react 1h under min, 1g fluorination lithium powders is added, then 12h is reacted at being 40 DEG C in temperature, obtains reaction solution；
2., by step 3 1. in obtained reaction solution be cooled to room temperature, then centrifuged in the case where centrifugal speed is 8000r/min
10min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 3 times first, reuses anhydrous second
It is neutrality, the solid matter after being cleaned that alcohol, which is cleaned to the pH value of cleaning solution,；
3., to step 3 2. in 100mL n,N-dimethylacetamide is added in solid matter after obtained cleaning, then
It is under protection of argon gas ultrasound 4h under 500W with ultrasonic power, then 10min is centrifuged in the case where centrifugal speed is 3000r/min, then takes
Supernatant, then 10min, then taking precipitate matter are centrifuged in the case where centrifugal speed is 10000r/min, then be added and go into deposit
Ionized water, then low whipping speed are to be stirred to react 20min under 300r/min, obtain the TiC nanometer sheet solution of size uniform distribution；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 2g/L, ruler
Very little is 0.3 μm~2 μm；
Four, it 1., by the graphene oxide solution of the TiC nanometer sheets solution of size uniform distribution and even size distribution mixes
It closes, then is stirred to react 12h under being 300r/min in room temperature and mixing speed, then the ultrasound 30min in the case where ultrasonic power is 1000W,
Obtain the mixed solution of titanium carbide and graphene oxide；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide
The volume ratio of solution is 7:14.6；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then in room
Temperature is lower to be filtered using Vacuum filtration device, is filtered 15h, then naturally dry at room temperature in the case where vacuum degree is 0.5MPa, is obtained height
The titanium carbide of dielectric/graphene composite thin film material.
Comparative example：The preparation method of pure graphene film, is specifically realized by the following steps：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in ice bath and stirring speed
Degree is to stir 1.5h under 300r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：
60mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionization is added into mixture A
Water, then the mixture that deionized water is added is warming up to 95 DEG C, then 30min is kept the temperature at being 95 DEG C in temperature, obtain mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added to mixture B
In, low whipping speed is to react 10min under 200r/min at room temperature, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant liquor after centrifugation；It will be obtained after centrifugation again
Supernatant liquor be centrifuged again under the centrifugal speed of 8000r/min, take centrifuge after deposit, then
Temperature is that 3h is dried at 70 DEG C, obtains graphene oxide；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2It is molten
The volume ratio of liquid is 1g:5mL；
Two, mixed solution is prepared：
1., 3. graphene oxide that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 10g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min, take the upper layer after centrifugation
Clear liquid；The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 10000r/min again, is obtained down
Layer precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is to be stirred under 300r/min
20min obtains the graphene oxide solution of even size distribution；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 10g/L, Size Distribution is equal
The size of graphene oxide is 1 μm~50 μm in even graphene oxide solution；
Three, the graphene oxide solution of even size distribution is added in the Buchner funnel for fixing filter paper, then in room
Mild vacuum degree is to be filtered by vacuum for 24 hours under 0.2MPa, then naturally dry at room temperature obtains pure graphene film.
Fig. 1 is dielectric constant figure, in Fig. 11 be pure graphene film dielectric constant curve, 2 prepare for embodiment one
The dielectric constant curve of the titanium carbide of high dielectric/graphene composite thin film material, 3 be high dielectric prepared by embodiment two
The dielectric constant curve of titanium carbide/graphene composite thin film material, 4 for embodiment three prepare high dielectric titanium carbide/
The dielectric constant curve of graphene composite thin film material；
From fig. 1, it can be seen that the dielectric constant of pure graphene film is 21, and the titanium carbide of high dielectric prepared by embodiment one/
The dielectric constant of graphene composite thin film material is 160, titanium carbide/graphene oxide of high dielectric prepared by embodiment two
The dielectric constant of composite film material is 123, titanium carbide/graphene composite thin film material of high dielectric prepared by embodiment three
The dielectric constant of material is 29.
Fig. 2 is raman spectrum, in Fig. 21 be pure graphene film Raman curve, the 2 high dielectrics prepared for embodiment one
Titanium carbide/graphene composite thin film material Raman curve；Titanium carbide/oxygen of the 3 high dielectrics prepared for embodiment two
The Raman curve of graphite alkene composite film material；
As can be seen from Figure 2,1350cm is respectively appeared in the relevant peaks D and G of graphene oxide-1、1590cm-1Near.
Fig. 3 is XRD spectra, in Fig. 31 be pure graphene film XRD curves, the 2 high dielectrics prepared for embodiment one
The XRD curves of titanium carbide/graphene composite thin film material；Titanium carbide/oxidation stone of the 3 high dielectrics prepared for embodiment two
The XRD curves of black alkene composite film material.
As can be seen from Figure 3, the diffraction maximum of graphene oxide and titanium carbide exists in laminated film.
Claims (10)
1. a kind of titanium carbide of high dielectric/graphene composite thin film material preparation method, it is characterised in that a kind of high dielectric
Titanium carbide-graphene composite thin film material preparation method complete according to the following steps：
One, graphene oxide is prepared：
1., natural graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then be in ice bath and mixing speed
1h~2h is stirred under 300r/min~400r/min, obtains mixture A；
Step 1 1. described in natural graphite and potassium permanganate mass ratio be 1:5；
Step 1 1. described in natural graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g：60mL~
100mL；
2., mixture A is heated to 35 DEG C, then keep the temperature 1h at being 35 DEG C in temperature, then deionized water is added into mixture A,
The mixture that deionized water is added is warming up to 90 DEG C~95 DEG C again, then heat preservation 30min at being 90 DEG C~95 DEG C in temperature~
35min obtains mixture B；
Step 1 2. described in mixture A and deionized water volume ratio be 1:1；
3., by mixture B cooled to room temperatures, then by mass fraction be 35% H2O2Solution is added in mixture B, room
The lower low whipping speed of temperature is to react 10min under 100r/min~300r/min, obtains graphene oxide water solution；By graphite oxide
Aqueous solution is centrifuged under the centrifugal speed of 3000r/min~3500r/min, takes the supernatant liquor after centrifugation；Again
The supernatant liquor obtained after centrifugation is centrifuged again under the centrifugal speed of 8000r/min~8500r/min,
The deposit after centrifuging is taken, then freeze-drying 20h~for 24 hours is carried out at being -80 DEG C in temperature, obtains graphene oxide powder
End；
Step 1 1. described in natural graphite quality and step 1 3. described in mass fraction be 35% H2O2Solution
Volume ratio is 1g:(5mL~6mL)；
Two, mixed solution is prepared：
1., 3. graphene oxide powder that step 1 obtains is dissolved into water, obtain graphene oxide solution；
Step 2 1. described in graphene oxide solution a concentration of 5g/L~15g/L；
2., graphene oxide solution is centrifuged under the centrifugal speed of 4000r/min~5000r/min, take centrifugation
Supernatant liquor afterwards；Again by the supernatant liquor obtained after centrifugation under the centrifugal speed of 9000r/min~10000r/min
Centrifuged again, obtain lower sediment, to centrifugation after deionized water is added again in obtained lower sediment, then in stirring speed
Degree is that 10min~30min is stirred under 100r/min~500r/min, obtains the graphene oxide solution of even size distribution；
Step 2 2. described in even size distribution graphene oxide solution a concentration of 5g/L~10g/L, Size Distribution
The size of graphene oxide is 1 μm~50 μm in uniform graphene oxide solution；
Three, TiC nanometer sheet solution is prepared：
1., by Ti3AlC2It is added in the concentrated sulfuric acid that mass fraction is 98%, then low whipping speed is 100r/min~300r/
It is stirred to react 0.5h~2h under min, fluorination lithium powder is added, then 10h~14h is reacted at being 35 DEG C~50 DEG C in temperature, obtains
To reaction solution；
Step 3 1. described in Ti3AlC2Quality and mass fraction be 98% the volume ratio of the concentrated sulfuric acid be (2g~4g):
30mL；
Step 3 1. described in fluorination lithium powder quality and mass fraction be 98% the concentrated sulfuric acid volume ratio be (0.5g~
2g):30mL；
2., reaction solution is cooled to room temperature, then in the case where centrifugal speed is 6000r/min~8000r/min centrifugation 10min~
20min, then supernatant is removed, obtain solid matter；It uses distilled water to clean solid matter 2 times~4 times first, reuses nothing
It is neutrality, the solid matter after being cleaned that water-ethanol, which is cleaned to the pH value of cleaning solution,；
3., n,N-dimethylacetamide is added into the solid matter after cleaning, then be with ultrasonic power under protection of argon gas
Ultrasound 3h~5h under 100W~500W, then 10min~20min is centrifuged in the case where centrifugal speed is 3000r/min~4000r/min,
Supernatant is taken again, then centrifuges 10min, then taking precipitate matter in the case where centrifugal speed is 10000r/min, then is added into deposit
Enter deionized water, then low whipping speed is to be stirred to react 10min~30min under 300r/min~500r/min, and it is equal to obtain size
The TiC nanometer sheet solution of even distribution；
Step 3 1. described in Ti3AlC2Quality and step 3 3. in DMAC N,N' dimethyl acetamide volume ratio be (2g~
4g):100mL；
Step 3 3. described in size uniform distribution TiC nanometer sheet solution in TiC nanometer sheets a concentration of 1g/L~2g/L,
Size is 0.3 μm~2 μm；
Four, it 1., by the TiC nanometer sheets solution that size uniform is distributed is mixed with the graphene oxide solution of even size distribution, then
Be stirred at room temperature speed be stirred to react 10h~14h under 300r/min~500r/min, then ultrasonic power be 500W~
Ultrasound 20min~40min, obtains the mixed solution of titanium carbide and graphene oxide under 1000W；
Step 4 1. described in size uniform distribution TiC nanometer sheets solution and even size distribution graphene oxide solution
Volume ratio be (1~7):(14~20)；
2., the mixed solution of titanium carbide and graphene oxide is added in the Buchner funnel for fixing filter paper, then at room temperature
It is filtered using Vacuum filtration device, filters 10h~20h in the case where vacuum degree is 0.2MPa~0.5MPa, then dry in the air naturally at room temperature
It is dry, obtain titanium carbide/graphene composite thin film material of high dielectric.
2. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
3. graphene oxide powder that step 1 obtains is dissolved into water in being characterized in that step 2 1., it is molten to obtain graphene oxide
Liquid；Step 2 1. described in graphene oxide solution a concentration of 5g/L~10g/L；Step 2 2. in graphene oxide is molten
Liquid is centrifuged under the centrifugal speed of 4000r/min~4500r/min, takes the supernatant liquor after centrifugation；It again will centrifugation
The supernatant liquor obtained after separation is centrifuged again under the centrifugal speed of 9500r/min~10000r/min, obtains lower layer
Precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is 100r/min~300r/
10min~20min is stirred under min, obtains the graphene oxide solution of even size distribution；Step 2 2. described in size point
A concentration of 5g/L~6g/L of the uniform graphene oxide solution of cloth aoxidizes stone in the graphene oxide solution of even size distribution
The size of black alkene is 1 μm~50 μm.
3. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
3. graphene oxide powder that step 1 obtains is dissolved into water in being characterized in that step 2 1., it is molten to obtain graphene oxide
Liquid；Step 2 1. described in graphene oxide solution a concentration of 10g/L~15g/L；Step 2 2. in by graphene oxide
Solution is centrifuged under the centrifugal speed of 4000r/min~5000r/min, takes the supernatant liquor after centrifugation；It again will be from
The supernatant liquor obtained after heart separation is centrifuged again under the centrifugal speed of 9000r/min~9500r/min, obtains lower layer
Precipitation, to centrifugation after deionized water is added again in obtained lower sediment, then low whipping speed is 300r/min~500r/
20min~30min is stirred under min, obtains the graphene oxide solution of even size distribution；Step 2 2. described in size point
A concentration of 7g/L~8g/L of the uniform graphene oxide solution of cloth aoxidizes stone in the graphene oxide solution of even size distribution
The size of black alkene is 1 μm~50 μm.
4. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
By Ti in being characterized in that step 3 1.3AlC2It is added in the concentrated sulfuric acid that mass fraction is 98%, then low whipping speed is 200r/
It is stirred to react 0.5h~1h under min~300r/min, adds fluorination lithium powder, then reacted at being 35 DEG C~40 DEG C in temperature
10h~12h obtains reaction solution.
5. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
Ti described in being characterized in that step 3 1.3AlC2Quality and mass fraction be 98% the concentrated sulfuric acid volume ratio be (2g~
3g):30mL。
6. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
The volume ratio for the concentrated sulfuric acid that the quality of fluorination lithium powder described in being characterized in that step 3 1. is 98% with mass fraction is
(0.5g~1g):30mL.
7. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
The graphene oxide of the TiC nanometer sheets solution and even size distribution of size uniform distribution described in being characterized in that step 4 1.
The volume ratio of solution is 7:14.6.
8. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
The graphene oxide of the TiC nanometer sheets solution and even size distribution of size uniform distribution described in being characterized in that step 4 1.
The volume ratio of solution is 1:(14~19).
9. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
The graphene oxide of the TiC nanometer sheets solution and even size distribution of size uniform distribution described in being characterized in that step 4 1.
The volume ratio of solution is (1~7):19.8.
10. a kind of titanium carbide/graphene composite thin film material preparation method of high dielectric according to claim 1,
It is characterized in that step 4 2. in the mixed solution of titanium carbide and graphene oxide is added to the Buchner funnel for fixing filter paper
In, then utilize Vacuum filtration device to filter at room temperature, suction filtration 10h~15h in the case where vacuum degree is 0.2MPa~0.3MPa, then
Naturally dry at room temperature obtains titanium carbide/graphene composite thin film material of high dielectric.
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| CN111372435A (en) * | 2020-04-25 | 2020-07-03 | 郑州大学 | MXene-based high-thermal-conductivity fireproof electromagnetic shielding composite film and preparation method thereof |
| CN111372435B (en) * | 2020-04-25 | 2022-04-12 | 郑州大学 | MXene-based high-thermal-conductivity fireproof electromagnetic shielding composite film and preparation method thereof |
| CN111999360A (en) * | 2020-09-01 | 2020-11-27 | 上海大学 | Graphene-based non-enzymatic glucose sensor and preparation method and application thereof |
| CN111999360B (en) * | 2020-09-01 | 2021-10-29 | 上海大学 | Graphene-based non-enzymatic glucose sensor and preparation method and application thereof |
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