CN104764779B - A kind of preparation method of spongy graphene/zinc oxide mixed structure flexibility gas sensor - Google Patents
A kind of preparation method of spongy graphene/zinc oxide mixed structure flexibility gas sensor Download PDFInfo
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- CN104764779B CN104764779B CN201510165996.6A CN201510165996A CN104764779B CN 104764779 B CN104764779 B CN 104764779B CN 201510165996 A CN201510165996 A CN 201510165996A CN 104764779 B CN104764779 B CN 104764779B
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Abstract
The present invention relates to a kind of preparation method of spongy graphene/zinc oxide mixed structure flexibility gas sensor, first foam metal is put into vacuum reaction stove heating region, vacuumize, while heated to predetermined temperature, by in hydrogen injection vacuum reaction stove, after being heated to predetermined temperature, it is passed through carbon source while keeps hydrogen flowing quantity constant, the substrate of Direct precipitation graphene is can obtain after 10 180 minutes；Then graphene/foam metal of preparation is immersed in etching solution, replaces the metal that defoams, Flexible graphene is pulled out from etching solution, cleaned, pulled out graphene with flexible substrate.Negative electrode finally is done to cover the flexible substrate of conductive graphene, platinized platinum is cooked to electrode, and Ag/Cl electrodes are reference electrode；In solution is filled, using the solution containing Zn as electrolyte, electrolytic growth nano structure of zinc oxide.Inventive sensor improves sensitivity and response speed, has important development prospect in environmental monitoring, chemical gas detection etc..
Description
Technical field
The present invention relates to a kind of preparation method of gas nanosensor, and in particular to one kind is based on three-dimensional grapheme and oxygen
Change the gas sensor preparation method of zinc nanometer mixed structure, belong to sensor technical field.
Background technology
Gas sensor has important work in current environment, chemical gas detection, food industry health detection etc.
With.The research of flexible substrate low temperature gas sensor makes to the monitoring range, optimization preparation process, reduction that expand sensor
Have great importance with loss and risk etc..Research and development have high sensitivity, high selectivity, quick response and stability good
Transparent/flexible gas sensitive to prepare high-performance gas sensor have the function that it is important.
Single graphene or zinc oxide gas sensor all have its defect, and not Portable belt, inflexibility, it is necessary to
New preparation technology is found to improve its performance and operational value, it is efficiently convenient to accomplish, large-scale production.Three-dimensional grapheme is significantly
Increase and gas-contact area, make its sensitivity higher.One-dimension zinc oxide nano-array is grown in Flexible graphene and built
Mix nanostructured, it is had the excellent air-sensitive performance of Flexible graphene and one-dimension zinc oxide nanostructured concurrently, be its in flexibility
New footpath is opened up in the application of low temperature gas sensor, has more excellent detection performance compared with traditional sensors.In theory should
There should be more preferable air-sensitive performance, up to now, we do not retrieve the experimental study of correlation, and this is the important of invention research
Starting point.
The content of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of spongy graphene/zinc oxide mixes
Close the preparation method of structural flexibility gas sensor.
The technical scheme that the present invention takes is：
A kind of preparation method of spongy graphene/zinc oxide mixed structure flexibility gas sensor, including step are as follows：
(1) chemical gaseous phase depositing process prepares spongy graphene material on foam metal
Foam metal is put into vacuum reaction stove heating region, vacuumizes, heats simultaneously, by hydrogen injection vacuum reaction stove
In, it is heated to constant temperature 10-30 minutes after 100-500 DEG C of predetermined temperature and then is annealed, is heated to predetermined temperature 900-
After 1100 DEG C, carbon source is passed through vacuum reaction stove, while keeps hydrogen flowing quantity constant, gas is closed simultaneously after growing 5-180 minutes
It is down to the substrate that room temperature can obtain Direct precipitation graphene, i.e. graphene/foam metal；
(2) flexible spongy graphene preparation and transfer graphene/foam metal of preparation is immersed in etching solution
In, control the reaction time its metal is displaced by chemistry and become Flexible graphene, seal style transfer method is used with flexible substrate
Graphene is pulled out, naturally dry, obtain flexible spongy graphene；
(3) three-electrode method on flexible substrate graphene growth of zinc oxide nano structure to cover flexible spongy stone
The flexible substrate of black alkene does negative electrode, and platinized platinum is cooked to electrode, and Ag/AgCl electrodes are reference electrode；In potassium chloride fills solution, with
Solution containing Zn is electrolyte, the electrolytic growth nano structure of zinc oxide under 20-80 DEG C of low temperature, obtains graphene/zinc oxide and mixes
Close structure；
(4) electrode material is prepared at graphene/zinc oxide mixed structure both ends, has just obtained corresponding gas sensor.
In above-mentioned preparation method,
Foam metal described in step (1) is nickel foam, palladium, ruthenium, iridium, one kind in copper or foamed alloy, described
The size of foam metal is 1cm × 1cm-30cm × 30cm, and the carbon source is the one or several kinds in methane, acetylene, ethene,
The flow control of the carbon source is higher than 99.99% in 1-300sccm, purity；The flow of the hydrogen is controlled in 1-100sccm,
Purity is higher than 99.99%, and the vacuum reaction stove evacuation degree is 3 × 10-3-3×10-6Torr, to remove the activity in furnace chamber
Gas, keeps the growing environment of cleaning, and described annealing refers to dispelling substrate surface the process of the magazines such as oxide, obtained
After the substrate of Direct precipitation graphene, carbon-source gas valve is closed, keeps the constant cooling of hydrogen flowing quantity, takes out the stone of deposition afterwards
Black alkene.
The method for taking out backing material is to wait after vacuum reaction furnace temperature drops to room temperature, closes hydrogen gas valve, true
Empty pump, an atmospheric pressure state is filled to by furnace cavity is reacted with air, then takes out backing material, the graphene of preparation/
The number of plies of graphene is 1-10 layers in foam metal.
Etching solution described in step (2) is iron chloride or iron nitrate solution, and the solution concentration is 0.5-5mol/L；
Described flexible substrate is the substrates such as PMMA, PDFS；The reaction time, the reaction temperature was between 15-1000 minutes
10-50℃；The seal style transfer method is specially：It is covered in flexible substrate in spongy graphene, it is light to press the 10-30 seconds, so
Slowly gently lifted from a side of substrate afterwards, using the small contact force between graphene and substrate, by graphene substrate
Pull out.
Filling solution described in step (3) is KCl solution, concentration 1.5-5mol/L；The electrolyte is zinc nitrate
The aqueous solution, concentration 1.5-5mol/L.
Electrode material is prepared in step (4) includes two methods, first, directly using adhesive tape or glue by stretchable conduction
The disconnected both ends for sticking at graphene/zinc oxide mixed structure of material；The electrode material include stretchable conductive carbon fibre,
The stretchable fiber electrodes such as conductive carbon nanotube fiber, conductive graphene fiber.The second is it can directly drawn using depositing device
The upper disconnected electrode material of both ends deposition of graphene/zinc oxide mixed structure is stretched, specifically includes following preparation process：
(1) graphene/zinc oxide mixed structure is put into low temperature depositing system；
(2) preparing both ends has the shutter of rectangle sky bar, is placed in the top of graphene/zinc oxide mixed structure, pays attention to
Mixed structure can not be contacted, in order to avoid gas sensitive prepared by damage；
(3) metal electrode of not UNICOM is deposited at graphene/zinc oxide mixed structure both ends using depositing device；
The depositing device includes the low temperature depositing systems such as magnetron sputtering deposition system, evaporator, impulse laser deposition system
System；Described electrode material includes the metal materials such as copper, iron, silver, platinum.
Graphene prepared by the present invention/zinc oxide mixed structure has extraordinary electric conductivity, it is not necessary to middle grid
Shape electrode, unlike Semiconductor gas sensors material.
The present invention prepares the graphene of large area different shape using chemical vapour deposition technique, and flexibility is transferred to by wet method
Substrate, through optimization two kinds of gas sensitives of graphene and zinc oxide, prepare gas sensor.Flexible substrate expands detection model
Enclose, environmental protection and cost is cheap is light flexible, and abandoning tradition rigid material is heavy, not Portable belt and the shortcomings that inflexibility；Three
Dimension structure adds and gas-contact area, takes full advantage of the adsorption capacity of graphene；Zinc oxide has excellent air-sensitive special
Property, the two mixes the excellent properties for making the invention have two kinds of gas sensitives concurrently, so as to improve sensitivity and response speed, in environment
Monitoring, chemical gas detection etc. have important development prospect.
The invention has the advantages that
1) spongy graphene growth temperature accurately controls；
2) the graphene defect peak of growth is low, has high crystal mass；
3) graphene of growth has fabulous electrical conductivity；
4) the graphene size of growth is only limited by CVD cavitys, and the large area deposition of graphene can be achieved；
5) PMMA glue need not be used in wet method transfer process, it is time saving and energy saving；
6) transfer process using seal style shift, graphene will not any drift in the solution, avoid stone in transfer process
The damage of black alkene, process are simple and easy.
Brief description of the drawings
Fig. 1 is the schematic diagram that the embodiment of the present invention prepares graphene/zinc oxide mixed structure.
Fig. 2 is the SEM figures that the embodiment of the present invention prepares graphene/zinc oxide mixed structure.
Fig. 3 flexibilities spongy graphene/zinc oxide mixed structure formation state (left side) and case of bending (right side) image.
Fig. 4 is that the air-sensitive property under the case of bending of graphene/zinc oxide mixed structure prepared by the embodiment of the present invention is surveyed
Attempt.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example and be only limitted to the interpretation present invention, be not intended to limit the present invention.The material unless otherwise instructed can be from open business
Industry approach and obtain.
Embodiment 1
Graphene/zinc oxide mixed structure is grown in nickel foam Grown graphene and finally, as shown in figure 1, bag
Include following preparation process：
1. size is taken to be placed in for 6cm × 8cm nickel foams in tube furnace；
2. open vavuum pump is evacuated to end vacuum state 3 × 10 by the air pressure of tube furnace-6Hold in the palm (Torr)；
3. keep vacuum state 3 × 10-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes
Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
After 5. tubular type furnace temperature is warming up to 300 DEG C, constant temperature is annealed for 20 minutes；
After 6. tubular type furnace temperature is warming up to 10000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as
200sccm, stop 30 minutes and grown；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with 30-60 DEG C/min speed；
8. close hydrogen flowmeter and vavuum pump；
9. opening valve, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. opening quartz ampoule vacuum interface, the nickel foam of deposited graphite alkene is taken out；
11. graphene/the nickel foam prepared is immersed in FeCl3180 minutes in (1mol/L) solution；
12. spongy graphene is respectively washed 3 minutes with acetone, ethanol and deionized water；
13. being covered in graphenic surface with flexible substrate, light pressure 15 seconds, then slowly gently lifted from a side of substrate
Rise；
14. dry in the air in an atmosphere 3 hours；
15. the Flexible graphene substrate of preparation is put into 1.5mol/L KCl solution, to cover the soft of conductive graphene
Property substrate does negative electrode, and platinized platinum is cooked to electrode, and Ag/AgCl electrodes are reference electrode, using zinc nitrate solution as electrolyte, at low temperature
Growth of zinc oxide nano structure；
Test prepares the gas-sensitive property of graphene/zinc oxide mixed structure：Accompanying drawing 2 is that the embodiment of the present invention prepares graphite
The SEM figures of alkene/zinc oxide mixed structure.Accompanying drawing 4 prepares the air-sensitive property figure of mixed structure for the present invention, has preferable air-sensitive
Performance.
16. preparing electrode material at graphene/zinc oxide mixed structure both ends, corresponding gas sensor has just been obtained.
Embodiment 2
Graphene/zinc oxide mixed structure is grown in foam copper Grown graphene and finally, as shown in figure 1, bag
Include following preparation process：
1. size is taken to be placed in for 6cm × 8cm foam coppers in tube furnace；
2. open vavuum pump is evacuated to end vacuum state 3 × 10 by the air pressure of tube furnace-6Hold in the palm (Torr)；
3. keep vacuum state 3 × 10-6Torr after 15 minutes (dispel inside quartz ampoule by the vacuum effect of 15 minutes
Impurity, air etc., it is ensured that reaction chamber is clean), the air pressure of quartz ampoule 3 is raised to 3 × 10-3Torr；
4. hydrogen flowmeter is set as 100sccm, by hydrogen injection vacuum chamber；
After 5. tubular type furnace temperature is warming up to 300 DEG C, constant temperature is annealed for 20 minutes；
After 6. tubular type furnace temperature is warming up to 10000 DEG C, methane is injected in vacuum chamber, gas flowmeter is set as
200sccm, stop 30 minutes and grown；
7. close methane gas flowmeter and tubular type furnace temperature is quickly down to room temperature with 30-60 DEG C/min speed；
8. close hydrogen flowmeter and vavuum pump；
9. opening valve, quartz ampoule air pressure is filled to an atmospheric pressure state with air；
10. opening quartz ampoule vacuum interface, the foam copper of deposited graphite alkene is taken out；
11. graphene/the foam copper prepared is immersed in FeCl3180 minutes in (1mol/L) solution；
12. spongy graphene is respectively washed 3 minutes with acetone, ethanol and deionized water；
13. graphenic surface is covered in the stretchable adhesive tapes of 3M of pre-stretching, light pressure 15 seconds, then slowly from the one of substrate
Gently lift individual side；
14. drying in the air in an atmosphere 3 hours, the substrate of pre-stretching is allowed to reply the original length；
15. the stretchable graphene substrate of preparation is put into 1.5mol/L KCl solution, to cover conductive graphene
Flexible substrate does negative electrode, and platinized platinum is cooked to electrode, and Ag/AgCl electrodes are reference electrode, using zinc nitrate solution as electrolyte, in low temperature
Lower growth of zinc oxide nano structure；
16. preparing electrode material at graphene/zinc oxide mixed structure both ends, corresponding gas sensor has just been obtained.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this hair is not limited to
Bright, although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or equivalent substitution is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc., protection scope of the present invention should be included in
Within.
Claims (3)
1. a kind of preparation method of spongy graphene/zinc oxide mixed structure flexibility gas sensor, it is characterized in that, including step
It is rapid as follows：
（One）Chemical gaseous phase depositing process prepares spongy graphene material on foam metal
Foam metal is put into vacuum reaction stove heating region, vacuumizes, heats simultaneously, by hydrogen injection vacuum reaction stove,
After being heated to 100-500 DEG C of predetermined temperature then constant temperature 10-30 minutes are annealed, and are heated to 900-1100 DEG C of predetermined temperature
Afterwards, carbon source is passed through vacuum as 3 × 10-3-3×10-6Torr vacuum reaction stoves, while keep hydrogen flowing quantity constant, carbon source
Flow control is higher than 99.99% in 1-300sccm, purity；The flow control of the hydrogen is higher than in 1-100sccm, purity
99.99%, close gas after growing 5-180 minutes and be down to the substrate that room temperature can obtain Direct precipitation graphene, i.e. graphite
Alkene/foam metal；
（Two）The preparation and transfer of flexible spongy graphene
Graphene/foam metal of preparation is immersed in 0.5-5mol/L iron chloride or ferric nitrate etching solution, control reaction
Minute time 15-1000, reaction temperature are 10-50 DEG C, its metal is displaced by chemistry and become Flexible graphene, use flexible liner
Graphene is pulled out using seal style transfer method in bottom, naturally dry, obtains flexible spongy graphene, the seal style transfer method tool
Body is light to press the 10-30 seconds to be covered in flexible substrate in spongy graphene, is then slowly gently lifted from a side of substrate
Rise, using the small contact force between graphene and substrate, graphene substrate is pulled out；
（Three）Three-electrode method growth of zinc oxide nano structure on flexible substrate graphene
Negative electrode is done to cover the flexible substrate of flexible spongy graphene, platinized platinum is cooked to electrode, and Ag/AgCl electrodes are reference electricity
Pole, concentration be 1.5-5mol/L KCl fill solution in, using concentration be 1.5-5mol/L zinc nitrate aqueous solutions as electrolyte,
Electrolytic growth nano structure of zinc oxide under 20-80 DEG C of low temperature, obtain graphene/zinc oxide mixed structure；
（Four）Electrode material, which is prepared, at graphene/zinc oxide mixed structure both ends obtains corresponding gas sensor
Described electrode material includes metal material, stretchable fiber electrode；Preparing electrode material includes two methods, first,
Directly with adhesive tape or glue by the disconnected both ends for sticking at graphene/zinc oxide mixed structure of stretchable fiber electrode；Secondly
It is that disconnected electrode material is directly deposited at the both ends of stretchable graphene/zinc oxide mixed structure using depositing device.
A kind of 2. preparation of spongy graphene according to claim 1/zinc oxide mixed structure flexibility gas sensor
Method, it is characterized in that, step（One）Described in foam metal be nickel foam, palladium, ruthenium, iridium, one kind in copper or foam close
Gold；The size of the foam metal is 1cm × 1cm-30cm × 30cm.
A kind of 3. preparation of spongy graphene according to claim 1/zinc oxide mixed structure flexibility gas sensor
Method, it is characterized in that, step（One）Described in carbon source be methane, acetylene, the one or several kinds in ethene.
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| CN107474461B (en) * | 2016-06-08 | 2019-08-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene/polymer three-dimensional foam base plate, preparation method and application |
| CN106814110B (en) * | 2017-01-05 | 2020-11-06 | 华中科技大学 | Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof |
| CN106970128A (en) * | 2017-04-13 | 2017-07-21 | 浙江大学 | A kind of flexible ZnO nano crystalline substance compound carbon fiber and graphene oxide glucose detector and preparation method thereof |
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| CN108226242A (en) * | 2017-12-29 | 2018-06-29 | 苏州南尔材料科技有限公司 | A kind of preparation method of three-dimensional grapheme sensor electrode material |
| CN108147399A (en) * | 2017-12-29 | 2018-06-12 | 苏州南尔材料科技有限公司 | A kind of preparation method of three-dimensional grapheme nickel oxide sensor material |
| CN108249423A (en) * | 2017-12-29 | 2018-07-06 | 苏州南尔材料科技有限公司 | A kind of preparation method of nano-cerium oxide sensor material |
| CN108896621A (en) * | 2018-04-08 | 2018-11-27 | 山东大学 | A kind of ammonia gas sensor and preparation method thereof loading platinum grain |
| CN111474213B (en) * | 2020-04-29 | 2021-06-18 | 荷氢新能源科技(山东)有限公司 | Three-layer cylindrical composite graphene-based hydrogen sensor and preparation method thereof |
| CN111474214B (en) * | 2020-04-29 | 2021-06-25 | 荷氢新能源科技(山东)有限公司 | Graphene-based high-sensitivity hydrogen sensor and preparation method thereof |
| CN113552182A (en) * | 2021-07-23 | 2021-10-26 | 河北工业大学 | Preparation method of flexible gas sensor for fabric |
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