CN106959320B - A kind of sensing element and preparation method thereof of ionomer graphene complex - Google Patents
A kind of sensing element and preparation method thereof of ionomer graphene complex Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- 229920000554 ionomer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 43
- 229920001661 Chitosan Polymers 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- -1 graphite alkene Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 230000008602 contraction Effects 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
The present invention provides a kind of sensing elements of ionomer graphene complex, the sensing element is by chitosan ionic liquid film, and be clipped in chitosan ionic liquid film two sides graphene film electrode composition, the sensing element be bent when, generate potential between two layers of graphene film electrode.The sensing element can be used for sensor-based system, and when applying outer plus displacement signal, potential difference can be generated between Graphene electrodes.Sensing element Electric double-layer capacitor with higher.More traditional IPMC sensing element, the voltage value that intermediate ion polymer graphite alkene electrode composite sensing element of the present invention generates increase 2.7~27 times.
Description
Technical field
The present invention relates to a kind of sensing elements of ionomer graphene complex, belong to intellectual material field.
Background technique
In recent years, due to the sensings such as blood pressure measurement, vibration detection under low frequency (1~10Hz) and the application in terms of energy stores
Demand, numerous scholars are dedicated to studying the electromechanical transformation effect of ionic polymer metal complex (IPMC).But due to moisture
Son is easy to greatly reduce the electromechanical transformation effect of IPMC from having leakage in crannied metal electrode, evaporation.It is therefore necessary to
The carbon polymer composite material for studying the free from flaw electrode based on ionic liquid, to avoid the leakage and evaporation of working media.
Single-walled carbon nanotube is applied to electrode preparation due to possessing the advantages of metals such as high conductivity, high capacitance do not have, but single
Wall carbon nano tube is very rare, prohibitively expensive, is difficult evenly dispersed.Graphene is outstanding since its unique structure can provide
Electricity, calorifics and mechanical property, at the same it is relatively cheap, easily prepared, it is possible to instead of single-walled carbon nanotube in many occasions
Application.Smart electronics fabric, operation tool, biosensor and disposable biological medical devices call biodegradable, life
The ion-exchange polymer of object compatibility, research find ionic liquid and have biodegradable, biocompatibility and biology living
The chitosan of property is compatible on a molecular scale, their composite material can be applied to sense.Therefore in order to obtain free from flaw electrode,
Biocompatibility and stability can be used graphene, chitosan and ionic liquid and prepares ionomer graphene complex biography
Sensing unit.
Summary of the invention
The object of the present invention is to provide a kind of sensing element and preparation method thereof of ionomer graphene complex, with
Obtain free from flaw electrode, biocompatibility and the good sensing element of stability.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of sensing element of ionomer graphene complex, the sensing element by chitosan ionic liquid film, with
And it is clipped in the graphene film electrode composition of chitosan ionic liquid film two sides, when which is bent, in two layers of graphene film
Potential is generated between electrode.
The thickness range of the chitosan film is 0.1mm~0.5mm, and the thickness range of graphene film electrode is 10~50 μ
m。
It include ionic liquid in the chitosan ionic liquid film, ionic liquid is selected from 1- ethyl-3-methylimidazole tetrafluoro
Borate EMImBF4, 1- ethyl-3-methylimidazole rhodanate EMImSCN, 1- butyl -3- methyl imidazolium tetrafluoroborate
BMImBF4One kind.
The graphene film electrode nearby has a small broad peak at 21 ° of Bragg angle.
Interlamellar spacing in the graphene film is 0.31nm.
A kind of preparation method of the sensing element of ionomer graphene complex, includes the following steps:
Step 1, the preparation of the graphene film electrode containing ionic liquid: graphene solution is prepared first；Then, it uses
Anodics membrane filtration graphene solution obtains graphene film；It is prepared using the graphene film by capillary force compression process
Graphene film electrode containing ionic liquid；
Step 2, the preparation of chitosan ionic liquid film: chitosan is added in acetic acid solution, by mixed solution 60
30min is stirred at DEG C to form uniform solution；Then, glycerol and ionic liquid are added in above-mentioned mixed solution at 60 DEG C
30min is stirred, suspension is obtained；The suspension of acquisition is poured onto dimethyl silicone polymer mold, is placed at 60 DEG C of oven
4h is toasted, chitosan/glycerol/ionic liquid electrolyte film is obtained；
Step 3, the preparation of three layers of sensing element: the graphene film electrode and step prepared using hot press heat-press step 1
Chitosan/glycerol/ionic liquid electrolyte film of two preparations, temperature are 70 DEG C, and obtaining both sides is Graphene electrodes film, and centre is
The composite material of chitosan ion liquid polymer film, the as described sensing element.
In step 1, the step of preparing graphene solution are as follows: prepared aoxidize from graphite using improved hummers method first
Graphite, specifically: graphite is mixed in sulfuric acid and sodium nitrate, 5h is stirred；Then, by potassium permanganate under condition of ice bath slowly
It is added in said mixture；After stirring 4h, hydrogen peroxide is added in above-mentioned mixed solution, forms brown yellow solution；It should
Brown yellow solution is cleaned using hydrochloric acid and enough deionized waters；By graphite oxide suspension ultrasound 1h to remove graphite oxide,
The homogeneous solution of generation is mixed in deionized water, hydrazine, in the mixed solution of ammonium hydroxide composition, 3h is stirred at 95 DEG C, to obtain stone
Black alkene solution.
In step 1, the mass density of the graphene film is 1.0mg/cm2。
In step 1, the graphene film containing ionic liquid is prepared by capillary force compression process using graphene film
Specific steps are as follows: graphene film is put into the mixed solution of volatile liquid and non-volatile liquid, in the revolving speed of 400rpm
Persistently stir 12h down so that mixed solution is exchanged to graphene film, then under vacuum conditions, 50 DEG C of evaporation 12h, wave
Hair property liquid evaporation produces the compression of the capillary force between graphene layer, leads to the contraction and graphene bulk density of film thickness
Increase, non-volatile liquid is retained in inside graphene film；And by the ratio of volatile liquid and non-volatile liquid come
Adjust the bulk density of graphene.
The volatile liquid is deionized water, and non-volatile liquid is 1- ethyl-3-methylimidazole tetrafluoroborate
EMImBF4, 1- ethyl-3-methylimidazole rhodanate EMImSCN, 1- butyl -3- methyl imidazolium tetrafluoroborate BMImBF4's
It is a kind of.
The utility model has the advantages that sensing element preparation method of the invention is simple, Electric double-layer capacitor (304.6mF with higher
cm-2), at amplitude 2mm, the sinusoidal displacement input of 2~10Hz of frequency, it can produce the voltage value of 3.5~13.56mV, it is more traditional
IPMC sensing element (Palmre V, et al.International Journal of Smart and Nano
Materials, 2014,5 (2), 99-113.), intermediate ion polymer graphite alkene electrode composite of the present invention generates voltage value and increases
2.7~27 times, by amplifying circuit (amplification factor 148.5), voltage is generated up to 0.52~2.01V.And due to material
Internal working media is the stronger ionic liquid of stability, and as time increases, the stability for generating voltage is preferable.
Detailed description of the invention
Fig. 1 is the schematic diagram of the sensing element of polymer graphite alkene compound；
Fig. 2 is that the X-ray diffraction (XRD) of graphene film electrode is analyzed；
Fig. 3 is the section SEM picture of graphene film electrode；
Fig. 4 a- Fig. 4 d is that the SEM of ionomer graphene complex sensing element schemes, wherein figure a, figure b are surface；
Figure c is section；Scheme the interface that d is electrode and base film；
Fig. 5 is ionomer graphene complex sensing element CV curve；
Fig. 6 a- Fig. 6 d is the sensing characteristics of ionomer graphene complex sensing element.
Specific embodiment
Further explanation is done to the present invention with reference to the accompanying drawing.
As shown in Figure 1, a kind of sensing element of ionomer graphene complex, the sensing element is by chitosan ion
Liquid film, and it is clipped in the graphene film electrode composition of chitosan ionic liquid film two sides, when which is bent, at two layers
Potential is generated between graphene film electrode, there are stable sensing capabilities.Wherein, the bending of crooked sensory element can be by external force reality
It is existing.
The thickness range of chitosan film is 0.1mm~0.5mm, and the thickness range of graphene film electrode is 10~50 μm.
It include ionic liquid in chitosan ionic liquid film, ionic liquid is selected from 1- ethyl-3-methylimidazole tetrafluoro boric acid
Salt EMImBF4, 1- ethyl-3-methylimidazole rhodanate EMImSCN, 1- butyl -3- methyl imidazolium tetrafluoroborate BMImBF4
One kind.
Graphene film electrode nearby has a small broad peak at 21 ° of Bragg angle.Interlamellar spacing in graphene film is 0.31nm.
Embodiment
The preparation of the sensing element of ionomer graphene complex and its sensing capabilities test
1. preparation process:
The preparation of graphene film electrode of the step 1) containing ionic liquid: use improved hummers method from graphite system first
1g graphite is mixed in the sulfuric acid and 1g sodium nitrate that 18ml concentration is 98wt%, stirs 5h by standby graphite oxide；Then, by 3g
Potassium permanganate is slowly added in said mixture under condition of ice bath；It is the double of 10wt% by 100ml concentration after stirring 4h
Oxygen water is added in above-mentioned mixed solution, forms brown yellow solution；The brown yellow solution uses 100ml concentration for the salt of 10wt%
Sour and enough deionized water cleanings；By graphite oxide suspension ultrasound 1h to remove graphite oxide, the 6ml homogeneous solution of generation
It is mixed in 6ml deionized water, 5 μ l concentration are the hydrazine of 35wt%, and 42 μ l concentration are to stir at 95 DEG C in the ammonia spirit of 28wt%
3h is mixed, to obtain graphene solution；Then, use Anodics film (specification for 47mm in diameter, 0.2 μm of pore
size；Purchased from GE Whatman company) filtering graphite alkene solution, obtain graphene film, mass density 1.0mg/cm2.Using
The graphene film prepares the graphene film containing ionic liquid, step are as follows: above-mentioned graphene by capillary force compression process
Film is put into volatility and non-volatile mixed solution, persistently stirs 12h under the revolving speed of 400rpm, so that mixed solution is handed over
It shifts to inside graphene film, then under the vacuum condition of 10Pa, 50 DEG C of evaporation 12h, evaporation of volatile liquid produces graphite
The capillary force of alkene interlayer is compressed, and the contraction of film thickness and the increase of graphene bulk density are caused, and non-volatile liquid retains
Inside graphene film, bulk density is adjusted by the ratio of volatile liquid and non-volatile liquid, using deionized water
As volatile liquid, 1- ethyl-3-methylimidazole tetrafluoroborate EMImBF4As non-volatile liquid, concentration is
The EMImBF of 0.065M4The bulk density of the graphene film of acquisition is 1.25g/cm3.By x-ray radiation diffraction (XRD) at 21 °
Observe a small and wide peak, as shown in Fig. 2, according to Bragg equation: the interlamellar spacing for calculating graphene film is 0.31nm,
This illustrates graphene film, and there is no be piled into graphite again.The section SEM of graphene film electrode is as shown in Figure 3.
The preparation of step 2) chitosan ionic liquid film: 200mg chitosan is added to the second that 5ml mass concentration is 2%
In acid solution；Mixed solution stirs 30min at 60 DEG C to form uniform solution；Then, by 0.8g glycerol and 100mg ion
Liquid 1- ethyl-3-methylimidazole tetrafluoroborate EMImBF4It is added in above-mentioned chitosan mixed solution and is stirred at 60 DEG C
30min；The suspension of acquisition is poured onto PDMS mold (being 50mm × 30mm × 40mm having a size of length × width × height), is placed in roasting
4h is toasted at 60 DEG C of case, obtains chitosan/glycerol/BMIBF4Ionic dielectric film.
The preparation of three layers of driver of step 3): hot press hot pressing Graphene electrodes film and polymer film, temperature 70 are used
DEG C, obtaining both sides is Graphene electrodes film, and centre is the composite material of chitosan ion liquid polymer film.The ionomer
The SEM on graphene complex sensing element surface such as Fig. 4 a, shown in Fig. 4 b, it can be seen that the Graphene electrodes surface compact does not have
There is the crack of metal electrode, therefore ionic liquid will not leak；Ionomer graphene complex sensing element section SEM
Such as Fig. 4 c, shown in Fig. 4 d, interface does not see obvious boundary, illustrates that graphene film electrode is tight in conjunction with matrix ions polymer
It is close, good bonding strength.
2. sensing characteristics
The CV curve (Fig. 5) that the sensing element is tested by electrochemical workstation, does not observe redox reaction,
Illustrate that the sensing element has Electric double-layer capacitor characteristic, visible sweep speed of working as is from 100m V s in figure-1It is down to 1m V s-1When,
Electric double-layer capacitor is from 0.79mF cm-2Increase to 304.6mF cm-2.It is inputted in the sinusoidal displacement of amplitude 2mm, 2~10Hz of frequency
Under, it can produce the voltage value (Fig. 6 a) of 3.5~13.56mV, the voltage generated under 10Hz is up to 13.56mV (Fig. 6 c).Compared with biography
IPMC sensing element (Palmre V, the et al.International Journal of Smart and Nano of system
Materials, 2014,5 (2), 99-113.), intermediate ion polymer graphite alkene electrode composite of the present invention generates voltage value and increases
2.7~27 times, and as time increases, sensing capabilities have preferable stability (Fig. 6 b), this is because in material
The working media in portion is the stronger ionic liquid of stability.By amplifying circuit (amplification factor 148.5), it is reachable to generate voltage
0.52~2.01V, such as Fig. 6 d.
According to above-described embodiment, the present invention can be better understood.However, as it will be easily appreciated by one skilled in the art that real
Specific material specification (Graphene electrodes, ionic liquid model), process conditions and its result described in example is applied to be only used for
The bright present invention, without the present invention described in detail in claims should will not be limited.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of sensing element of ionomer graphene complex, it is characterised in that: the sensing element is by chitosan ion
Liquid film, and it is clipped in the graphene film electrode composition of chitosan ionic liquid film two sides, when which is bent, at two layers
Potential is generated between graphene film electrode；
The chitosan ionic liquid film is chitosan/glycerol/ionic liquid electrolyte film, and graphene film electrode is containing ionic liquid
The graphene film electrode of body.
2. the sensing element of ionomer graphene complex according to claim 1, it is characterised in that: the shell is poly-
The thickness range of sugared ionic liquid film is the mm of 0.1 mm ~ 0.5, and the thickness range of graphene film electrode is 10 ~ 50 μm.
3. the sensing element of ionomer graphene complex according to claim 1, it is characterised in that: the shell is poly-
It include ionic liquid in sugared ionic liquid film, ionic liquid is selected from 1- ethyl-3-methylimidazole tetrafluoroborate EMImBF4, 1-
Ethyl-3-methylimidazole rhodanate EMImSCN, 1-- 3-methyl imidazolium tetrafluoroborate of butyl BMImBF4One kind.
4. the sensing element of ionomer graphene complex according to claim 1 or 2, it is characterised in that: described
Graphene film electrode nearby has a small broad peak at 21 ° of Bragg angle.
5. the sensing element of ionomer graphene complex according to claim 1 or 2, it is characterised in that: described
Interlamellar spacing in graphene film electrode is 0.31nm.
6. a kind of preparation method of the sensing element of ionomer graphene complex, characterized by the following steps:
Step 1, the preparation of the graphene film electrode containing ionic liquid: graphene solution is prepared first；Then, using inorganic oxide
Aluminium film filtering graphite alkene solution obtains graphene film；Contained using the graphene film by the preparation of capillary force compression process
The graphene film electrode of ionic liquid；
Step 2, the preparation of chitosan ionic liquid film: chitosan is added in acetic acid solution, by mixed solution at 60 DEG C
30 min are stirred to form uniform solution；Then, glycerol and ionic liquid are added in above-mentioned mixed solution at 60 DEG C and are stirred
30 min are mixed, suspension is obtained；The suspension of acquisition is poured onto dimethyl silicone polymer mold, is placed at 60 DEG C of oven and dries
Roasting 4 h, obtain chitosan/glycerol/ionic liquid electrolyte film；
Step 3, the preparation of three layers of sensing element: the graphene film electrode and step 2 system prepared using hot press heat-press step 1
Standby chitosan/glycerol/ionic liquid electrolyte film, temperature are 70 DEG C, and obtaining both sides is Graphene electrodes film, and centre is that shell is poly-
The composite material of sugared ion liquid polymer film, the as described sensing element.
7. the preparation method of the sensing element of ionomer graphene complex according to claim 6, feature exist
In: in step 1, the step of preparing graphene solution are as follows: graphite oxide is prepared from graphite using improved hummers method first,
Specifically: graphite is mixed in sulfuric acid and sodium nitrate, 5h is stirred；Then, potassium permanganate is slowly added under condition of ice bath
Into said mixture；After stirring 4 h, hydrogen peroxide is added in above-mentioned mixed solution, forms brown yellow solution；This is pale brown
Color solution is cleaned using hydrochloric acid and enough deionized waters；By 1 h of graphite oxide suspension ultrasound to remove graphite oxide, generate
Homogeneous solution be mixed in deionized water, hydrazine, ammonium hydroxide composition mixed solution in, 3h is stirred at 95 DEG C, to obtain graphene
Solution.
8. the preparation method of the sensing element of ionomer graphene complex according to claim 6, feature exist
In: in step 1, the mass density of the graphene film is 1.0mg/cm2。
9. the preparation method of the sensing element of ionomer graphene complex according to claim 6, feature exist
In: in step 1, the specific step of the graphene film containing ionic liquid is prepared by capillary force compression process using graphene film
Suddenly are as follows: graphene film is put into the mixed solution of volatile liquid and non-volatile liquid, is continued under the revolving speed of 400 rpm
Stir 12h so that mixed solution is exchanged to graphene film, then under vacuum conditions, 50 DEG C of evaporation 12h, volatility liquid
Evacuator body produces the compression of the capillary force between graphene layer, leads to the contraction of film thickness and the increase of graphene bulk density,
Non-volatile liquid is retained in inside graphene film；And stone is adjusted by the ratio of volatile liquid and non-volatile liquid
The bulk density of black alkene.
10. the preparation method of the sensing element of ionomer graphene complex according to claim 9, feature exist
In: the volatile liquid is deionized water, and non-volatile liquid is 1- ethyl-3-methylimidazole tetrafluoroborate EMImBF4,
1- ethyl-3-methylimidazole rhodanate EMImSCN, 1-- 3-methyl imidazolium tetrafluoroborate of butyl BMImBF4One kind.
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