CN115020120B - Composite graphene-bismuth alkene aerogel with staggered stacked intercalation structure, preparation method and application - Google Patents
Composite graphene-bismuth alkene aerogel with staggered stacked intercalation structure, preparation method and application Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 129
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- -1 bismuth alkene Chemical class 0.000 claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 40
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- 239000003990 capacitor Substances 0.000 claims description 23
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- 230000008859 change Effects 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 8
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- 239000004743 Polypropylene Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
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- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 18
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- 238000001514 detection method Methods 0.000 abstract 1
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- 238000007710 freezing Methods 0.000 description 7
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- 238000010438 heat treatment Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- CXSGLNBWVYMAPN-UHFFFAOYSA-H O.[Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound O.[Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O CXSGLNBWVYMAPN-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
- G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
- G01L1/148—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors using semiconductive material, e.g. silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a composite graphene-bismuth alkene aerogel with a staggered stacking intercalation structure, a preparation method and application thereof. According to the invention, the bismuth alkene thin sheet is inserted into the graphene thin sheet, so that a staggered stacking intercalation structure is realized, wherein 80-100 tiny units exist on each unit centimeter thickness, and each tiny unit is formed by stacking 800-900 layers of single-layer graphene and 80-100 layers of stacked single-layer bismuth alkene in a staggered manner. The graphene-bismuth alkene aerogel has high elastic compressibility, and has 0.326kPa within the stress range of 1.5-4.5 kPa ‑1 Is high in sensitivity; the strain-electricity response and ultrasensitive detection limit are stable, and the low voltage is effectively detected; has super capacitance characteristic of 400 W.Kg ‑1 45.55Wh Kg is provided ‑1 The cycle stability reached 89.24% even after 3600 charge-discharge cycles.
Description
Technical Field
The invention relates to a graphene-bismuth alkene aerogel with a composite type staggered stacked intercalation structure, a preparation method thereof and application thereof to a super-capacitor type pressure sensor, and belongs to the field of electronic material devices.
Background
The graphene aerogel has good conductivity and high strength, and is paid attention to the fields of energy storage, energy absorption, sensing and the like, and the preparation method comprises a hydrothermal method, freezing casting, 3D (three-dimensional) printing, chemical bonding and a template method, wherein the hydrothermal method and the freezing casting are the simplest and most convenient to implement. Bismuth has large reserve on the earth, has the abundance equivalent to silver, has wide application and higher ion conductivity, and is an important optical material, electronic material, superconducting material and the like. The capacitive pressure sensor has the advantages of high response speed, low cost, high sensitivity, small hysteresis and the like.
The prior Chinese patent 'a flexible capacitive pressure sensor based on graphene and a preparation method thereof' (publication No. CN 112781757A), wherein the sensor is formed by arranging two graphene electrode layers which are parallel up and down, wherein the inside of the electrode layers is formed by combining C-C bonds, and the density is 13.21 mg.cm -3 A porous elastomer is arranged between the two graphene electrode layers, and a silver paste wire is led out of the graphene electrode layers to form a peripheral lead. The sensitivity of the sensor is 1.1kPa -1 The error of the pressure result is large and the stress sensitivity is low.
In the prior art, M.Ciszewski et al [ Ionics 21,557-563 (2014).]Mention is made of converting a composite material of bismuth oxalate hydrate and graphene oxide into bismuth oxide and reducing the graphene oxide by thermal decomposition in a muffle furnace, the composite material having a current density of 0.2 A.g -1 When the specific capacitance reaches 94 F.g -1 . The cyclic voltammetry was used, and the scanning rate was 5 mV.s in the potential range of 0 to 1V -1 At the time of the specific capacitance of 55 F.g -1 . After 3000 cycles, the material showed long-term cycling stability with a specific capacitance maintained at 90%. However, the composite material does not realize the combination of bismuth and graphene, but rather Bi 2 O 3 The advantages and characteristics of bismuth in graphene aerogel intercalation are not fully reflected when the bismuth is mixed in graphene oxide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the graphene-bismuth-alkene aerogel with the composite type staggered stacking intercalation structure, wherein bismuth alkene layers are inserted between the layered structures of graphene, and the synergistic effect of the bismuth alkene and the graphene staggered stacking intercalation structure realizes the design and construction of an ion/electron double transmission channel in a layered porous aerogel frame. This structure facilitates electrolyte permeation and ensures electron transfer between layers, effectively increasing mass capacitance. In addition, the conductive bismuth nano-sheet coated on the reduced graphene can be used as a main body for constructing an additional electron transmission channel, and generates additional electrochemical active sites, so that the interlayer conductivity is improved, and the interlayer electron transmission is ensured.
The invention also provides a preparation method of the composite graphene-bismuth graphene staggered stacked intercalation structure aerogel and application of the composite graphene-bismuth graphene staggered stacked intercalation structure aerogel to a super-capacitor type pressure sensor, and the preparation method comprises the preparation of the composite graphene-bismuth graphene hydrogel with the staggered stacked intercalation structure, the preparation of the composite graphene-bismuth graphene aerogel with the staggered stacked intercalation structure and application of the composite graphene-bismuth graphene aerogel with the staggered stacked intercalation structure to the field of the super-capacitor type pressure sensor.
Preferably, the preparation steps of the composite type bismuth alkene-graphene aerogel with the staggered stacked intercalation structure are as follows:
1) Preparation of bismuth alkene: taking bismuth powder and (NH) 4 ) 2 S 2 O 8 Mixing in a flask; then, adding concentrated H into the mixed solution 2 SO 4 And H 2 O 2 Sealing at room temperature, and then washing with ethanol to remove residual H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the And then carrying out ultrasonic treatment in a closed environment. Finally, the mixture is filtered to remove the unpeeled bismuth powder, and 0.014-0.017 g.mL is obtained from the supernatant -1 Bismuth alkene.
2) Preparation of graphene-bismuth alkene hydrogel with composite type staggered stacking intercalation structure: firstly, graphene oxide is put into a mixed solution of deionized water and ammonia solution, and is subjected to ultrasonic treatment. The graphene solution is then mixed with the bismuth alkene solution. The precursor solution was sealed in a 10mL autoclave lined with polytetrafluoroethylene at a temperature of 120 c for 12-14 h. Subsequently, the hydrogel is on CH 3 CH 2 OH/H 2 The mixture of O (1:100, V: V) was dialyzed and cooled to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite type staggered stacking intercalation structure. The ammonia solution is common ammonia water with the concentration of 25-28%.
3) Preparation of composite graphene-bismuth graphene aerogel with staggered stacking intercalation structure: and (3) performing freezing treatment on the hydrogel obtained in the step (2) in a refrigerator, and then placing the hydrogel in a freeze drying box for freeze drying to obtain the graphene-bismuth alkene aerogel with the composite staggered stacking intercalation structure.
Preferably, the preparation steps of the super-capacitor pressure sensor are as follows:
1) First PVA powder and concentrated H 2 SO 4 Mixing, adding deionized water, stirring in a water bath kettle, and heating at 80-85 ℃ to completely dissolve to form gel electrolyte.
2) Fixing the composite graphene-bismuth alkene staggered stacking intercalation structure aerogel on a titanium electrode through conductive silver paste, and drying to obtain the composite graphene-bismuth alkene aerogel electrode with the staggered stacking intercalation structure, namely a graphene-bismuth alkene aerogel/Ti electrode. Two graphene-bismuth alkene aerogel/Ti electrodes serving as a negative electrode and a positive electrode are respectively soaked in the prepared gel electrolyte. Between two electrodes, a thin film of 0.7-1.0 cm in size is sandwiched 2 The polypropylene diaphragm paper of the utility model realizes a symmetrical all-solid super capacitor, namely a super capacitor type pressure sensor.
The pressure sensor has the sensitivity of 0.326kPa within the stress range of 1.5-4.5 kPa -1 And can provide a rapid current response to changes in external pressure; after 1000 times of cyclic pressure, the relative change of the capacitance still keeps 87% of the original value, has high stress stability, and can sense small changes of strain and pressure.
The principle of the invention is as follows:
when bismuth alkene is prepared: by mixing bismuth powder with (NH) 4 ) 2 S 2 O 8 Mixing in a flask to obtain a uniform dispersion; then, adding concentrated H into the mixed solution 2 SO 4 And H 2 O 2 Stripping bismuth powder with strong oxidizing property, sealing in a closed environment, and washing with ethanol to remove residual H 2 SO 4 The resulting powder was mixed with deionized water and sonicated in a sealed environment to thoroughly mix. Finally, the mixture was filtered to remove the unpeeled bismuth powder,bismuth alkene is obtained from the supernatant. Bismuth alkene mainly comprises metallic element bismuth, and bismuth alkene inserts the interlaminar structure of graphite alkene, can effectual interact between reinforcing graphite alkene piece, forms electron/ion double transmission passageway, is favorable to the infiltration of electrolyte, slows down the decline of interlaminar conductivity, ensures interlaminar electron's transmission to provide higher accessible surface area, this characteristic helps electrolyte ion to permeate fast and get into the interior surface of electrode material.
When the graphene-bismuth alkene hydrogel with the composite type staggered stacking intercalation structure is prepared: firstly, graphene oxide is put into a mixed solution of deionized water and ammonia solution, and is subjected to ultrasonic dispersion to promote solid-liquid reaction. Then dispersing the precursor solution, mixing the precursor solution with the graphene oxide solution, the regenerated bismuth alkene solution and deionized water, so that the particle size of a dispersed phase is reduced, the interphase interface is increased, and the particles are uniformly dispersed; heating the precursor solution in a polytetrafluoroethylene-lined high-pressure reaction kettle for reaction, cooling to room temperature to obtain hydrogel, and then placing the hydrogel in CH 3 CH 2 OH/H 2 Dialyzing in a mixture of O (1:100, V:V) to remove impurities, and preparing the graphene-bismuth alkene hydrogel with the composite type staggered stacked intercalation structure. When the hydrogel is prepared by adopting a hydrothermal method, bismuth alkene layers are inserted between the layered structures of graphene, 80-100 tiny units exist per unit centimeter thickness as shown in figure 1 by observing and measuring density of electron microscope images of the gel, each tiny unit consists of 800-900 layers of single-layer graphene and 80-100 layers of bismuth alkene layers, the bismuth alkene layers and the graphene layers are formed by combining strong hydrogen bonds and C-Bi bonds, and the synergistic effect of the bismuth alkene and the graphene realizes the design and construction of ion/electron double transmission channels in the staggered stacked intercalation structure aerogel frame. The bismuth-treated graphene frame shows cross-linked hierarchical structures with different sizes, namely from hundreds of nanometers to a few micrometers, and the structure is beneficial to electrolyte permeation, ensures interlayer electron transfer and effectively increases mass capacitance. In addition, the conductive bismuth nano-sheet coated on the reduced graphene can be used as a main body for constructing an additional electron transmission channel, and generates additional electrochemical active sites, so that the interlayer conductivity is improved, and the interlayer electron transmission is ensured.The nano-anchor can also be used for enhancing the bonding strength between the multi-layer graphene sheets, so that the mechanical property of the gel is enhanced; meanwhile, an additional electron transmission channel is constructed between graphene sheets, interlayer electron transmission is ensured, and therefore interlayer conductivity reduction caused by interlayer interval insertion is relieved.
When preparing the graphene-bismuth alkene aerogel with the composite type staggered stacking intercalation structure, dialyzing the obtained graphene hydrogel with the composite type staggered stacking intercalation structure in a mixed solution of ethanol and water, separating and purifying to remove gel floating, freezing in a refrigerator to protect a hydrogel carrier and a colloidal particle structure, freeze-drying again, removing the moisture of the composite type graphene hydrogel to lead the graphene sheets to be propped open to form a porous network structure, and preparing the graphene-bismuth alkene aerogel with the composite type staggered stacking intercalation structure as shown in figure 2;
the composite type graphene-bismuth alkene aerogel with the staggered and stacked intercalation structure is a three-dimensional nano material formed by taking two-dimensional graphene as a construction unit, has the characteristics of high conductivity, large specific surface area, ultralow density, high porosity and the like, has higher specific capacitance, can be used for modifying electrodes, and is used for constructing a supercapacitor type pressure sensor. Compared with a pressure sensor prepared from graphene aerogel without bismuth, the pressure sensor prepared from the graphene-bismuth aerogel with the composite type staggered stacking intercalation structure has the advantages of larger relative change of capacitance and resistance and higher sensitivity. The superior performance of the super capacitor is that 80-100 tiny units exist on each unit centimeter thickness due to the synergistic effect of the staggered intercalation structure formed by the stacked bismuth graphene layers and the stacked graphene layers, and each tiny unit consists of 800-900 single-layer graphene layers and 80-100 bismuth graphene layers; as shown in fig. 4, the deconvoluted C1s peaks show peak binding energies of 284.1, 284.71, 285.69, 286.1 and 288.42eV, corresponding to C-Bi, C-C, C-O, C-N, C =o bonds, respectively; the bismuth graphene layer and the graphene layer are formed by combining strong hydrogen bonds and C-Bi bonds, and the design and construction of an ion/electron double transmission channel in the aerogel frame of the staggered intercalation structure are realized by the synergistic effect of the bismuth graphene and the graphene. These structures have rich electrochemical active centers, high conductivity, low interface resistance and rapid ion/electron transport, facilitate electrolyte permeation, ensure electron transfer between layers, and effectively increase mass capacitance.
The beneficial effects of the invention are as follows:
1) Compared with the prior art, the aerogel has the advantages that bismuth graphene is inserted between graphene layered structures, and the bismuth graphene frames show cross-linked layered structures with different sizes, which are different from hundreds of nanometers to a few micrometers. The layered pores not only provide transport channels for ions or ionic groups in the electrolyte, but also help to reveal active centers and improve double-layer capacitance, thereby improving electrochemical and pressure sensor performance; its density is 10-15 mg cm -3 The structure consists of elements C, O, N, bi, and the atomic number ratio ranges are 78.7-80%, 14-15%, 5-6% and 0.2-0.3% respectively.
2) The graphene-bismuth alkene aerogel disclosed by the invention does not undergo chemical reaction deterioration due to the excessive active electrochemical activity; the prepared symmetrical super capacitor battery is 400 W.Kg -1 The energy density at the time is 45.55 Wh.Kg -1 The cycle stability after 3600 charge-discharge cycles was 89.24%. The ion/electron capacitance sensor was fabricated with a pressure of 0.326kPa -1 And has satisfactory durability during 1000 pressure loading cycles.
3) In addition, the super-capacitor type pressure sensor based on the graphene aerogel with the composite type staggered stacked intercalation structure has 0.326kPa in the stress range of 1.5-4.5 kPa -1 Is 0.99; after 1000 times of cyclic pressure, the relative change of the capacitance still keeps 87% of the original value, and the stress stability is high; can sense small changes of strain (0.012%) and pressure (0.25 Pa), and effectively detect low pressure; a rapid current response to changes in external pressure can be provided; the super capacitor has the characteristics of super capacitor, can provide high capacitance response and has good electrochemical energy storage.
Drawings
FIG. 1 is a schematic structural diagram of a super-capacitor pressure sensor according to the present invention, wherein 1 is a titanium foil, 2 is silver colloid, 3 is a micro unit formed by graphene and bismuth alkene, and N 1 80-100, with a single microcell on the right side, wherein 4 is a graphene layer, and the single microcell contains about N 2 Layer N 2 A bismuth alkene layer having a size of 800-900,5, and a single microunit containing about N 3 Layer N 3 The size is 80-100;
fig. 2 is a schematic preparation diagram and a partial microscopic enlarged view of a graphene-bismuth alkene aerogel with a composite type staggered stacked intercalation structure according to the present invention;
fig. 3 is an SEM image of an aerogel according to the present invention, wherein (a-c) is an SEM image of redox graphene at different magnification, and (d-f) is an SEM image of graphene-bismuth graphene aerogel of a composite type staggered stacked intercalation structure at different magnification.
FIG. 4 is a graph of XPS analysis of sample C of example 2 of the present invention, showing deconvoluted C1s peaks showing peak binding energies of 284.1, 284.71, 285.69, 286.1 and 288.42eV, corresponding to C-Bi, C-C, C-O, C-N, C =O bonds, respectively;
FIG. 5 shows GCD (constant current charge and discharge) behavior of sample electrode of example 3 of the present invention at different densities, current density of 0.64 A.g -1 To 3 A.g -1 ；
FIG. 6 is a graph showing the relative capacitance change for samples of example 4 of the present invention at different compressive strains, with stress changes ranging from 0.5kPa to 4.5kPa;
fig. 7 is a graph showing electrochemical cycling stability of the supercapacitor after 3600 charge-discharge cycles for the sample of example 5 of the present invention.
FIG. 8 is a graph showing the relative change in capacitance at a force of 1kPa and a cyclic pressure of 14k for a sample of example 6 of the present invention; wherein the left and right illustrations represent enlarged views of some selected cycles from the beginning and end of the test.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description of the specific embodiment is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in this description of the invention are for the purpose of describing particular embodiments only and are not intended to be limiting of the invention.
Example 1
A preparation method of a composite graphene-bismuth alkene aerogel with a staggered stacked intercalation structure comprises the following steps:
1) Preparation of bismuth alkene: 100mg bismuth powder and 0.50g (NH) 4 ) 2 S 2 O 8 Mixing in a flask; then, 5mL of concentrated H was added to the above mixed solution 2 SO 4 And 1.2mL H 2 O 2 Sealing at room temperature for 12 hours, and then washing with ethanol 5 times to remove residual H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the 20mg of the resulting dry powder and 1mL of deionized water were sonicated in a sealed environment for 6 hours. Finally, the mixture is filtered to remove the unpeeled bismuth powder, and the concentration of the bismuth powder is 0.014 to 0.017 g.mL from the supernatant -1 Bismuth alkene solution of (a).
2) Preparation of composite type staggered stacked intercalation structure hydrogel: first, 100mg of graphene oxide was put into a mixed solution of 20mL of deionized water and 0.8mL of ammonia solution, and ultrasonically dispersed for 60 minutes. Then, 5mL of the reduced graphene oxide solution was mixed with 0.2mL of the bismuth alkene solution to prepare a mixed solution. The precursor solution was sealed in a 10mL autoclave lined with polytetrafluoroethylene at a temperature of 120 c for 12h. Subsequently, the hydrogel is on CH 3 CH 2 OH/H 2 The mixture of O (1:100, V: V) was dialyzed for 6 hours and cooled to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite type staggered stacking intercalation structure.
3) Preparation of composite graphene-bismuth alkene staggered stacked intercalation structure aerogel: freezing the hydrogel obtained in the step 2) in a refrigerator for 12 hours to obtain aerogel, and naming the aerogel as BiGA1.
In contrast, when no bismuth alkene solution was added in step 2), the other steps were unchanged, and graphene aerogel was prepared, named NGA.
In this example, as shown in FIG. 3, the increase in the surface wrinkling degree and porosity of the SEM frame of the BiGA1 sample compared with the increase in the NGA was measured, and in the SEM image of the NGA, it was found that the surface was smoother, the porosity was small, and the density of the BiGA1 sample was 11.1mg cm -3 The comparative NGA increases in volume. The stacking between graphene sheets in the BiGA1 sample is obviously reduced, the interior of the BiGA1 sample contains a hybrid structure, the structure consists of elements C, O, N, bi, and the atomic number ratio ranges of the elements C, O, N, bi are 79.8%,15%,6% and 0.2%, respectively. It was measured that the sample only required 11.5kPa force when compressed to 50% strain for the first time, whereas the NGA sample required 125kPa force, indicating that the bismuth-added BiGA1 sample was softer, which was beneficial for improved sensitivity.
Example 2
A preparation method of a composite graphene-bismuth alkene aerogel with a staggered stacked intercalation structure comprises the following steps:
1) Preparation of bismuth alkene: 90mg bismuth powder and 0.40g (NH) 4 ) 2 S 2 O 8 Mixing in a flask; then, 4mL of concentrated H was added to the above mixed solution 2 SO 4 And 1mL H 2 O 2 Sealing at room temperature for 10 hours, then washing with ethanol 4 times to remove residual H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the 18mg of the resulting dry powder and 1mL of deionized water were sonicated in a sealed environment for 6 hours. Finally, the mixture was filtered to remove the unpeeled bismuth powder, and bismuth alkene was obtained from the supernatant.
2) Preparation of composite type staggered stacked intercalation structure hydrogel: first, 80mg of graphene oxide was put into a mixed solution of 15mL of deionized water and 0.5mL of ammonia solution, and ultrasonically dispersed for 50 minutes. Then, 5mL of the reduced graphene oxide solution was mixed with 0.4mL of the bismuth alkene solution to prepare a mixed solution. The precursor solution was sealed in a 10mL autoclave lined with polytetrafluoroethylene at a temperature of 120 c for 12h. Subsequently, the hydrogel is on CH 3 CH 2 OH/H 2 The mixture of O (1:100, V: V) was dialyzed for 5-6 hours and cooled to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite type staggered stacking intercalation structure.
3) Preparation of composite graphene-bismuth alkene staggered stacked intercalation structure aerogel: freezing the hydrogel obtained in the step 2) in a refrigerator for 12 hours to obtain aerogel, and naming the aerogel as BiGA2.
Example 3
A preparation method of composite graphene-bismuth alkene staggered stacked intercalation structure aerogel comprises the following steps:
1) Preparation of bismuth alkene: 90mg bismuth powder and 0.40g (NH) 4 ) 2 S 2 O 8 Mixing in a flask; then, 4mL of concentrated H was added to the above mixed solution 2 SO 4 And 1mL H 2 O 2 Sealing at room temperature for 10 hours, then washing with ethanol 4 times to remove residual H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the 18mg of the resulting dry powder and 1mL of deionized water were sonicated in a sealed environment for 6 hours. Finally, the mixture was filtered to remove the unpeeled bismuth powder, and bismuth alkene was obtained from the supernatant.
2) Preparation of composite type staggered stacked intercalation structure hydrogel: first, 80mg of graphene oxide was put into a mixed solution of 15mL of deionized water and 0.5mL of ammonia solution, and ultrasonically dispersed for 50 minutes. Then, 5mL of the reduced graphene oxide solution was mixed with 0.8mL of the bismuth alkene solution to prepare a mixed solution. The precursor solution was sealed in a 10mL autoclave lined with polytetrafluoroethylene at a temperature of 120 c for 12h. Subsequently, the hydrogel is on CH 3 CH 2 OH/H 2 The mixture of O (1:100, V: V) was dialyzed for 5-6 hours and cooled to room temperature. And preparing the composite graphene-bismuth alkene hydrogel.
3) Preparation of composite graphene-bismuth alkene staggered stacked intercalation structure aerogel: freezing the hydrogel obtained in the step 2) in a refrigerator for 12 hours to obtain aerogel, and naming the aerogel as BiGA3.
In this example, the SEM frames of the BiGA3 samples were measured to have a small number of complex network of folds interconnected, with a density of 14.1mg cm, as compared to the increase in surface folds and porosity of NGA -3 The comparative NGA increases in volume. Measured at a current density of 0.67 A.g -1 The mass specific capacitance of the BiGA3 sample electrode was 400.83 F.g -1 Mass specific capacitance 275 F.g compared with NGA sample electrode -1 Greatly improves, which indicates that the graphene-bismuth alkene frameworkCan provide good environment for ions, and provide high specific capacitance and excellent rate performance. As shown in FIG. 5, the GCD behavior of BiGA3 sample at high operating current density was observed, and the current density was from 0.64 A.g -1 To 3 A.g -1 The curve is still in a triangular symmetry shape, which shows the working potential of the BiGA3 sample electrode in a high-rate charge-discharge mode.
Example 4
Preparation of super-capacitor type pressure sensor
1) Preparation of gel electrolyte: 3g PVA and 1.5g concentrated H were added to 30mL deionized water 2 SO 4 Completely dissolving at 80deg.C for 60min to form gel electrolyte.
2) Preparation of upper and lower electrodes on a graphene-bismuth alkene aerogel with a composite type staggered stacked intercalation structure: fixing the composite graphene-bismuth alkene staggered stacking intercalation structure aerogel on a titanium electrode through conductive silver paste, and drying to obtain the composite graphene-bismuth alkene aerogel electrode with the staggered stacking intercalation structure, namely a graphene-bismuth alkene aerogel/Ti electrode. Two graphene-bismuth alkene aerogel/Ti electrodes serving as a negative electrode and a positive electrode are respectively soaked in the prepared gel electrolyte for 60min. And a polypropylene diaphragm paper with the size of 0.7-1.0 cm < 2 > is clamped between the two electrodes, so that a symmetrical all-solid-state supercapacitor, namely the supercapacitor type pressure sensor, is realized.
In the embodiment, the pressure sensor prepared based on the BiGA3 sample is of a sandwich structure, the upper layer and the lower layer of the sensor are both titanium electrodes, the middle layer is a composite type graphene-bismuth alkene aerogel with a staggered stacking intercalation structure, and the composite type graphene-bismuth alkene aerogel is injected with gel electrolyte, as shown in FIG. 6, and shows that the stress sensitivity is 0.052kPa when the pressure range is 0-1.5 kPa -1 In the range of 1.5 to 4.5kPa, the sensitivity thereof is 0.326kPa -1 While NGA-based sensors show a sensitivity of 0.024kPa at pressures ranging from 0 to 2.5kPa -1 The linear sensitivity is 0.282kPa in the pressure range of 2.5-4.5 kPa -1 The data comparison shows that compared with a pressure sensor prepared from an NGA sample without bismuth alkene, the sensor has the advantages of increased stress sensitivity and improved performance.
Example 5
Preparation of super-capacitor type pressure sensor
1) Preparation of gel electrolyte: 3g PVA and 1.5g concentrated H were added to 30mL deionized water 2 SO 4 Completely dissolving at 80deg.C for 60min to form gel electrolyte.
2) Preparation of upper and lower electrodes on a graphene-bismuth alkene aerogel with a composite type staggered stacked intercalation structure: two graphene-bismuth alkene aerogel/Ti electrodes serving as a negative electrode and a positive electrode are respectively soaked in the prepared gel electrolyte for 60min. A size of 1.0cm is sandwiched between two electrodes 2 The polypropylene diaphragm paper of the utility model realizes a symmetrical all-solid super capacitor.
In this embodiment, the pressure sensor prepared based on the BiGA3 sample is a sandwich structure, the upper layer and the lower layer of the sensor are both electrodes, the middle layer is a composite graphene-bismuth alkene aerogel with a staggered stacking intercalation structure into which gel electrolyte is injected, and as shown in fig. 7, the sensor shows a significant capacity retention rate of 89.24% after 3600 charge and discharge cycles.
Example 6
Preparation of super-capacitor type pressure sensor
1) Preparation of gel electrolyte: 3g PVA and 1.5g concentrated H were added to 30mL deionized water 2 SO 4 Completely dissolving at 80deg.C for 60min to form gel electrolyte.
2) Preparation of upper and lower electrodes on a graphene-bismuth alkene aerogel with a composite type staggered stacked intercalation structure: two graphene-bismuth alkene aerogel/Ti electrodes serving as a negative electrode and a positive electrode are respectively soaked in the gel electrolyte prepared by the method for 60min. A size of 1.0cm is sandwiched between two electrodes 2 The polypropylene diaphragm paper of the utility model realizes a symmetrical all-solid super capacitor.
In the embodiment, the pressure sensor is prepared based on a BiGA3 sample, as shown in fig. 8, after the sensor is circularly pressed for 1000 times, the relative change of the capacitance still keeps 87% of the original value, and the sensor has high stress stability; the sensor has sandwich structure, electrodes on upper and lower layers, gel electrolyte injection in middle layerGraphene-bismuth alkene aerogel with combined staggered stacked intercalation structure and stress sensitivity of 0.73kPa -1 The fitting degree is 0.99; pressure sensor based on NGA sample preparation with stress sensitivity of 0.04kPa -1 The fitting degree is 0.96; pressure sensor prepared based on BiGA1 sample, with stress sensitivity of 0.10kPa -1 The fitting degree is 0.99; pressure sensor prepared based on BiGA2 sample and with stress sensitivity of 0.15kPa -1 The fitting degree is 0.99.
TABLE 1
The data comparison shows that compared with NGA, biGA1 and BiGA2, the pressure sensor prepared based on the BiGA3 sample has the advantages of best sensitivity, highest fitting degree, best elastic compressibility, capability of sensing small change of strain and pressure, capability of providing quick current response to external pressure change, great advantages in electrochemical energy storage, super-capacitor characteristics and cycle stability, and most excellent performance.
In summary, as described in the examples, compared with the pressure sensors prepared based on the samples of BiGA1, biGA2 and BiGA3, the pressure sensor based on the sample of BiGA3 was found to have the best stress sensitivity and the best performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A composite graphene-bismuth alkene aerogel with a staggered stacking intercalation structure is formed by inserting bismuth alkene layers between the layered structures of graphene, wherein 80-100 tiny units are arranged on each unit centimeter thickness, and each tiny unit consists of 800-900 stacked single-layer graphene layers and 80-100 stacked single-layer bismuth alkene layers.
2. The composite type graphene-bismuth alkene aerogel with a staggered and stacked intercalation structure as claimed in claim 1, wherein the bismuth alkene layer and the graphene layer are formed by combining strong hydrogen bonds and C-Bi bonds, and the density of the aerogel is 10-15 mg cm -3 The structure is formed by constructing an ion and electron double transmission channel in an aerogel frame with a staggered stacked intercalation structure, wherein the structure consists of elements C, O, N, bi, and the atomic number ratio ranges of the elements C, O, N, bi to C, O, N, bi are 78.7-80%, 14-15%, 5-6% and 0.2-0.3% respectively.
3. The preparation method of the graphene-bismuth alkene aerogel with the composite type staggered stacked intercalation structure is characterized by comprising the following steps of:
1) Preparation of bismuth alkene: taking bismuth powder and (NH) 4 ) 2 S 2 O 8 Mixing in a flask; adding concentrated H 2 SO 4 And H 2 O 2 Sealing reaction, washing with ethanol to remove residual H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the Adding deionized water into the obtained powder, and carrying out ultrasonic treatment; filtering to remove non-stripped bismuth powder, and obtaining the concentration of 0.014-0.017 g.mL from the supernatant -1 Bismuth alkene solution;
2) Preparation of graphene-bismuth alkene hydrogel with composite type staggered stacking intercalation structure:
firstly, graphene oxide powder is put into a mixed solution of deionized water and ammonia solution, and ultrasonic dispersion is carried out to obtain the graphene oxide powder with the concentration of 0.004-0.008 g.mL -1 Is a reduced graphene oxide solution;
then, the reduced graphene oxide solution and the bismuth alkene solution prepared in 1) are mixed according to the volume ratio of (3-5): (0.2-1.2) mixing to prepare a precursor solution; the precursor solution is sealed in an autoclave with a polytetrafluoroethylene lining and kept at the temperature of 100-120 ℃ for 10-14 h to obtain hydrogel with a staggered stacked intercalation structure;
subsequently, the hydrogel of the staggered stacked intercalation structure was subjected to CH at V: v=1:100 3 CH 2 OH/H 2 Dialyzing the mixture of O for 3-6 h, and cooling to room temperature to obtain the graphene-bismuth alkene hydrogel with the composite staggered stacking intercalation structure;
3) Preparation of composite graphene-bismuth graphene aerogel with staggered stacking intercalation structure: and (3) freeze-drying the hydrogel obtained in the step (2) in a freeze drying box at the temperature of-18 to-20 ℃ for 10-12 hours to obtain aerogel.
4. A composite type graphene-bismuth alkene aerogel with a staggered and stacked intercalation structure according to claim 1 or 2 or obtained by the preparation method according to claim 3, which is characterized in that the current density is 0.6-1.0 a.g -1 The mass specific capacitance is 360-420 F.g -1 。
5. The application of the composite type graphene-bismuth alkene aerogel with the staggered and stacked intercalation structure in the super-capacitor type pressure sensor, which is disclosed in claim 4, is characterized in that the super-capacitor type pressure sensor is of a sandwich structure, the upper layer and the lower layer of the super-capacitor type pressure sensor are both electrodes, the middle layer is the composite type graphene-bismuth alkene aerogel with the staggered and stacked intercalation structure, and gel electrolyte is filled in the composite type graphene-bismuth alkene aerogel with the staggered and stacked intercalation structure.
6. The use of claim 5, wherein the super-capacitor pressure sensor is prepared by the method comprising the steps of:
1) PVA and concentrated H are firstly added into deionized water 2 SO 4 Completely dissolving at 80-85 ℃ to form gel electrolyte;
2) Fixing the composite graphene-bismuth alkene staggered stacking intercalation structure aerogel on a titanium electrode through conductive silver paste, and drying to obtain a composite graphene-bismuth alkene aerogel electrode with a staggered stacking intercalation structure, namely a graphene-bismuth alkene aerogel/electrode; respectively soaking two graphene-bismuth alkene aerogel/electrodes serving as a negative electrode and a positive electrode in the gel electrolyte prepared in the step 1) for 50-60 min; between two electrodes, a thin film of 0.7-1.0 cm in size is sandwiched 2 The polypropylene diaphragm paper of the utility model realizes a symmetrical all-solid super capacitor.
7. The use according to any one of claims 5-6, whereinThe pressure sensor has 0.326kPa in the stress range of 1.5-4.5 kPa -1 After 1000 pressure loading cycles, the relative change of the capacitance can still be kept to be 87% of the original value respectively; at 400 W.Kg -1 45.55Wh Kg is provided -1 After 3600 charge-discharge cycles, the cycle stability reached 89.24%.
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