CN115020120A - Graphene-bismuth alkene aerogel with composite staggered and stacked intercalation structure, and preparation method and application thereof - Google Patents
Graphene-bismuth alkene aerogel with composite staggered and stacked intercalation structure, and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a graphene-bismuth ene aerogel with a composite staggered and stacked intercalation structure, and a preparation method and application thereof. According to the invention, the bismuth-alkene sheet is inserted into the grapheme sheet layer, so that a staggered stacking intercalation structure is realized, wherein 80-100 tiny units exist in each unit centimeter of thickness, and each tiny unit is formed by staggering 800-900 stacked single-layer grapheme layers and 80-100 stacked single-layer bismuth-alkene layers. The graphene-bismuth alkene aerogel disclosed by the invention has high elasticity and compressibility, and has the stress range of 1.5-4.5 kPa and the stress range of 0.326kPa ‑1 High sensitivity of (2); the strain-electric response is stable, the detection limit is ultra-sensitive, and low voltage is effectively detected; has super capacitance characteristic of 400 W.Kg ‑1 When the yield is 45.55 Wh.Kg ‑1 Energy density of (i.e.The cycle stability after 3600 charge-discharge cycles is also up to 89.24%.
Description
Technical Field
The invention relates to a composite type staggered-stacked intercalation structure graphene-bismuth alkene aerogel, a preparation method thereof and application of the aerogel in a super-capacitor type pressure sensor, and belongs to the field of electronic material devices.
Background
The graphene aerogel is good in conductivity and high in strength, and has great interest in the fields of energy storage, energy absorption, sensing and the like, and the preparation method comprises a hydrothermal method, freeze casting, 3D (three-dimensional) printing, chemical bonding and a template method, wherein the hydrothermal method and the freeze casting are the simplest and the most convenient. The storage capacity of bismuth on the earth is large, the abundance of bismuth is equivalent to that of silver, the application is wide, the bismuth has higher ion conduction performance, and the bismuth is an important optical material, an electronic material, a superconducting material and the like. The capacitance type pressure sensor has the advantages of high response speed, low cost, high sensitivity, small lag and the like.
In the existing chinese patent, "a flexible capacitive pressure sensor based on graphene and a method for manufacturing the same" (publication No. CN112781757A), the sensor is provided with two graphene electrode layers parallel to each other, the inside of each electrode layer is formed by combining C-C bonds, and the density of the electrode layer is 13.21mg · cm -3 And a porous elastomer is arranged between the two graphene electrode layers, and a silver paste lead is led out of the graphene electrode layers to form a peripheral lead. The sensitivity of the sensor is 1.1kPa -1 The pressure result error is large and the stress sensitivity is low.
In the prior art, M.Ciszewski et al [ Ionics 21, 557-.]Mention is made of the conversion of a composite of hydrated bismuth oxalate and graphene oxide by thermal decomposition in a muffle furnaceBismuth oxide is formed and graphene oxide is reduced, and the current density of the composite material is 0.2 A.g -1 When the specific capacitance reaches 94F g -1 . Using cyclic voltammetry, the scanning rate is 5 mV.s in the potential range of 0-1V -1 When the specific capacitance is 55F g -1 . After 3000 cycles, the material shows long-term cycling stability, and the specific capacitance is kept at 90%. However, the composite material does not realize the combination of bismuth and graphene, but Bi is used 2 O 3 The bismuth is mixed in the graphene oxide, so that the advantages and the characteristics of bismuth in the intercalation of the graphene aerogel are not fully embodied.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a graphene-bismuth-alkene aerogel with a composite staggered and stacked intercalation structure, wherein a bismuth-alkene layer is inserted between the layered structures of graphene, and the design and construction of an ion/electron double-transmission channel in a layered porous aerogel frame are realized through the synergistic effect of bismuth alkene and the graphene staggered and stacked intercalation structure. This structure facilitates electrolyte permeation and ensures electron transfer between layers, effectively increasing mass capacitance. In addition, the conductive bismuth nanosheets coated on the reduced graphene can be used as a main trunk for constructing an additional electron transmission channel, and generate 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 alkene staggered stacking intercalation structure aerogel and an application of the composite graphene-bismuth alkene staggered stacking intercalation structure aerogel on a super-capacitance pressure sensor, and the preparation method comprises the preparation of the composite graphene-bismuth alkene hydrogel with the staggered stacking intercalation structure, the preparation of the composite graphene-bismuth alkene aerogel with the staggered stacking intercalation structure and the application of the composite graphene-bismuth alkene aerogel in the field of the super-capacitance pressure sensor.
Preferably, the preparation steps of the composite type staggered-stacked intercalation structure bismuth graphene-graphene aerogel are as follows:
1) preparing bismuth alkene: mixing bismuth powder and (NH) 4 ) 2 S 2 O 8 Mixing in a flask; then, concentrated H is added to the above mixed solution 2 SO 4 And H 2 O 2 Sealed at room temperature and then washed with ethanol to remove residual H 2 SO 4 (ii) a And then carrying out ultrasonic treatment in a closed environment. Finally, the mixture is filtered to remove the un-peeled bismuth powder, and 0.014-0.017 g/mL of bismuth powder is obtained from the supernatant -1 Bismuth ene.
2) Preparing the graphene-bismuth ene hydrogel with the composite staggered and stacked intercalation structure: firstly, putting graphene oxide into a mixed solution of deionized water and an ammonia solution, and carrying out ultrasonic treatment. The graphene solution is then mixed with the bismuth alkene solution. The precursor solution is sealed in a 10mL autoclave with a polytetrafluoroethylene lining, the temperature is 120 ℃, and the precursor solution is kept for 12-14 h. Subsequently, the hydrogel is in CH 3 CH 2 OH/H 2 Dialyzing the mixture of O (1:100, V: V) and cooling to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite staggered and stacked intercalation structure. The ammonia solution is common ammonia water with the concentration of 25-28%.
3) Preparing a graphene-bismuth alkene aerogel with a composite staggered and stacked intercalation structure: freezing the hydrogel obtained in the step 2) in a refrigerator, and then placing the hydrogel in a freeze drying oven for freeze drying to obtain the graphene-bismuth alkene aerogel with the composite staggered and stacked intercalation structure.
Preferably, the super-capacitor pressure sensor is prepared by the following steps:
1) firstly, mixing PVA powder with 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 the gel electrolyte.
2) Fixing the composite graphene-bismuth alkene staggered-stacked intercalation structure aerogel on a titanium electrode through conductive silver paste, and drying to obtain the composite graphene-bismuth alkene aerogel electrode, namely the graphene-bismuth alkene aerogel/Ti electrode. Two graphene-bismuth ene aerogel/Ti electrodes serving as a negative electrode and a positive electrode are respectively soaked in the prepared gel electrolyte. A size of 0.7-1.0 cm is clamped between the two electrodes 2 The polypropylene diaphragm paper realizes a symmetrical all-solid-state supercapacitor, namely a supercapacitor pressure sensor.
The pressure sensor has the sensitivity of 0.326kPa in the stress range of 1.5-4.5 kPa -1 And can provide a fast current response to external pressure changes; after 1000 times of cyclic pressing, the relative change of the capacitance still retains 87 percent of the original value, has high stress stability, and can sense the small changes of the strain and the pressure.
The principle of the invention is as follows:
when preparing the bismuth alkene: by mixing bismuth powder and (NH) 4 ) 2 S 2 O 8 Mixing in a flask to obtain uniform dispersion liquid; then, concentrated H is added to the above mixed solution 2 SO 4 And H 2 O 2 Stripping bismuth powder by using its strong oxidizing property, sealing in a sealed 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 unstripped bismuth powder, and bismuth alkene was obtained from the supernatant. Bismuth alkene mainly comprises metallic element bismuth, bismuth alkene inserts the interjacent structure of graphite alkene, can the effectual interact that strengthens between the graphite alkene piece, forms electron/ion double transmission channel, is favorable to the infiltration of electrolyte, slows down the decline of interlaminar conductivity, ensures the transmission of interlaminar electron to provide higher accessible surface area, this characteristic helps electrolyte ion to permeate fast and enter the internal surface of electrode material.
When preparing the graphene-bismuth alkene hydrogel with the composite staggered and stacked intercalation structure: firstly, putting graphene oxide into a mixed solution of deionized water and an ammonia solution, and performing ultrasonic dispersion to promote solid-liquid reaction. Dispersing the precursor solution, and mixing the precursor solution with the graphene oxide solution, the regenerated bismuth alkene solution and the deionized water to reduce the size of dispersed phase particles, increase interphase interfaces and uniformly disperse the particles; 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 And (3) dialyzing the mixture of O (1:100, V: V) to remove impurities, and preparing the graphene-bismuth alkene hydrogel with the composite staggered and stacked intercalation structure. MiningWhen the hydrogel is prepared by a hydrothermal method, a bismuth-graphene layer is inserted between the layered structures of graphene, and observation and density measurement are carried out on an electron microscope image of the gel, so that 80-100 micro units exist in the thickness per unit centimeter shown in figure 1, each micro unit is composed of 800-900 single-layer graphene layers and 80-100 bismuth-graphene layers, the bismuth-graphene layer and the graphene layers are combined by strong hydrogen bonds and C-Bi bonds, and the design and construction of an ion/electron double transmission channel in an aerogel frame with a staggered and stacked structure are realized by the synergistic effect of bismuth-graphene and graphene. The bismuthated graphene framework shows cross-linked hierarchical structures of different sizes, ranging from hundreds of nanometers to several micrometers, which are beneficial to electrolyte permeation, ensure the electron transfer between layers and effectively increase mass capacitance. In addition, the conductive bismuth nanosheets coated on the reduced graphene can be used as a main trunk for constructing an additional electron transmission channel, and generate additional electrochemical active sites, so that the interlayer conductivity is improved, and the interlayer electron transmission is ensured. The graphene oxide gel can also be used as a nano anchor to enhance the bonding strength among 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 sheet layers, so that interlayer electron transmission is ensured, interlayer conductivity reduction caused by interlayer interval insertion is relieved, and meanwhile, the bismuth-alkene material of the structure which can be used as a pseudo-capacitance active material can provide additional redox sites.
When the composite staggered-stacked intercalation structure graphene-bismuth alkene aerogel is prepared, dialyzing the obtained composite staggered-stacked intercalation structure graphene hydrogel in a mixed solution of ethanol and water, separating and purifying to remove gel floating, freezing the gel in a refrigerator to protect a hydrogel carrier and a colloidal particle structure, and then freeze-drying to remove moisture of the composite graphene hydrogel and strut graphene sheets to form a porous reticular structure, wherein as shown in figure 2, the composite staggered-stacked intercalation structure graphene-bismuth alkene aerogel is prepared;
the composite type staggered-stacked intercalation structure graphene-bismuth alkene aerogel disclosed by the invention 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 constructs a super-capacitor pressure sensor. Compared with a pressure sensor prepared from graphene aerogel without bismuth alkene, the pressure sensor prepared from the graphene aerogel with the composite staggered and stacked intercalation structure has the advantages of larger relative change of capacitance and resistance and higher sensitivity. The super capacitor has the advantages that due to the synergistic effect of a staggered intercalation structure formed by stacked bismuth-graphene layers and stacked graphene layers, 80-100 micro units exist in each unit centimeter of thickness, and each micro unit is composed of 800-900 single-layer graphene layers and 80-100 bismuth-graphene layers; as shown in fig. 4, the deconvolved peaks of C1s 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 composite aerogel frame is characterized in that a bismuth-graphene layer and a graphene layer are combined by strong hydrogen bonds and C-Bi bonds, and the ion/electron double transmission channels are designed and constructed in the aerogel frame with the staggered intercalation structure under the synergistic effect of bismuth-graphene and graphene. These structures have abundant electrochemically active centers, high conductivity, low interfacial resistance and fast ion/electron transport, facilitate electrolyte permeation, and ensure interlayer electron transfer, effectively increasing mass capacitance.
The beneficial effects of the invention are:
1) compared with the prior art, the bismuth-graphene composite aerogel has the advantages that bismuth-graphene is inserted between graphene laminated structures, and bismuth-graphene frameworks show cross-linked hierarchical structures with different sizes, which are different from hundreds of nanometers to several micrometers. The layered pores not only provide a transmission channel for ions or ion groups in the electrolyte, but also help to reveal active centers and improve double-layer capacitance, thereby improving the performance of electrochemistry and pressure sensors; the density of the material is 10-15 mg/cm -3 The structure consists of C, O, N, Bi elements, 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 cannot be deteriorated by chemical reaction due to excessively active electrochemical activity; prepared symmetrical super capacitorThe device battery is 400 W.Kg -1 The energy density at that time was 45.55 Wh.Kg -1 The cycle stability after 3600 charge-discharge cycles was 89.24%. The ion/electron capacitance sensor has 0.326kPa -1 And has satisfactory durability during 1000 pressure load cycles.
3) In addition, the super-capacitor pressure sensor based on the graphene aerogel with the composite staggered and stacked intercalation structure has the stress of 0.326kPa within the range of 1.5-4.5 kPa -1 The fitting degree is 0.99; after the voltage is cycled for 1000 times, the relative change of the capacitance still keeps 87 percent of the original value, and the stress stability is high; the micro-change of strain (0.012%) and pressure (0.25Pa) can be sensed, and low pressure can be effectively detected; can provide fast current response to external pressure changes; the super-capacitor has super-capacitor characteristics, 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 of the present invention, in which 1 is titanium foil, 2 is silver colloid, 3 is a micro-unit formed by graphene and bismuth-alkene, and N is 1 The size of (a) is 80-100, the right side is an enlarged view of a single micro unit, wherein 4 is a graphene layer, and the single micro unit approximately contains N 2 Layer, N 2 800-900, 5 is a bismuth-alkene layer, and a single tiny unit contains about N 3 Layer, N 3 The size is 80-100;
fig. 2 is a schematic diagram of preparation of graphene-bi-graphene aerogel with a composite staggered and stacked intercalation structure according to the present invention and a partially microscopic enlarged view;
fig. 3 is SEM images of the aerogel of the present invention, wherein (a-c) are SEM images of redox graphene at different scales, and (d-f) are SEM images of composite type staggered-stacked intercalation structure graphene-bismuth ene aerogel at different scales.
FIG. 4 is an XPS analysis of sample C of example 2 of the present invention, with deconvoluted peaks of C1s 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 is the bookInventive example 3 GCD (constant current charge and discharge) behavior of sample electrode at different densities, the current density was from 0.64A · g -1 To 3 A.g -1 ；
FIG. 6 is a graph showing the relative capacitance change at different compressive strains for the samples of example 4 of the present invention, with the stress varying in the range of 0.5kPa to 4.5 kPa;
fig. 7 is a graph of electrochemical cycling stability of a supercapacitor after 3600 charge-discharge cycles for a sample of example 5 of the present invention.
FIG. 8 is a graph of the relative change in capacitance at 1kPa force and 14k cycles for the sample of example 6 of the present invention; where the left and right hand insets represent magnified views of some selected cycles from the beginning and end of the test.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention.
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 terminology used herein in the description of the present invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention.
Example 1
A preparation method of graphene-bismuth alkene aerogel with a composite staggered and stacked intercalation structure comprises the following steps:
1) preparing bismuth alkene: mixing 100mg bismuth powder with 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 of H 2 O 2 Sealed at room temperature for 12 hours and then washed 5 times with ethanol to remove residual H 2 SO 4 (ii) a 20mg of the resulting dry powder was sonicated with 1mL of deionized water in a sealed environment for 6 hours. Finally, filtering the mixture to remove the un-peeled bismuth powder, and obtaining the bismuth powder with the concentration of 0.014-0.017g·mL -1 The bismuth-alkene solution of (1).
2) Preparing composite type staggered stacking intercalation structure hydrogel: first, 100mg of graphene oxide was put into a mixed solution of 20mL of deionized water and 0.8mL of an 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 12 h. Subsequently, the hydrogel is in CH 3 CH 2 OH/H 2 Dialyzing the mixture of O (1:100, V: V) for 6 hours, and cooling to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite staggered and stacked intercalation structure.
3) Preparing composite type aerogel with a graphene-bismuth alkene staggered stacking intercalation structure: freezing the hydrogel obtained in the step 2) in a refrigerator for 12 hours to obtain aerogel, which is named BiGA 1.
For comparison, when the bismuth-graphene solution is not added in the step 2), and other steps are not changed, the graphene aerogel is prepared, and named as NGA.
In this example, as shown in FIG. 3, the surface waviness and porosity of the SEM frame of the BiGA1 sample were measured to be increased compared with NGA, which was found to have a smoother surface and a small porosity in the SEM image, and the density of the BiGA1 sample was 11.1 mg-cm -3 The comparative NGA volume increases. Stacking between graphene sheet layers in the BiGA1 sample is obviously reduced, the interior of the BiGA1 sample contains a hybrid structure, the structure is composed of C, O, N, Bi, and the atomic number ratio ranges are 79.8%, 15%, 6% and 0.2%, respectively. It was determined that the sample required only 11.5kPa force at the first compression to 50% strain, whereas the NGA sample required 125kPa force, indicating that the BiGA1 sample with added bismuth ene was softer and more sensitive.
Example 2
A preparation method of graphene-bismuth alkene aerogel with a composite staggered and stacked intercalation structure comprises the following steps:
1) preparing bismuth alkene: mixing 90mg of bismuth powder with 0.40g of (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 of H 2 O 2 Sealed at room temperature for 10 hours and then washed 4 times with ethanol to remove residual H 2 SO 4 (ii) a 18mg of the resulting dry powder was sonicated with 1mL of deionized water in a sealed environment for 6 hours. Finally, the mixture was filtered to remove the unstripped bismuth powder, and bismuth alkene was obtained from the supernatant.
2) Preparing composite type staggered stacking intercalation structure hydrogel: first, 80mg of graphene oxide was put into a mixed solution of 15mL of deionized water and 0.5mL of an ammonia solution, and ultrasonically dispersed for 50 minutes. Then, 5mL of the reduced graphene oxide solution was mixed with 0.4mL of the bismuth ene 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 12 h. Subsequently, the hydrogel is in CH 3 CH 2 OH/H 2 Dialyzing the mixture of O (1:100, V: V) for 5-6 hours, and cooling to room temperature. And preparing the graphene-bismuth alkene hydrogel with the composite staggered and stacked intercalation structure.
3) Preparing composite graphene-bismuth alkene staggered stacking intercalation structure aerogel: freezing the hydrogel obtained in the step 2) in a refrigerator for 12h to obtain aerogel, which is named BiGA 2.
Example 3
A preparation method of composite graphene-bismuth alkene staggered stacking intercalation structure aerogel comprises the following steps:
1) preparing bismuth alkene: mixing 90mg of bismuth powder with 0.40g of (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 of H 2 O 2 Sealed at room temperature for 10 hours and then washed 4 times with ethanol to remove residual H 2 SO 4 (ii) a 18mg of the resulting dry powder was sonicated with 1mL of deionized water in a sealed environment for 6 hours. Finally, the mixture was filtered to remove the non-exfoliated bismuth powder, and the bismuth alkene was obtained from the supernatant.
2) Preparing composite type staggered stacking intercalation structure hydrogel: first, 80mg of graphene oxide was put into a mixed solution of 15mL of deionized water and 0.5mL of an 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. Precursor bodyThe solution was sealed in a 10mL autoclave lined with Teflon at 120 ℃ for 12 h. Subsequently, the hydrogel is in CH 3 CH 2 OH/H 2 Dialyzing the mixture of O (1:100, V: V) for 5-6 hours, and cooling to room temperature. And preparing the composite graphene-bismuth alkene hydrogel.
3) Preparing composite graphene-bismuth alkene staggered stacking intercalation structure aerogel: freezing the hydrogel obtained in the step 2) in a refrigerator for 12h to obtain aerogel, which is named BiGA 3.
In this example, it was determined that the SEM frames of the BiGA3 samples had a small number of complex networks interconnected by rugose lines, with a density of 14.1mg cm, increased in rugose and porosity compared to NGA surfaces -3 The comparative NGA volume increases. Measured at a current density of 0.67 A.g -1 The mass specific capacitance of the BiGA3 sample electrode was 400.83F g -1 Mass specific capacitance 275F g compared to NGA sample electrode -1 The method is greatly improved, and the result shows that the graphene-bismuth alkene framework can provide a good environment for ions and provide high specific capacitance and excellent rate performance. As shown in FIG. 5, the GCD behavior of the BiGA3 sample was observed at high operating current densities, from 0.64A-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: to 30mL of deionized water were added 3g of PVA and 1.5g of concentrated H 2 SO 4 And completely dissolving at 80 ℃ for 60min to form the gel electrolyte.
2) Preparing upper and lower electrodes of the composite graphene-bismuth alkene aerogel with the staggered and 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 the 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 60 min. And polypropylene diaphragm paper with the size of 0.7-1.0 cm2 is clamped between the two electrodes, so that a symmetrical all-solid-state supercapacitor, namely a supercapacitor pressure sensor, is realized.
In the present embodiment, the pressure sensor is prepared based on the BiGA3 sample, the sensor is a sandwich structure, the upper layer and the lower layer are both titanium electrodes, and the middle layer is a graphene-bismuth-ene aerogel with a composite staggered-stacked intercalation structure and impregnated with a gel electrolyte, as shown in fig. 6, it shows that the stress sensitivity is 0.052kPa when the pressure is in the range of 0 to 1.5kPa -1 In the range of 1.5 to 4.5kPa, the sensitivity is 0.326kPa -1 The NGA-based sensor showed a sensitivity of 0.024kPa over a pressure range of 0 to 2.5kPa -1 The linear sensitivity is 0.282kPa in the pressure range of 2.5 to 4.5kPa -1 And the data comparison shows that compared with a pressure sensor prepared by an NGA sample without adding the 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: to 30mL of deionized water were added 3g of PVA and 1.5g of concentrated H 2 SO 4 And completely dissolving at 80 ℃ for 60min to form the gel electrolyte.
2) Preparing upper and lower electrodes of the composite graphene-bismuth alkene aerogel with the staggered and 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 60 min. A size of 1.0cm is sandwiched between two electrodes 2 The polypropylene diaphragm paper realizes a symmetrical all-solid-state supercapacitor.
In the present embodiment, the pressure sensor is prepared based on the BiGA3 sample, the sensor is of a sandwich structure, the upper layer and the lower layer are both electrodes, and the intermediate layer is a graphene-bismuth alkene aerogel of a composite staggered-stacked intercalation structure injected with a gel electrolyte, as shown in fig. 7, it shows a significant capacity retention rate of 89.24% after 3600 charge-discharge cycles.
Example 6
Preparation of super-capacitor type pressure sensor
1) Preparation of gel electrolyte: to 30mL of deionized water were added 3g of PVA and 1.5g of concentrated H 2 SO 4 And completely dissolving at 80 ℃ for 60min to form the gel electrolyte.
2) Preparing upper and lower electrodes of the composite graphene-bismuth alkene aerogel with the staggered and stacked intercalation structure: and respectively soaking two graphene-bismuth alkene aerogel/Ti electrodes serving as a negative electrode and a positive electrode in the prepared gel electrolyte for 60 min. A size of 1.0cm is clamped between the two electrodes 2 The polypropylene diaphragm paper realizes a symmetrical all-solid-state supercapacitor.
In this example, a pressure sensor was prepared based on the BiGA3 sample, and as shown in fig. 8, the sensor still has 87% of the original value of the relative change in capacitance after 1000 cycles of pressure cycling, and has high stress stability; the sensor is of a sandwich structure, the upper layer and the lower layer of the sensor are both electrodes, the middle layer is the graphene-bismuth alkene aerogel of a composite staggered and stacked intercalation structure injected with gel electrolyte, and the stress sensitivity of the graphene-bismuth alkene aerogel is 0.73kPa -1 The degree of fit is 0.99; pressure sensor prepared based on NGA sample and having stress sensitivity of 0.04kPa -1 The degree of fit is 0.96; pressure sensor prepared based on BiGA1 sample and having stress sensitivity of 0.10kPa -1 The fitting degree is 0.99; pressure sensor prepared based on BiGA2 sample and having stress sensitivity of 0.15kPa -1 The degree of fit was 0.99.
TABLE 1
Compared with NGA, BiGA1 and BiGA2, the pressure sensor prepared based on the BiGA3 sample is found to have the advantages of being optimal in BiGA3 sensitivity, highest in fitting degree, best in elastic compressibility, capable of sensing small changes of strain and pressure, capable of providing rapid current response to external pressure changes, and excellent in electrochemical energy storage, super-capacitor characteristics and cycle stability.
In summary of the examples, it was found that the pressure sensors based on the BiGA3 samples had the best stress sensitivity and the best performance compared to pressure sensors prepared based on the BiGA1, BiGA2, BiGA3 samples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A bismuth-graphene layer is inserted between layered structures of graphene to form a staggered and stacked intercalation structure, each unit centimeter of thickness is provided with 80-100 micro units, and each micro unit is composed of 800-900 stacked single-layer graphene layers and 80-100 stacked single-layer bismuth-graphene layers.
2. The graphene-bismuth ene aerogel with the composite staggered and stacked intercalation structure according to claim 1, wherein the bismuth ene layer and the graphene layer are bonded by strong hydrogen bonds and C-Bi bonds, and the density of the aerogel is 10-15 mg-cm -3 The structure of ion and electron double transmission channels is formed in the staggered and stacked intercalation structure aerogel frame, the structure is composed of C, O, N, Bi, and the atomic number ratio ranges are 78.7% -80%, 14% -15%, 5% -6%, and 0.2% -0.3%, respectively.
3. A preparation method of graphene-bismuth alkene aerogel with a composite staggered and stacked intercalation structure is characterized by comprising the following steps:
1) preparing bismuth alkene: mixing 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 (ii) a Adding deionized water into the obtained powder, and carrying out ultrasonic treatment; filtering to remove un-peeled bismuth powder, and obtaining the bismuth powder with the concentration of 0.014-0.017 g.mL from the supernatant -1 Bismuth-alkene solution;
2) preparing the graphene-bismuth ene hydrogel with the composite staggered and stacked intercalation structure:
firstly, putting graphene oxide powder into a mixed solution of deionized water and an ammonia solution, and performing ultrasonic dispersion to obtain graphene oxide powder with the concentration of 0.004-0.008 g/mL -1 The reduced graphene oxide solution of (1);
then, mixing the reduced graphene oxide solution with the bismuth alkene solution prepared in the step 1) according to a volume ratio of (3-5): (0.2-1.2) preparing a precursor solution by mixing; sealing the precursor solution in an autoclave with a polytetrafluoroethylene lining, and keeping the temperature of 100-120 ℃ for 10-14 h to obtain hydrogel with a staggered stack intercalation structure;
then, the hydrogel of the staggered and stacked intercalation structure is placed in CH 3 CH 2 OH/H 2 Dialyzing the mixture of O (1:100, V: V) for 3-6 h, and cooling to room temperature to obtain the graphene-bismuth ene hydrogel with the composite staggered and stacked intercalation structure;
3) preparing a graphene-bismuth alkene aerogel with a composite staggered and stacked intercalation structure: and (3) keeping the hydrogel obtained in the step 2) in a freeze drying oven at the temperature of-18 to-20 ℃ for freeze drying for 10 to 12 hours to obtain the aerogel.
4. The graphene-bismuth ene aerogel with the composite type staggered and intercalated structure, which is described in claim 1 or 2 or obtained by the preparation method in claim 3, and is characterized in that the current density is 0.6-1.0A-g -1 The mass specific capacitance is 360- -1 。
5. The application of the graphene-bismuth ene aerogel with the composite type staggered and stacked intercalation structure in the super-capacitor pressure sensor as claimed in claim 4, wherein the super-capacitor pressure sensor has a sandwich structure, the upper layer and the lower layer are both electrodes, the intermediate layer is the graphene-bismuth ene aerogel with the composite type staggered and stacked intercalation structure, and the graphene-bismuth ene aerogel with the composite type staggered and stacked intercalation structure is filled with gel electrolyte.
6. The use of claim 5, wherein the super capacitor type pressure sensor is prepared by the following steps:
1) first, PVA and concentrated H were added to deionized water 2 SO 4 Completely dissolving at 80-85 ℃ to form a 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 staggered stacking intercalation structure graphene-bismuth alkene aerogel electrode, namely a graphene-bismuth alkene aerogel/electrode; 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 respectively; a gap of 0.7-1.0 cm is arranged between the two electrodes 2 The polypropylene diaphragm paper realizes a symmetrical all-solid-state supercapacitor.
7. The use according to any one of claims 5 to 6, wherein the pressure sensor has a stress of 0.326kPa in the range of 1.5 to 4.5kPa -1 And after 1000 pressure load cycles, the relative change of the capacitance can still be respectively retained as 87% of the original value; at 400 W.Kg -1 When the yield is 45.55 Wh.Kg -1 The energy density of (2) was 89.24% after 3600 charge-discharge cycles.
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