CN113441094A - Boron-graphene composite aerogel, preparation and application thereof - Google Patents
Boron-graphene composite aerogel, preparation and application thereof Download PDFInfo
- Publication number
- CN113441094A CN113441094A CN202110822880.0A CN202110822880A CN113441094A CN 113441094 A CN113441094 A CN 113441094A CN 202110822880 A CN202110822880 A CN 202110822880A CN 113441094 A CN113441094 A CN 113441094A
- Authority
- CN
- China
- Prior art keywords
- boron
- graphene
- graphene composite
- composite aerogel
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000004964 aerogel Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 69
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000017 hydrogel Substances 0.000 claims abstract description 21
- -1 boron alkene Chemical class 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000011245 gel electrolyte Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 11
- 238000001514 detection method Methods 0.000 abstract description 10
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000012827 research and development Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 230000035945 sensitivity Effects 0.000 description 16
- 230000008859 change Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/12—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in capacitance, i.e. electric circuits therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a boron alkene-graphene composite aerogel and application of a pressure sensor of the boron alkene-graphene composite aerogel, and belongs to the technical field of sensors. The preparation method comprises the following steps: 1) preparing boron alkene; 2) preparing boron alkene-graphene composite hydrogel; 3) dialyzing the boron alkene-graphene composite hydrogel; 4) freeze-drying the boron alkene-graphene composite hydrogel; 5) preparing the boron-graphene composite aerogel; 5) and (5) packaging the pressure sensor. The boron-graphene composite aerogel has a porous structure and excellent mechanical properties, can be used as an elastic dielectric layer, and is applied to the research and development of a high-sensitivity capacitance pressure sensor. The capacitance pressure sensor has 0.89kPa in the range of 0-3 kPa‑1With a minimum detection force of 8.7Pa, and a response time of 110 ms. The boron-graphene composite aerogel monolith of the inventionThe body manufacturing process is simple, the functions are various, and the pressure sensor has a good application prospect in the field of pressure sensors.
Description
Technical Field
The invention relates to a boron graphene-graphene composite aerogel, a preparation method and application thereof, and belongs to the field of electronic material devices.
Background
Graphene, which is a two-dimensional material that is peeled from graphite and has a single atomic thickness composed of carbon atoms, has excellent elasticity and electrical conductivity, and a mechanical device based on graphene has high sensitivity, so that graphene materials are widely applied to various flexible mechanical devices by scientists. The graphene aerogel has the characteristics of small density, high elasticity, strong adsorption and porous material, so that the graphene aerogel has a great application prospect in the aspects of mechanics and adsorption. Boron alkene is a new material that is more flexible, lighter, more stable and range of application wider than graphite alkene, has the potentiality to combine with graphite alkene, promotes electricity, mechanical stability.
The pressure sensor is the most common sensor in industrial practice, is widely applied to various industrial automatic control environments, and relates to a plurality of industries such as water conservancy and hydropower, railway traffic, intelligent buildings, production automatic control, aerospace, military industry, petrochemical industry, oil wells, electric power, ships, machine tools, pipelines and the like. At present, common pressure sensors mainly comprise a capacitance type pressure sensor and a piezoresistive type pressure sensor, and compared with the piezoresistive type pressure sensor, the capacitance type pressure sensor has the advantages of short response time, wide temperature range and the like. The capacitance pressure sensor comprises a polar distance change type and an area change type, and compared with the area change type, the polar distance change type capacitance pressure sensor has small influence on a system to be measured and high sensitivity.
In the existing Chinese patent, "a preparation method of three-dimensional nitrogen and boron co-doped graphene aerogel" (publication number CN160829929B), boron nitride is used as a nitrogen source and a boron source, and a hydrothermal method and freeze drying are adopted to prepare the graphene aerogel with high adsorption performance, but the boron nitride does not have good elasticity, so that the elasticity of the aerogel is reduced. In another Chinese patent, "a graphene pressure sensor and a structure and a preparation method thereof" (publication number CN110207867A), the sensor is composed of an interdigital electrode layer, an embedded graphene elastic substrate layer and a flexible packaging layer. The preparation process is complex, and the excellent mechanical property of the graphene is not fully exerted, so that the sensitivity of the sensor is low.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a boron-graphene composite aerogel and application of a pressure sensor thereof. According to the invention, a liquid phase stripping method is adopted, the boron alkene is prepared by ultrasonic crushing, and the composite aerogel is prepared by a hydrothermal method, so that the preparation process is simpler. According to the method, ammonia water and boron alkene are used as a nitrogen source and a boron source, wherein the ammonia water also plays a role in reduction, and graphene oxide is reduced. The obtained aerogel has better conductivity and a porous cellular structure, greatly improves the elasticity of the aerogel, simultaneously selects a freeze-drying method to make the aerogel more stable, has simpler preparation process, and is suitable for serving as a pressure sensor.
The invention also provides a preparation method of the boron-graphene composite aerogel and application of the boron-graphene composite aerogel in a pressure sensor, and the preparation method comprises preparation of boron, preparation of boron-graphene composite hydrogel, dialysis of the boron-graphene composite hydrogel, preparation of the boron-graphene composite aerogel and application of the boron-graphene composite aerogel in the field of pressure sensors.
The invention relates to a boron-graphene composite aerogel, which is mainly formed by compounding boron and graphene, wherein two-dimensional boron and graphene jointly form a three-dimensional reticular aerogel structure, and the atomic number percentage ranges of C, O, N, B elements are respectively 68% -70%, 10% -12%, 16% -18% and 4% -5%.
The preparation method of the boron-graphene composite aerogel can adopt the following steps:
1) preparing a boron alkene-graphene mixed precursor solution: ultrasonically crushing 5-15 mg of amorphous boron powder in 10-30 ml of DMF (N, N-dimethylformamide) solution at normal temperature for 3-5 hours, centrifuging at 3000-5000 rpm for 20-40 minutes, and taking supernatant to obtain the DMF solution dispersed with the borane; adding graphene oxide into a deionized water solution and continuously performing ultrasonic treatment to obtain a dispersion solution; preparing a mixed precursor solution, wherein the mass ratio of graphene oxide, ammonia water, a boron-alkene-dispersed DMF solution and deionized water is (15-30) to (50-100): (600-700): (1800-1900). The mixed precursor solution is prepared by uniformly mixing ammonia water, a DMF solution dispersed with the boron alkene and a dispersion solution of the graphene oxide. The ammonia water is common ammonia water, and the concentration is 25-28 percent (mass).
2) Preparing the boron alkene-graphene composite hydrogel: adding the mixed precursor solution into a reaction kettle, placing the reaction kettle in an oven for hydrothermal reaction, wherein the temperature of the oven for hydrothermal reaction is 90-140 ℃, and carrying out hydrothermal reaction for 8-10 hours to obtain the boron alkene-graphene composite hydrogel; and then mixing the absolute ethyl alcohol and the water in a ratio of 1: (90-110) preparing a mixed dialysate, and finally immersing the boron graphene-graphene composite hydrogel into the dialysate for dialysis, wherein the temperature is kept between 15 ℃ and 25 ℃, and dialyzing for 5-8 hours;
3) preparing the boron graphene-graphene composite aerogel: freezing the hydrogel obtained in the step 2) at the temperature of-10 to-20 ℃ for 6 to 14 hours. Then carrying out freeze drying under vacuum, wherein the freeze drying temperature is-40 ℃ to-30 ℃, and drying for 18-24 hours to obtain the boron-graphene composite aerogel;
the preparation method of the pressure sensor specifically comprises the following steps:
1) pre-treating an electrode; cleaning the electrode to remove impurities and oil stains on the surface of the electrode;
2) preparation of gel electrolyte: preparing PVA solid powder and concentrated sulfuric acid into an aqueous solution, wherein the mass percentage ranges of PVA, concentrated sulfuric acid and deionized water are (5-10): (1-2): (50-80), and heating and stirring for 1-2 hours in a water bath at the temperature of 90-100 ℃;
3) preparing a pressure sensor: brushing the gel electrolyte prepared in the step 2) on the electrode prepared in the step 1) to form a PVA (polyvinyl alcohol) adhesive film, soaking the boron-graphene composite aerogel in the gel electrolyte for 5-15 min, and fixing the boron-graphene composite aerogel on a metal sheet electrode through the PVA adhesive film to assemble: the electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure is placed in an oven for drying, the drying temperature is 30-50 ℃, and the drying time is 18-24 hours.
The application principle of the preparation of the boron-graphene composite aerogel and the pressure sensor thereof is as follows: the boron-graphene composite aerogel is prepared from materials such as boron-graphene and graphene by a composite hydrothermal method, wherein the two-dimensional boron-graphene and the two-dimensional graphene jointly form the boron-graphene composite aerogel with a three-dimensional reticular aerogel structure. The two-dimensional boron graphene has good mechanical property and electrical property, the mechanical stability of the graphene structure is reinforced, and the electrical activity of the graphene is enhanced. Therefore, compared with pure graphene aerogel, the boron-graphene composite aerogel has more internal porous structures and better mechanical properties.
Compared with the prior art, the boron-graphene composite aerogel disclosed by the invention has a porous honeycomb structure, very strong mechanical elasticity and stability, a simple manufacturing process and a good prospect in the field of pressure sensing application.
Drawings
Fig. 1 is an SEM scanning electron micrograph of a boron graphene-graphene composite aerogel in samples 1, 2, 3 prepared according to examples 1, 2 of the present invention;
fig. 2 is a block diagram of a pressure sensor prepared according to the present invention. Wherein 1 is an electrode; 2 is a boron-graphene composite aerogel dielectric layer; and 3 is a PVA film.
Fig. 3 is a graph of test results and sensitivity of a pressure sensor assembled based on a borane-graphene composite aerogel prepared in sample 1 of example 3;
fig. 4 is a graph of test results and sensitivity of a pressure sensor assembled based on a borane-graphene composite aerogel prepared in sample 2 of example 3;
fig. 5 is a graph of test results and sensitivity of a pressure sensor assembled based on a borane-graphene composite aerogel prepared in sample 3 of example 4;
fig. 6 is a response time detection graph of a pressure sensor assembled based on a boron graphene-graphene composite aerogel prepared in sample 3 of example 4;
fig. 7 is a minimum pressure detection diagram of a pressure sensor assembled based on a boron graphene-graphene composite aerogel prepared in example 4, sample 3;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be noted, however, that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as terms in the field of the present invention, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention.
Example 1 preparation of B-graphene composite aerogels
1) Preparing a boron alkene-graphene mixed precursor solution: ultrasonically crushing 10mg of amorphous boron powder in 20ml of DMF solution at normal temperature for 4 hours by using a cell crusher, centrifuging for 30 minutes at the rotating speed of 4000rpm, and taking supernate to obtain the DMF solution dispersed with boron alkene; adding graphene oxide into a deionized water solution and continuously performing ultrasonic treatment to obtain a dispersion solution; preparing mixed precursor solution samples 1 and 2, wherein the ratio of sample 1: the mass ratio range of the graphene oxide, the ammonia water and the deionized water is 20: 80: 1800. as a control, sample 1 was not added to the DMF solution with dispersed borane. Sample 2: the mass ratio of graphene oxide to ammonia water to the DMF solution dispersed with boron to deionized water is 20: 80: 600: 1800.
2) preparing the boron alkene-graphene composite hydrogel: adding the mixed precursor solution of the samples 1 and 2 into a reaction kettle, placing the reaction kettle into an oven, and carrying out hydrothermal reaction, wherein the oven temperature is 120 ℃ and the hydrothermal time is 10 hours during the hydrothermal reaction to obtain the boron graphene-graphene hydrogel; and then mixing the absolute ethyl alcohol and the water in a ratio of 1: preparing mixed dialysate according to the volume ratio of 100, immersing the boron alkene-graphene composite hydrogel into the dialysate for dialysis, and keeping the temperature at 25 ℃ for 7 hours;
3) preparing the boron graphene-graphene composite aerogel: freezing the sample 1 and 2 boron alkene-graphene composite hydrogel obtained in the step 2) at-10 ℃ for 12h, and then carrying out vacuum freeze drying at-30 ℃ for 24h to obtain a sample 1 and 2 boron alkene-graphene composite aerogel; sample 1 is actually graphene aerogel.
The prepared boron-graphene composite aerogel is compounded by boron-graphene, graphene and other materials, two-dimensional boron-graphene and two-dimensional graphene jointly form a three-dimensional reticular aerogel structure in a space, wherein atomic number percentages of elements C, O, N in a sample 1 boron-graphene composite aerogel are respectively 70%, 12% and 18%; the atomic number percentages of the elements of the sample 2-boracene-graphene composite aerogel C, O, N, B are 69%, 10%, 17% and 4%, respectively. In fig. 1, (a) and (b) are SEM images of sample 1 and 2 b graphene-graphene composite aerogel, respectively, it can be seen that the interior of the sample 1 is a three-dimensional mesh structure, and the sample 2 is denser than the three-dimensional mesh of the interior of the sample 1.
Example 2 preparation of B-graphene composite aerogels
1) Preparing a boron alkene-graphene mixed precursor solution: ultrasonically crushing 10mg of amorphous boron powder in 20ml of DMF solution for 4 hours at normal temperature, centrifuging for 30 minutes at the rotating speed of 4000rpm, and taking supernate to obtain the DMF solution dispersed with boron alkene; adding graphene oxide into an aqueous solution and continuously performing ultrasonic treatment to obtain a dispersion solution; preparing a mixed precursor solution sample 3, wherein the mass ratio of the graphene, ammonia water, the DMF solution dispersed with the boron alkene and deionized water in the sample 3 is 20: 80: 700: 1800.
2) preparing the boron alkene-graphene composite hydrogel: adding the sample 3 mixed precursor solution into a reaction kettle, placing the reaction kettle in an oven, and carrying out hydrothermal reaction, wherein the temperature of the oven is 120 ℃ in the hydrothermal reaction, and carrying out hydrothermal reaction for 10 hours to obtain a boron graphene-graphene hydrogel; mixing absolute ethyl alcohol and water according to the ratio of 1: preparing mixed dialysate according to the volume ratio of 100, immersing the boron graphene-graphene hydrogel into the dialysate for dialysis, keeping the temperature at 25 ℃, and dialyzing for 7 hours;
3) preparing the boron graphene-graphene composite aerogel: freezing the sample 3 boron alkene-graphene composite hydrogel obtained in the step 2) at-10 ℃ for 12h, and then carrying out vacuum freeze drying at-30 ℃ for 24h to obtain a sample 3 boron alkene-graphene composite aerogel;
the boron-graphene composite aerogel is formed by compounding boron and graphene, a two-dimensional boron and two-dimensional graphene form a three-dimensional reticular aerogel structure together, and the atomic number percentages of C, O, N, B elements in the sample 3 boron-graphene composite aerogel are respectively 68%, 11%, 16% and 5%. Fig. 1 (c) shows SEM images of 3-borographene-graphene composite aerogel, and it can be seen that the inside of the sample is a three-dimensional network structure, and the sample 3 is denser than the three-dimensional meshes inside the samples 1 and 2.
In summary, comparing examples 1, 2 and 3, it can be found that the internal three-dimensional meshes of the 3-borographene-graphene composite aerogel sample are more dense.
EXAMPLE 3 preparation of pressure sensor
1) Pretreatment of an electrode: cleaning a sample by using a titanium sheet as an electrode and sequentially using distilled water, ethanol and acetone to remove impurities and oil stains on the surface of the sample;
2) preparation of gel electrolyte: preparing PVA solid powder and concentrated sulfuric acid into an aqueous solution, wherein the mass ratio of PVA to sulfuric acid to deionized water is 8: 2: 70, heating and stirring the mixture in a water bath kettle at the temperature of 90 ℃ for 1 hour;
3) preparing a pressure sensor: brushing the gel electrolyte prepared in the step 2 on the electrode prepared in the step 1) to form a PVA (polyvinyl alcohol) viscous film, soaking the sample 1 and the sample 2 boron alkene-graphene composite aerogel prepared in the step 1 in the gel electrolyte for 10min, fixing the sample on a metal sheet electrode through the PVA viscous film, assembling into an electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure, placing the electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure in an oven for drying, wherein the drying temperature is 50 ℃, and the drying time is 24 hours, and obtaining the sample 1 and the sample 2 pressure sensors.
Fig. 2 shows a structure diagram of the pressure sensor, in which 1 is an electrode, 2 is a boron graphene-graphene composite aerogel dielectric layer, and 3 is a PVA film. Fig. 3 shows the capacitance change curve and the sensitivity curve of the pressure sensor based on sample 1 under different forces, where the sensitivity is 0.54KPa-1The detection limit interval is 20-2000Pa, and the fitting degree is 0.99. Fig. 4 shows the capacitance change curve and the sensitivity curve of the pressure sensor based on sample 2 under different forces, where the sensitivity is 0.72KPa-1The detection limit interval is 18-2000Pa, and the fitting degree is 0.99. The data comparison shows that the pressure sensor based on the sample 2 has higher sensitivity, larger detection limit range and better performance compared with the pressure sensor based on the sample 1.
EXAMPLE 4 preparation of pressure sensor
1) Cleaning of the electrode: cleaning a sample by using a titanium sheet as an electrode and sequentially using distilled water, ethanol and acetone to remove impurities and oil stains on the surface of the sample;
2) preparation of gel electrolyte: preparing PVA solid powder and concentrated sulfuric acid into an aqueous solution, wherein the mass percentages of PVA, sulfuric acid and deionized water are respectively 8: 2: 70, heating and stirring the mixture in a water bath kettle at the temperature of 90 ℃ for 1 hour;
3) preparing a pressure sensor: brushing the gel electrolyte prepared in the step 2 on the electrode prepared in the step 1) to form a PVA (polyvinyl alcohol) viscous film, soaking the sample 3 boron alkene-graphene composite aerogel prepared in the step 2 in the gel electrolyte for 10min, fixing the sample on a metal sheet electrode through the PVA viscous film to assemble an electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure, and placing the electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure in an oven for drying at the drying temperature of 50 ℃ for 24 hours to obtain the sample 3 pressure sensor.
FIG. 5 is a graph showing the capacitance change curve and the sensitivity curve of the pressure sensor based on the sample 3 under different forces, wherein the sensitivity isS＝0.89KPa-1The detection limit interval is 8.7-3000Pa, and the fitting degree is 0.99.
Combining examples 3 and 4, it can be seen that the pressure sensor based on sample 3 has higher sensitivity, larger detection limit range and best performance compared with the pressure sensors based on samples 1, 2 and 3 according to the measured data of the pressure sensor in table 1.
TABLE 1
Example 5 detection of response time and minimum pressure
Combining examples 3 and 4, the sample 3-based pressure sensor has higher sensitivity, and is detected with response time and minimum pressure.
1) A force of 0.25kPa was applied to the sample 3 pressure sensor by the press to detect the response time. As shown in fig. 6, the response time of the collected capacitance signal was 110ms during the application of the force of 0.25kPa, while the recovery time of the collected capacitance signal was 180ms during the unloading of the force. The pressure sensor is shown to have a faster response and recovery time.
2) The capacitive response of the sample 3 pressure sensor was detected by applying a slight pressure of 8.7Pa to it. As can be seen in fig. 7, when the sensor is subjected to a slight pressure of 8.7Pa, the sensor can still exhibit a good capacitive response.
The pressure sensor is in a stress range of 0-3 kPa, and the sensitivity is 0.89kPa at most-1The response time was 110ms and the minimum stress detection was 8.7 Pa.
In summary, the invention provides a preparation method of a boron-graphene composite aerogel and an application of a pressure sensor thereof. The boron alkene is prepared by ultrasonic liquid phase stripping, the aerogel is prepared by a hydrothermal method, and the method is applied to the field of pressure sensors. It should be noted that the application of the present invention is not limited to the above examples, and that modifications and variations can be made by persons skilled in the art in light of the above description, and all such modifications and variations are intended to fall within the scope of the invention as defined in the appended claims.
Claims (5)
1. A boron-graphene composite aerogel is mainly formed by compounding boron and graphene, wherein two-dimensional boron and graphene jointly form a three-dimensional reticular aerogel structure, and the atomic number percentage ranges of C, O, N, B elements are respectively 68% -70%, 10% -12%, 16% -18% and 4% -5%.
2. A method for preparing the borane-graphene composite aerogel according to claim 1, comprising the steps of:
1) preparing a boron alkene-graphene mixed precursor solution: ultrasonically crushing 5-15 mg of amorphous boron powder in 10-30 ml of DMF solution for 3-5 hours, centrifuging at the rotating speed of 3000-5000 rpm for 20-40 minutes, and taking supernatant to obtain the DMF solution dispersed with boron alkene; adding graphene oxide into a deionized water solution and continuously performing ultrasonic treatment to obtain a dispersion solution; preparing a mixed precursor solution, wherein the mass ratio of graphene oxide, ammonia water, a boron-alkene-dispersed DMF solution and deionized water is (15-30) to (50-100): (600-700): (1800-1900).
2) Preparing the boron alkene-graphene composite hydrogel: adding the mixed precursor solution into a reaction kettle for hydrothermal reaction at the temperature of 90-140 ℃ for 8-10 hours to obtain the boron graphene-graphene composite hydrogel; then, mixing absolute ethyl alcohol and water according to the proportion of 1: (90-110) preparing a dialysate by mixing, and finally immersing the boron graphene-graphene composite hydrogel into the dialysate for dialysis, wherein the temperature is kept between 15 ℃ and 25 ℃, and dialyzing for 5-8 hours;
3) preparing the boron graphene-graphene composite aerogel: freezing the hydrogel obtained in the step 2) at the temperature of-10 to-20 ℃ for 6 to 14 hours; and then carrying out freeze drying under vacuum, wherein the freeze drying temperature is-40 ℃ to-30 ℃, and drying for 18-24 hours to obtain the boron-graphene composite aerogel.
3. A pressure sensor comprising the boron graphene-graphene composite aerogel according to claim 1 or obtained by the preparation method according to claim 2.
4. The pressure sensor of claim 3, comprising an electrode/PVA film/graphene-graphene composite aerogel/PVA film/electrode structure in that order.
5. A method of making a pressure sensor according to claim 4, comprising the steps of:
1) pre-treating an electrode; cleaning the electrode to remove impurities and oil stains on the surface of the electrode;
2) preparation of gel electrolyte: preparing PVA solid powder and concentrated sulfuric acid into an aqueous solution, wherein the mass ratio of PVA to concentrated sulfuric acid to deionized water is (5-10): (1-2): (50-80), and heating and stirring for 1-2 hours in a water bath at the temperature of 90-100 ℃;
3) preparing a pressure sensor: using the gel electrolyte prepared in the step 2) to brush on the electrode prepared in the step 1) to form a PVA (polyvinyl alcohol) viscous film, soaking the boron-graphene composite aerogel in the gel electrolyte for 5-15 min, and finally fixing the boron-graphene composite aerogel on a metal sheet electrode through the PVA viscous film to assemble: the electrode/PVA film/boron alkene-graphene composite aerogel/PVA film/electrode structure is placed in an oven for drying, the drying temperature is 30-50 ℃, and the drying time is 18-24 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021105630676 | 2021-05-21 | ||
| CN202110563067 | 2021-05-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113441094A true CN113441094A (en) | 2021-09-28 |
| CN113441094B CN113441094B (en) | 2023-06-20 |
Family
ID=77816882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110822880.0A Active CN113441094B (en) | 2021-05-21 | 2021-07-20 | Boron alkene-graphene composite aerogel and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113441094B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114018446A (en) * | 2021-11-01 | 2022-02-08 | 安徽大学 | Partially degradable self-powered pressure sensor, preparation method and test circuit thereof |
| CN114136508A (en) * | 2021-11-03 | 2022-03-04 | 南京航空航天大学 | Flexible boron-olefin pressure sensor and preparation method and application thereof |
| CN114512656A (en) * | 2021-12-29 | 2022-05-17 | 清华大学 | Preparation method and preparation container of boron-graphene and graphene composite aerogel electrode slice |
| CN115020120A (en) * | 2022-05-26 | 2022-09-06 | 安徽大学 | Graphene-bismuth alkene aerogel with composite staggered and stacked intercalation structure, and preparation method and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103560268A (en) * | 2013-10-10 | 2014-02-05 | 中山大学 | Preparation method for boron-doped graphene-modified gel polymer electrolyte |
| CN103633333A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
| CN104637898A (en) * | 2014-12-08 | 2015-05-20 | 上海大学 | Thermally conductive composite layer of integrated circuit device and electronic device thermal conduction structure packaging method |
| CN106006615A (en) * | 2016-05-25 | 2016-10-12 | 哈尔滨工业大学 | Natural drying preparation method of graphene aerogel |
| CN107771354A (en) * | 2015-04-01 | 2018-03-06 | 爱法组装材料公司 | Engineering polymers electron-like material |
| CN108489644A (en) * | 2018-02-12 | 2018-09-04 | 华中科技大学 | High sensitive sensor based on MXene/rGO complex three-dimensional structures |
| CN108615621A (en) * | 2018-06-22 | 2018-10-02 | 安徽大学 | Composite graphene aerogel electrode, and preparation method and application thereof |
| CN108622924A (en) * | 2018-06-27 | 2018-10-09 | 清华大学 | Silver sulfide quantum dot-graphene aerogel composite material and preparation method |
| CN108711522A (en) * | 2018-04-26 | 2018-10-26 | 武汉工程大学 | A kind of boron doping graphene/polyaniline composite aerogel and preparation method thereof |
| CN109336127A (en) * | 2018-11-30 | 2019-02-15 | 深圳大学 | A kind of boron alkene and preparation method thereof |
| CN109562933A (en) * | 2016-05-31 | 2019-04-02 | 新泽西鲁特格斯州立大学 | The hollow bead formed by two-dimensional material |
| CN110461764A (en) * | 2017-03-28 | 2019-11-15 | 曼彻斯特大学 | Thin-film material transfer method |
| CN111696793A (en) * | 2020-05-28 | 2020-09-22 | 杭州电子科技大学 | Preparation method of NBGA// RGO/PPy/Ag asymmetric elastic super-capacitor type piezoelectric sensor |
| CN112218752A (en) * | 2018-04-09 | 2021-01-12 | 应用石墨烯材料英国有限公司 | Method for making an object from a composite material and object formed by the method |
| CN112429721A (en) * | 2020-11-24 | 2021-03-02 | 安徽大学 | Composite graphene aerogel, preparation method and application of composite graphene aerogel in super-capacitor pressure sensor |
-
2021
- 2021-07-20 CN CN202110822880.0A patent/CN113441094B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633333A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
| CN103560268A (en) * | 2013-10-10 | 2014-02-05 | 中山大学 | Preparation method for boron-doped graphene-modified gel polymer electrolyte |
| CN104637898A (en) * | 2014-12-08 | 2015-05-20 | 上海大学 | Thermally conductive composite layer of integrated circuit device and electronic device thermal conduction structure packaging method |
| CN107771354A (en) * | 2015-04-01 | 2018-03-06 | 爱法组装材料公司 | Engineering polymers electron-like material |
| CN106006615A (en) * | 2016-05-25 | 2016-10-12 | 哈尔滨工业大学 | Natural drying preparation method of graphene aerogel |
| CN109562933A (en) * | 2016-05-31 | 2019-04-02 | 新泽西鲁特格斯州立大学 | The hollow bead formed by two-dimensional material |
| CN110461764A (en) * | 2017-03-28 | 2019-11-15 | 曼彻斯特大学 | Thin-film material transfer method |
| CN108489644A (en) * | 2018-02-12 | 2018-09-04 | 华中科技大学 | High sensitive sensor based on MXene/rGO complex three-dimensional structures |
| CN112218752A (en) * | 2018-04-09 | 2021-01-12 | 应用石墨烯材料英国有限公司 | Method for making an object from a composite material and object formed by the method |
| CN108711522A (en) * | 2018-04-26 | 2018-10-26 | 武汉工程大学 | A kind of boron doping graphene/polyaniline composite aerogel and preparation method thereof |
| CN108615621A (en) * | 2018-06-22 | 2018-10-02 | 安徽大学 | Composite graphene aerogel electrode, and preparation method and application thereof |
| CN108622924A (en) * | 2018-06-27 | 2018-10-09 | 清华大学 | Silver sulfide quantum dot-graphene aerogel composite material and preparation method |
| CN109336127A (en) * | 2018-11-30 | 2019-02-15 | 深圳大学 | A kind of boron alkene and preparation method thereof |
| CN111696793A (en) * | 2020-05-28 | 2020-09-22 | 杭州电子科技大学 | Preparation method of NBGA// RGO/PPy/Ag asymmetric elastic super-capacitor type piezoelectric sensor |
| CN112429721A (en) * | 2020-11-24 | 2021-03-02 | 安徽大学 | Composite graphene aerogel, preparation method and application of composite graphene aerogel in super-capacitor pressure sensor |
Non-Patent Citations (7)
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114018446A (en) * | 2021-11-01 | 2022-02-08 | 安徽大学 | Partially degradable self-powered pressure sensor, preparation method and test circuit thereof |
| CN114018446B (en) * | 2021-11-01 | 2024-02-13 | 安徽大学 | Partially degradable self-powered pressure sensor, preparation method and test circuit thereof |
| CN114136508A (en) * | 2021-11-03 | 2022-03-04 | 南京航空航天大学 | Flexible boron-olefin pressure sensor and preparation method and application thereof |
| CN114512656A (en) * | 2021-12-29 | 2022-05-17 | 清华大学 | Preparation method and preparation container of boron-graphene and graphene composite aerogel electrode slice |
| CN114512656B (en) * | 2021-12-29 | 2024-08-27 | 清华大学 | Preparation method and preparation container of boron alkene and graphene composite aerogel electrode plate |
| CN115020120A (en) * | 2022-05-26 | 2022-09-06 | 安徽大学 | Graphene-bismuth alkene aerogel with composite staggered and stacked intercalation structure, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113441094B (en) | 2023-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113441094B (en) | Boron alkene-graphene composite aerogel and preparation and application thereof | |
| Wang et al. | A simple and universal method for preparing N, S co-doped biomass derived carbon with superior performance in supercapacitors | |
| Wu et al. | Carbonaceous hydrogels and aerogels for supercapacitors | |
| Guo et al. | Free-standing reduced graphene oxide/polypyrrole films with enhanced electrochemical performance for flexible supercapacitors | |
| CN108329495B (en) | Graphene-cellulose nanocrystalline composite heat-conducting film with bionic structure and preparation thereof | |
| Shi et al. | Low cost and flexible mesh-based supercapacitors for promising large-area flexible/wearable energy storage | |
| CN107973283B (en) | Elastic carbon aerogel and preparation method and application thereof | |
| CN108615621B (en) | Composite graphene aerogel electrode, and preparation method and application thereof | |
| Shan et al. | Wood-based hierarchical porous nitrogen-doped carbon/manganese dioxide composite electrode materials for high-rate supercapacitor | |
| CN112374490B (en) | Three-dimensional porous graphene/polyurethane flexible stress-strain sensor and preparation method thereof | |
| Xu et al. | Synthesis and characterization of free-standing activated carbon/reduced graphene oxide film electrodes for flexible supercapacitors | |
| CN108548619B (en) | Method for improving sensitivity of piezoresistive sensor based on fragmented structure | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| Zhang et al. | All-carbon composite paper as a flexible conducting substrate for the direct growth of polyaniline particles and its applications in supercapacitors | |
| Wang et al. | Scalable, superelastic, and superhydrophobic MXene/silver nanowire/melamine hybrid sponges for high-performance electromagnetic interference shielding | |
| Jin et al. | Tree leaves-derived three-dimensional porous networks as separators for graphene-based supercapacitors | |
| CN112629718A (en) | Three-dimensional layered MXene-wood sponge electrode and preparation method and application thereof | |
| Lu et al. | In Situ Construction of NiCoMn‐LDH Derived from Zeolitic Imidazolate Framework on Eggshell‐Like Carbon Skeleton for High‐Performance Flexible Supercapacitors | |
| Cui et al. | A ternary MnO 2-deposited RGO/lignin-based porous carbon composite electrode for flexible supercapacitor applications | |
| CN105374574B (en) | A kind of preparation method and applications of cobalt hydroxide/graphene flexible electrode material | |
| Zhang et al. | The production of activated carbon from cation exchange resin for high-performance supercapacitor | |
| Chen et al. | The large electrochemical capacitance of nitrogen-doped mesoporous carbon derived from egg white by using a ZnO template | |
| CN106146833A (en) | A kind of flexible layer/polyaniline conductive graphene film and preparation method thereof | |
| CN103762356A (en) | Ni nanowire, NiO/Ni self-support membrane and preparation method and application thereof | |
| CN113692211A (en) | Preparation method of composite film electromagnetic protection material based on MXene-rGO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |