CN113517144B - Carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and preparation method thereof - Google Patents
Carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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
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Abstract
The invention relates to a carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and a preparation method thereof, and belongs to the field of research on new energy materials and devices. The invention obtains the activated carbon fiber felt by mixed acid acidification, and further adopts the activated carbon felt and the surface thereof to directly grow one-dimensional VO 2 The binary material formed by compounding the nano belts is used as a positive electrode material, and a layer of compact activated carbon is coated on the carbon felt and used as a negative electrode material. CFF @ VO 2 The binary nano composite material has the advantages of uniform size, compact arrangement, obvious pseudo-capacitance effect, good conductivity, excellent stability and excellent rate performance.
Description
Technical Field
The invention relates to a carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and a preparation method thereof, and belongs to the field of research on new energy materials and devices.
Background
As a new energy storage device, the super capacitor has a series of advantages of high charging and discharging speed, long service cycle and the like. The super capacitor mainly comprises three blocks, namely an electrode material, electrolyte and a diaphragm. The electrode material is the most critical factor for determining the performance of the device, and the super capacitor can be divided into three categories according to the difference of energy storage mechanisms of the electrode material: double layer capacitance, faraday pseudocapacitance, hybrid.
The electric double layer capacitance type and Faraday pseudo capacitance type materials have respective advantages and disadvantages. Single electric double layer materials, such as activated carbon, carbon cloth, etc., have good stability and rate capability, but have low specific capacitance. The specific capacitance value of a single pseudocapacitance material, such as manganese-based material, copper-based material and the like, is high, but the structure is easy to collapse, and ions are easy to accumulate. Therefore, researchers focus on the diversified and multidimensional field combining the carbon material and the pseudocapacitance material, and focus on the advantages of the carbon material and the pseudocapacitance material together, and meanwhile, the defects of the carbon material and the pseudocapacitance material are prevented from being exposed, and a device with excellent performance is prepared.
In a plurality of pseudo-capacitive electrode materialsIn addition, vanadium has rich valence and high redox activity. The compound of vanadium widely studied by researchers is V 2 O 5 、VO 2 And the like. VO (vacuum vapor volume) 2 The material has excellent electrochemical performance, and has the advantages of large theoretical specific capacity, wide voltage window, high energy density and the like. But VO 2 There are also some disadvantages such as low electron conduction rate, slow ion diffusion rate, poor cycling stability, and poor rate capability. Therefore, it is necessary to subject VO to 2 And measures such as modification are taken to improve the electrochemical performance of the catalyst.
In addition, the performance of the electrode material is closely related to the micro-morphology thereof, and the micro-structure thereof determines the number of binding sites of active substances (such as oxygen-containing functional groups) on the surface of the electrode material. How to design and prepare the nanoscale electrode material with uniform size, uniform appearance and larger specific surface area so as to fully and stably load the binding sites of the surface active substances is one of the key problems of the current research. Compared with zero-dimensional nano-particles or one-dimensional nano-wires and other types of materials, the one-dimensional banded VO 2 The method has the more remarkable advantage that the one-dimensional strip-shaped structure has larger specific surface area, so that the movement of anions and cations in the electrolyte between the strips is facilitated, and the electrochemical reaction between the anions and the electrode material is promoted in dynamics. Currently, VO with one-dimensional ribbon structure 2 There are few reports of use as a metamaterial.
On the other hand, with the help of the carbon fiber felt with a three-dimensional structure, the overall design of the composite material is a three-dimensional structure, and the performance of the device is comprehensively improved: (1) Carbon fiber skeleton with high strength as VO 2 VO, a growth substrate of 2 The size and the shape of the carbon felt are controlled, and VO generated when the carbon felt is not introduced is effectively avoided 2 Thick film belt, mass accumulation, inconsistent size and the like. (2) The three-dimensional conductive carbon felt with rich pore structure enhances VO 2 The conductivity of the device improves the energy density and power density of the device. (3) VO with high pseudo capacitance 2 Directly grows on the carbon felt, avoids the introduction of a conductive agent and a polymer binder in the test process, and has more real performanceBy this means. (4) The introduction of the carbon felt with good flexibility and excellent mechanical property enables the preparation of the miniature flexible all-solid-state device to be realized, and the practical development of the device is promoted.
Currently, the main materials studied for the flexible substrates are metal substrates and highly conductive carbon materials. The conductive carbon material has the advantages of environmental friendliness, direct contact with human skin and the like, but the untreated flexible carbon substrate hardly reacts with an inorganic compound. Therefore, a stable and reliable method is designed and developed to grow one-dimensional VO with high pseudo capacitance on a carbon material substrate 2 The nano-band electrode material and the binary material are used as the anode material of the flexible device, and have great significance for promoting the development of the electrode material of the super capacitor and the practical application of the device.
Disclosure of Invention
In order to solve the key problems, the invention firstly proposes that the mixed acid is used for activating the commercial carbon felt to ensure that the commercial carbon felt is rich in a large amount of functional groups, and a chemical bath is further adopted for depositing to grow one-dimensional VO on the activated carbon felt 2 The nanoribbon is used as a positive electrode material, and a novel flexible all-solid-state supercapacitor is designed.
The flexible all-solid-state supercapacitor comprises a positive electrode, a negative electrode and a gel electrolyte, and is characterized in that the positive electrode is a homogeneous one-dimensional VO (vanadium oxide) grown on the surface of a carbon fiber felt with a three-dimensional space structure 2 The nano-belts are orderly arranged to form the binary composite electrode material. The binary composite electrode material is VO (vanadium oxide) which is prepared by taking a plurality of fibrous carbon rods in a carbon felt as a supporting substrate and a conductive bracket 2 The nanobelts are completely wrapped on the surface of the carbon felt in a winding state, the structure provides a large specific surface area and binding sites for a large number of functional groups, and meanwhile, the non-totally-enclosed three-dimensional structure provides a large amount of space for free flow of anions and cations in electrolyte and direct contact with an electrode material to generate effects and store energy, so that the activity of the electrode material is improved, and the electrochemical reaction rate of the electrode material is improved from the aspect of dynamics. The three-dimensional structure can also stably maintain VO 2 The shape of the nano belt effectively avoids a single filmVO 2 The accumulation is continuous, and the pseudo-capacitive performance of the capacitor is influenced. The negative electrode is prepared by coating a layer of activated carbon on a carbon felt. As a typical carbon material, the activated carbon has the advantages of good conductivity, good stability and the like, and when the activated carbon is used as a cathode material of a supercapacitor, the excellent structural stability of the activated carbon can be utilized to improve the rate capability, the cycle life and the like of a device. The gel electrolyte is PVA/LiCl gel electrolyte. Compared with an aqueous electrolyte, the gel electrolyte obviously widens the working voltage interval due to the addition of the organic polymer. In addition, the all-solid-state structure of the gel electrolyte can solve a series of problems of volume expansion, liquid overflow and the like of a device, and guarantees are provided for the preparation and practical application of the flexible supercapacitor.
The preparation method of the flexible all-solid-state supercapacitor comprises the following steps:
(1) Cleaning the surface of the carbon felt: the commercial carbon felt is sequentially cleaned by 1mol/L HCl solution, 1mol/L NaOH solution, 95% ethanol solution with mass concentration and deionized water in an ultrasonic mode, and then placed in an oven to be dried for later use.
(2) Activating the surface of the carbon felt: placing a piece of dry carbon felt with proper size in a beaker; respectively preparing 1-6mol/L H 2 SO 4 Mixing the solution with 1-6mol/L HNO 3 A solution; and the two are poured into a beaker in sequence according to the volume ratio of 3; stirring the beaker at room temperature for 45min at a constant speed; then transferring the mixture into a 70 ℃ water bath kettle and stirring the mixture for 45min at a constant speed; after stirring, taking out the carbon felt and cleaning the carbon felt by using an ethanol solution with the mass concentration of 95% for three times; and finally, drying the carbon felt for 5 hours in a drying oven at the temperature of 65 ℃, and taking out the carbon felt to weigh the carbon felt.
(3) Preparing a binary material: weighing in turn the quantity C 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 Pouring the powder into a beaker with deionized water added in advance to obtain a mixed solution; stirring the mixed solution at a constant speed at room temperature, transferring the mixed solution into a constant-temperature water bath kettle at 75 ℃ after the color of the solution is observed to change from dark yellow to green and then to light blue, continuously stirring at the constant speed, and simultaneously immersing an activated and dried carbon felt into a beaker for chemical bath deposition; stirring at constant speed for 40-60min, and collecting carbon feltWashing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; drying at 65 deg.C for 3h; finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; to record VO carried on carbon felt 2 Net mass of nanoribbons.
(4) Preparing an all-solid-state supercapacitor: calculating the load capacity of the negative active carbon according to the charge conservation law of the positive electrode and the negative electrode; weighing quantitative PVA, liCl and deionized water to prepare PVA/LiCl gel electrolyte; respectively soaking the anode and the cathode in the gel electrolyte for 10-20min; taking out and adding a diaphragm between the two electrodes; and then wrapping a layer of plastic film outside, and finally maintaining the device under certain pressure for a certain time to obtain the all-solid-state supercapacitor.
In the step (1), the ultrasonic cleaning time is controlled to be 15min.
H added in the step (2) above 2 SO 4 Solution with HNO 3 The molarity of the solution should be kept consistent, with volumes of 60mL and 20mL, respectively.
In the step (2), the stirring speed of the beaker at room temperature and the stirring speed of the beaker in the water bath are both controlled to be 900r/min.
In the above step (3), said C 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 And deionized water in a mass ratio of 0.6303-0.6325:0.1-0.12:0.2925-0.3035:30. wherein C is 2 H 2 O 4 ·2H 2 O as an activator and CTAB as an initiator and inducer.
In the step (3), the beaker is stirred at the room temperature of 1200r/min and is stirred at the water bath speed of 900r/min.
VO loaded on the carbon felt in the step (3) 2 The net mass of the nano belt is 1.58-2.47mg/cm 2 。
In the step (4), the loading amount of the negative active carbon is 3.20-5.60mg/cm 2 (ii) a The mass ratio of PVA to LiCl to deionized water is 3-3.5:6.3-6.56:30-35; the pressure is 0.1-0.15MPa; the maintaining time is 10-15min.
Therefore, the flexible all-solid-state asymmetric super capacitor obtained by the invention hasHas the following advantages: (1) excellent electrochemical performance: the working voltage is stabilized at 1.4V, and the highest energy density reaches 0.715mWh/cm 3 The highest power density reaches 52.5mW/cm 3 And the two devices are connected in series to light the LED bulb, so that good practicability is shown. (2) The device is light in weight and good in flexibility, and is expected to provide energy support for portable wearing equipment. And (3) the anode and cathode materials are wide in source and low in cost. (4) The preparation of the gel electrolyte and the assembly process of the device are simple, direct, stable, safe and controllable.
Drawings
FIG. 1 is a schematic diagram of experimental process routes and assembled devices taken in examples 1-4 of the present invention.
FIG. 2 shows the pure carbon felt and the prepared CFF @ VO of the invention in example 1 2 Scanning electron microscope pictures of the binary composite material in a selected area.
Fig. 3 is a performance test curve of the assembled flexible all-solid-state asymmetric device of example 1 of the present invention.
Fig. 4 is a lighting schematic diagram of the flexible all-solid-state asymmetric device assembled in embodiment 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments.
Example 1:
1) Cleaning the surface of the carbon felt: preparing 1mol/L HCl and 1mol/L NaOH solution in advance; a commercial carbon felt with the size of 3.5cm x 1.5cm x 3mm (length x width x height) is taken, and is ultrasonically cleaned for 15min by 30mL of HCl solution, 30mL of NaOH solution, 30mL of ethanol solution with the mass concentration of 95% and 30mL of deionized water, and then is placed in an oven to be dried for later use.
2) Activating the surface of the carbon felt: preparing 3mol/L H in advance 2 SO 4 With 3mol/L HNO 3 Solution, namely placing the medium carbon felt obtained in the step (1) into a beaker; 60mL of H were weighed in the order of the volume ratio of 3 2 SO 4 And 20mL HNO 3 Pouring into a beaker; uniformly stirring the beaker at room temperature at the rotating speed of 900r/min for 45min; then transferring the mixture into a 70 ℃ water bath kettle to continue stirring for 45min at a constant speed of 900r/min; after the end of the stirring, the mixture is stirred,taking out the carbon felt and cleaning the carbon felt for three times by using an ethanol solution with the mass concentration of 95%; and finally, drying the carbon felt for 5 hours in a drying oven at the temperature of 65 ℃, and taking out the carbon felt to weigh the carbon felt.
3) Preparing a binary material: 0.6303g of C was weighed in order 2 H 2 O 4 ·2H 2 O、0.1g CTAB、0.2925gNH 4 VO 3 Pouring the powder into a beaker into which 30mL of deionized water is added in advance; when the mixed solution is rapidly stirred for 4 hours at the room temperature at the speed of 1200r/min, the color of the mixed solution is changed from dark yellow to green and then to light blue, the mixed solution is transferred to a constant-temperature water bath kettle at the temperature of 75 ℃ to be continuously stirred at the speed of 900r/min, and simultaneously a piece of activated carbon felt is immersed in a beaker for chemical bath deposition; stirring at a constant speed for 60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring to an oven; drying at 65 ℃ for 3h. Finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; recording to obtain VO loaded on the carbon felt 2 The net mass of the nanobelt is 2.21mg/cm 2 . FIG. 2 shows the pure carbon felt and CFF @ VO in this embodiment 2 VO can be seen from SEM picture of binary composite material 2 The nanobelts successfully grow on the surface of the carbon felt, and are uniformly distributed and uniform in size.
4) Preparing an all-solid-state supercapacitor: the loading capacity of the negative active carbon is calculated to be 3.76mg/cm according to the charge conservation law of the positive electrode and the negative electrode 2 And coating on the carbon felt according to the loading amount. Then 3g of PVA, 6.3g of LiCl and 30mL of deionized water are weighed to prepare PVA/LiCl gel electrolyte; then respectively immersing the positive electrode and the negative electrode into electrolyte for soaking for 10min, taking out the positive electrode and the negative electrode, and adding a diaphragm between the two electrodes; wrapping a layer of plastic film outside; and finally, maintaining the device under the pressure of 0.1mPa for 15min to obtain the all-solid-state supercapacitor. FIG. 3 is a performance test chart of the device in this embodiment, which can be calculated to obtain the maximum specific capacitance of 1051mF/cm 2 . Fig. 4 is a lighting diagram of the device in this embodiment, which shows its good practicability.
Example 2:
1) Cleaning the surface of the carbon felt: this procedure is the same as in example 1.
2) Activating the surface of the carbon felt: configuring 1m in advanceol/L H 2 SO 4 With 1mol/L HNO 3 Solution, other steps are the same as in example 1.
3) Preparing a binary material: 0.6303g of C was weighed in order 2 H 2 O 4 ·2H 2 O、0.1g CTAB、0.2925gNH 4 VO 3 Pouring the powder into a beaker into which 30mL of deionized water is added in advance; when the mixed solution is rapidly stirred for 4 hours at room temperature at the speed of 1200r/min, the color of the mixed solution is changed from dark yellow to green and then to light blue, the mixed solution is transferred to a constant-temperature water bath kettle at the temperature of 75 ℃ to be continuously stirred at the speed of 900r/min, and simultaneously, an activated carbon felt is immersed into a beaker for chemical bath deposition; stirring at a constant speed for 60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; drying at 65 deg.C for 3h. Finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; recording to obtain VO loaded on the carbon felt 2 The net mass of the nanobelt is 1.58mg/cm 2 。
4) Preparing an all-solid-state supercapacitor: the load capacity of the negative active carbon is calculated to be 4.58mg/cm according to the charge conservation law of the positive electrode and the negative electrode 2 And coating on the carbon felt according to the loading amount. Then 3g of PVA, 6.3g of LiCl and 30mL of deionized water are weighed to prepare PVA/LiCl gel electrolyte; respectively soaking the anode and the cathode in the electrolyte for 10min; taking out and adding a diaphragm between the two electrodes; wrapping a layer of plastic film outside; and finally, maintaining the device under the pressure of 0.1mPa for 15min to obtain the all-solid-state supercapacitor. Through calculation, the maximum specific capacitance of the device is 893mF/cm 2 。
Example 3:
1) Cleaning the surface of the carbon felt: this procedure is the same as in example 1.
2) Activating the surface of the carbon felt: preparing 6mol/L H in advance 2 SO 4 With 6mol/L HNO 3 Solution, other steps are the same as in example 1.
3) Preparing a binary material: 0.6303g of C was weighed in order 2 H 2 O 4 ·2H 2 O、0.1g CTAB、0.2925gNH 4 VO 3 Pouring the powder into a beaker into which 30mL of deionized water is added in advance; when the mixed solution is at room temperature at 1After fast stirring for 4 hours at the speed of 200r/min, changing the color of the mixed solution from dark yellow to green and then to light blue, transferring the mixed solution into a constant-temperature water bath kettle at the temperature of 75 ℃ to continue stirring at the speed of 900r/min, and simultaneously soaking an activated carbon felt into a beaker to carry out chemical bath deposition; stirring at a constant speed for 60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; drying at 65 ℃ for 3h. Finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; recording to obtain VO loaded on the carbon felt 2 The net mass of the nanobelt is 2.47mg/cm 2 。
4) Preparing an all-solid-state supercapacitor: the loading capacity of the cathode active carbon is calculated to be 3.20mg/cm according to the charge conservation law of the anode and the cathode 2 And coating on the carbon felt according to the loading amount. And weighing 3g of PVA, 6.3g of LiCl and 30mL of deionized water to prepare PVA/LiCl gel electrolyte, respectively soaking the positive electrode and the negative electrode in the electrolyte for 10min, taking out the electrolyte, adding a diaphragm between the two electrodes, wrapping a plastic film outside the electrolyte, and finally maintaining the wrapped device under the pressure of 0.1mPa for 15min to obtain the all-solid-state supercapacitor. Through calculation, the maximum specific capacitance of the device is 857mF/cm 2 。
Examples 1-3 to compare the effect of using the concentration of mixed acid on the electrochemical performance of the composite material and the electrochemical performance of the device, it can be seen that H 2 SO 4 With HNO 3 When the concentration of the solution is 3mol/L, the device has the best performance.
Example 4:
1) Cleaning the surface of the carbon felt: this procedure is the same as in example 1.
2) Activating the surface of the carbon felt: this procedure is the same as in example 1.
3) Preparing a binary material: 0.6325g of C was weighed in turn 2 H 2 O 4 ·2H 2 O、0.12g CTAB、0.3035gNH 4 VO 3 Pouring the powder into a beaker into which 30mL of deionized water is added in advance; rapidly stirring at 1200r/min for 4 hr at room temperature, transferring to 75 deg.C constant temperature water bath, stirring at 900r/min,simultaneously, a piece of activated carbon felt is immersed into a beaker for chemical bath deposition; stirring at a constant speed for 60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; drying at 65 ℃ for 3h. Finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; recording to obtain VO loaded on the carbon felt 2 The net mass of the nanobelt is 1.96mg/cm 2 。
4) Preparing an all-solid-state supercapacitor: the loading capacity of the cathode active carbon is calculated to be 3.64mg/cm according to the charge conservation law of the anode and the cathode 2 And coating on the carbon felt according to the loading amount. And weighing 3g of PVA, 6.3g of LiCl and 30mL of deionized water to prepare PVA/LiCl gel electrolyte, respectively soaking the positive electrode and the negative electrode in the electrolyte for 10min, taking out the electrolyte, adding a diaphragm between the two electrodes, wrapping a plastic film outside the electrolyte, and finally maintaining the wrapped device under the pressure of 0.1mPa for 15min to obtain the all-solid-state supercapacitor. The maximum specific capacitance of the device is calculated to be 962mF/cm 2 . Indicating deposition by chemical bath 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 When the mass exceeds a certain range, VO 2 The nanobelts can generate excessive accumulation on the carbon felt, so that a certain inhibiting effect is realized on the release of the binary electrode material and the device performance.
Claims (8)
1. The carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor comprises a positive electrode, a negative electrode and a gel electrolyte, and is characterized in that the positive electrode is a homogeneous one-dimensional VO (volatile organic solvent) grown on the surface of a carbon fiber felt with a three-dimensional space structure 2 A binary composite electrode material formed by orderly arranging nanobelts; the binary composite electrode material is VO (vanadium oxide) which is prepared by taking a plurality of fibrous carbon rods in a carbon felt as a supporting substrate and a conductive bracket 2 The nanobelts are completely coated on the surface of the carbon felt in a winding state, the structure provides a large specific surface area and binding sites for a large number of functional groups, and meanwhile, the non-totally-enclosed three-dimensional structure provides a large amount of space for free flow of anions and cations in electrolyte and direct contact with electrode materials to generate effects and store energy, so that the carbon felt can be used for producing and storing energyThe activity of the electrode material is improved, so that the electrochemical reaction rate of the electrode material is improved from the aspect of dynamics; the three-dimensional structure can also stably maintain VO 2 The shape of the nano belt effectively avoids single film-shaped VO 2 The accumulation is continuous, and the pseudo-capacitive performance of the capacitor is influenced; the preparation method of the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor comprises the following specific steps:
(1) Cleaning the surface of the carbon felt: ultrasonically cleaning a commercial carbon felt by using HCl solution, naOH solution, ethanol solution and deionized water in sequence, and then drying the carbon felt in an oven for later use;
(2) Activating the surface of the carbon felt: placing a piece of dry carbon felt with proper size in a beaker; are respectively configured with H 2 SO 4 Solution with HNO 3 A solution; pouring the two into a beaker in sequence; stirring the beaker at a constant speed at room temperature, transferring the beaker to a 70 ℃ water bath kettle, and continuously stirring at a constant speed; after stirring, taking out the carbon felt and cleaning the carbon felt by using an ethanol solution; finally, taking out the carbon felt after drying, and weighing the mass of the carbon felt;
(3) Preparing a binary material: weighing in turn the quantity C 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 Pouring the powder into a beaker with deionized water added in advance to obtain a mixed solution; stirring the mixed solution at a constant speed at room temperature, transferring the mixed solution into a constant-temperature water bath kettle at 75 ℃ after the color of the solution is observed to change from dark yellow to green and then to light blue, continuously stirring at the constant speed, and simultaneously immersing an activated and dried carbon felt into a beaker for chemical bath deposition; stirring at constant speed for 40-60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; drying at 65 deg.C for 3h; finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; to record VO carried on carbon felt 2 The net mass of the nanoribbon;
(4) Preparing an all-solid-state supercapacitor: calculating the load capacity of the negative active carbon according to the charge conservation law of the positive electrode and the negative electrode; weighing quantitative PVA, liCl and deionized water to prepare PVA/LiCl gel electrolyte; respectively soaking the anode and the cathode in the gel electrolyte for 10-20min; taking out and adding a diaphragm between the two electrodes; and then wrapping a layer of plastic film outside, and finally maintaining the device under certain pressure for a certain time to obtain the all-solid-state supercapacitor.
2. The carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor as claimed in claim 1, wherein the negative electrode is made by coating a layer of activated carbon on a carbon felt.
3. The carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor as claimed in claim 1, wherein the gel electrolyte is a PVA/LiCl gel electrolyte.
4. The preparation method of the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor as claimed in claim 1, which comprises the following specific steps:
(1) Cleaning the surface of the carbon felt: ultrasonically cleaning a commercial carbon felt by using HCl solution, naOH solution, ethanol solution and deionized water in sequence, and then drying the carbon felt in an oven for later use;
(2) Activating the surface of the carbon felt: placing a piece of dry carbon felt with proper size in a beaker; are respectively configured with H 2 SO 4 Solution with HNO 3 A solution; pouring the two into a beaker in sequence; stirring the beaker at a constant speed at room temperature, transferring the beaker to a 70 ℃ water bath kettle, and continuously stirring at a constant speed; after stirring, taking out the carbon felt and cleaning the carbon felt by using an ethanol solution; finally, drying the carbon felt and taking out the carbon felt to weigh the carbon felt;
(3) Preparing a binary material: weighing in turn the quantity C 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 Pouring the powder into a beaker with deionized water added in advance to obtain a mixed solution; stirring the mixed solution at a constant speed at room temperature, transferring the mixed solution to a constant-temperature water bath kettle at 75 ℃ after the color of the solution is observed to be changed from dark yellow to green and then to light blue, continuously stirring at a constant speed, and simultaneously immersing a piece of activated and dried carbon felt into a beaker for chemical bath deposition; stirring at constant speed for 40-60min, taking out the carbon felt, washing with deionized water and 95% ethanol by mass concentration, and transferring into an oven; at 65Drying at the temperature of 3 hours; finally, taking out the carbon felt, and weighing the mass of the binary composite electrode material; to record VO carried on carbon felt 2 The net mass of the nanoribbon;
(4) Preparing an all-solid-state supercapacitor: calculating the load capacity of the negative active carbon according to the charge conservation law of the positive electrode and the negative electrode; weighing quantitative PVA, liCl and deionized water to prepare PVA/LiCl gel electrolyte; respectively soaking the anode and the cathode in the gel electrolyte for 10-20min; taking out and adding a diaphragm between the two electrodes; and then wrapping a layer of plastic film outside, and finally maintaining the device under certain pressure for a certain time to obtain the all-solid-state supercapacitor.
5. The method for preparing the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor as claimed in claim 4, wherein in the step (1), the concentrations of the HCl solution and the NaOH solution are 1mol/L, the mass percentage concentration of the ethanol solution is 95%, and the ultrasonic cleaning time is controlled to be 15min.
6. The method for preparing the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor as claimed in claim 4, wherein in the step (2), H is 2 SO 4 Solution with HNO 3 The molar concentration of the solution is kept consistent and is 1-6mol/L, H 2 SO 4 Solution with HNO 3 The volume ratio of the solution is 3; the stirring speed of the beaker at room temperature and in the water bath is controlled to be 900r/min; stirring for 45min; the mass percentage concentration of the ethanol solution adopted for cleaning is 95 percent, and the cleaning is carried out for three times; drying means drying in an oven at 65 ℃ for 5h.
7. The method for preparing the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor according to claim 4, wherein in the step (3), the C is 2 H 2 O 4 ·2H 2 O、CTAB、NH 4 VO 3 And deionized water in a mass ratio of 0.6303-0.6325:0.1-0.12:0.2925-0.3035:30, of a nitrogen-containing gas; wherein C 2 H 2 O 4 ·2H 2 O as activator, CTAB as initiator andan inducer; stirring the mixed solution at room temperature at a constant speed, wherein the stirring speed is 1200r/min; continuously stirring in a water bath kettle at a constant speed of 900r/min for 40-60min; VO loaded on carbon felt 2 The net mass of the nanobelt is 1.58-2.47mg/cm 2 。
8. The method for preparing the carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor according to claim 4, wherein in the step (4), the loading amount of the negative active carbon is 3.20-5.60mg/cm 2 (ii) a The mass ratio of PVA to LiCl to deionized water is 3-3.5:6.3-6.56:30-35; the pressure is 0.1-0.15MPa; the maintaining time is 10-15min.
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