CN114743802A - Wide-temperature-zone supercapacitor electrode material, wide-temperature-zone supercapacitor electrode device and preparation method of wide-temperature-zone supercapacitor electrode material - Google Patents
Wide-temperature-zone supercapacitor electrode material, wide-temperature-zone supercapacitor electrode device and preparation method of wide-temperature-zone supercapacitor electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/18—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against thermal overloads, e.g. heating, cooling or ventilating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a super capacitor, in particular to a wide-temperature-zone super capacitor electrode material, a wide-temperature-zone super capacitor device and a preparation method of the wide-temperature-zone super capacitor electrode material. The super capacitor comprises a positive electrode, a negative electrode and a gel electrolyte, and is characterized in that the positive electrode is made of NiCo-MOF electrode materials with high pseudocapacitance performance, and a raspberry-like NiCo-MOF ball is prepared by adjusting the proportion of Ni and Co main metal ions in the NiCo-MOF electrode materials. A large number of ultrathin nanosheets exist on the surface of the sphere, the nanosheets have ultrahigh specific surface areas, and gaps exist among the nanosheet layers. The negative electrode is ultrathin MnO self-made in a laboratory2. What is needed isThe gel electrolyte is PVA/KOH 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 the problems of volume expansion, electrolyte overflow and the like of a device, and lays a foundation for the preparation and practical application of the flexible super capacitor.
Description
Technical Field
The invention relates to a super capacitor, in particular to a wide-temperature-zone super capacitor electrode material, a wide-temperature-zone super capacitor device and a preparation method of the wide-temperature-zone super capacitor electrode material.
Background
As a new energy storage device, the super capacitor has the advantages of high charging and discharging speed, long service cycle and the like. The super capacitor mainly comprises three major parts, namely an electrode material, electrolyte and a diaphragm. The electrode material is the most critical factor in determining the performance of the device. According to the difference of energy storage mechanism of electrode materials, supercapacitors can be divided into three main categories: double layer capacitive, faraday pseudocapacitive and 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 diversification and multidimensional combination of the pseudocapacitance material and other materials, so that the pseudocapacitance material and other materials exert the advantages of the pseudocapacitance material and other materials, and meanwhile, the defects are prevented from being exposed, and a device with excellent performance is prepared.
Among many pseudocapacitive electrode materials, metal-organic framework (MOF) materials have both the characteristics of inorganic materials and organic materials, and have the advantages of high porosity, large specific surface area, controllable structure and function, and the like. However, most of the currently prepared MOFs are solid powder materials, and have poor cycling stability and poor conductivity, which are not favorable for performance exertion, and seriously hinder the application of the MOFs in the energy field. Therefore, modification measures are needed to improve the electrochemical performance of MOFs.
In addition, the performance of the electrode material is closely related to the microstructure thereof, and the microstructure thereof determines the number of binding sites of the surface active substances (such as oxygen-containing functional groups) of the electrode material. How to design and prepare the nano electrode material which has uniform size, uniform appearance, larger specific surface area and can fully and stably load the surface active substance is one of the key problems in the current research. MOFs are mostly dominated by two-and three-dimensional structures. Compared with a low-dimensional material, the three-dimensional material has more advantages in the aspects of overall size, specific surface area, ion transmission, charge distribution and the like, and is convenient for anions and cations in the electrolyte to move in the electrode material, and the electrochemical reaction between the anions and the electrode material is promoted in dynamics.
On the other hand, with the help of the carbon fiber felt that has spatial structure, the performance of device obtains promoting comprehensively: (1) the three-dimensional conductive carbon felt with a rich pore structure can enhance the conductivity of the MOF and improve the energy density and power density of a device. (2) The introduction of the carbon felt with good flexibility and excellent mechanical property realizes the preparation of the miniature flexible all-solid-state device and can promote the multifunctional development of the device.
At present, the preparation of morphology-controllable composite structural materials serving as electrode materials by taking single metal MOF as a substrate has been preliminarily studied, but the research on bimetallic MOF-based electrode materials prepared by utilizing the synergistic coupling effect of bimetal is less. Therefore, a stable and reliable method is designed and developed to prepare the NiCo-MOF super capacitor electrode material with a double-metal ion organic framework structure and high pseudocapacitive performance, and the binary material is used as the anode material of a flexible device, so that the method has great significance for promoting the development of the super capacitor electrode material and the practical application of the device.
Disclosure of Invention
The invention provides a method for activating a commercial carbon felt by using mixed acid to enable the commercial carbon felt to be rich in a large number of functional groups, and a one-step hydrothermal method is used for preparing a NiCo-MOF (NiCo-Metal organic framework) bimetallic organic framework material which is used as an anode material, so that a novel flexible asymmetric supercapacitor is designed and assembled.
The flexible asymmetric supercapacitor comprises a positive electrode, a negative electrode and a gel electrolyte, and is characterized in that the positive electrode is NiCo-MOF electrode material with high pseudocapacitance performance, and the electrode material is prepared into a similar electrode material by adjusting the proportion of Ni and Co main metal ions in the electrode materialResembling raspberry-shaped NiCo-MOF spheres. The surface of the sphere is provided with a large number of ultrathin nanosheets with ultrahigh specific surface area, and a certain gap is formed between the nanosheet layers, so that the non-totally-enclosed three-dimensional structure provides a large amount of space for free flow of anions and cations in the electrolyte, and the three-dimensional structure is in direct contact with an electrode material, so that the activity of the electrode material is improved, the electrochemical reaction rate of the electrode material is improved, and the pseudocapacitance effect is more remarkable. The negative electrode is ultrathin MnO made by a laboratory2. The gel electrolyte is PVA/KOH gel electrolyte. Compared with a water-based 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 the problems of volume expansion, electrolyte overflow and the like of a device, and lays a foundation for the preparation and practical application of the flexible super capacitor.
The preparation method of the flexible asymmetric supercapacitor comprises the following steps:
(1) cleaning and activating the surface of the carbon felt: ultrasonically cleaning a commercial carbon felt by using an ethanol solution and deionized water in sequence; then separately configure H2SO4Solution with HNO3Pouring the solution and the solution into a beaker filled with carbon felt 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 is finished, taking out the carbon felt and cleaning the carbon felt with an ethanol solution for three times; and finally, placing the carbon felt in an oven for drying, taking out the carbon felt, and weighing the carbon felt for later use.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: firstly, a certain amount of Ni (NO)3)2·6H2O、Co(NO3)2·6H2O and H3Dissolving BTC in a DMF solution, stirring at room temperature, transferring the mixed solution into a reaction kettle, heating to 120 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal reaction at the temperature; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge for centrifugation, and then sequentially washing the sample with DMF, deionized water and ethanol solution; and finally, putting the obtained precipitate into a drying oven for drying to obtain a NiCo-MOF sample.
(3) Preparing an asymmetric device: firstly, NiCo-MO is weighed in sequenceF. Acetylene black and PVDF, and pouring into a mortar containing an NMP solvent for grinding into slurry; then coating the obtained slurry on a carbon felt, and drying overnight for later use; similarly, weighing ultrathin MnO manufactured by a laboratory2Pouring acetylene black and PVDF into a mortar containing an NMP solvent, grinding into slurry, coating the slurry on a carbon felt, and drying overnight to obtain a negative electrode material; subsequently, PVA, KOH, deionized water, K are weighed3[Fe(CN)6]And C3H8O3Synthesizing PVA/KOH gel electrolyte in water bath at 85 ℃; finally, soaking the positive electrode and the negative electrode in the gel electrolyte respectively; taking out and then aligning and closing the two electrodes; and (3) wrapping a layer of plastic film on the surface of the electrode, and applying pressure to the device to obtain the all-solid-state supercapacitor.
In the step (1), the ultrasonic cleaning time is controlled to be 15 min; the concentration of the ethanol solution is 95 wt%; said H2SO4Solution and HNO3The concentration of the solution is 3mol/L, H2SO4Solution and HNO3The volume ratio of the solution is 3: 1; the oven temperature was 65 ℃.
In the above step (2), the Ni (NO)3)2·6H2O、Co(NO3)2·6H2O and H3The molar ratio of BTC is 1: 1:1,1: 2:1,2: 1:1,4: 1: 1; DMF as activating agent, H3BTC is used as an initiator and an inducer, and the stirring speed is 900 rpm/min.
In the step (2), the hydrothermal reaction time of the reaction kettle is controlled to be 15 h; the rotating speed of the centrifugal machine is 10000rpm/min, and the centrifugal time is 3 min; the concentration of the ethanol solution is 95 wt%; the temperature of the drying oven is 60 ℃, and the drying time is 24 h.
In the step (3), the net mass of the NiCo-MOF anode material prepared is 1.89-2.33mg/cm2。
In the step (3), the mass ratio of NiCo-MOF, acetylene black and PVDF is 8:1:1, and the ultrathin MnO is2The mass ratio of the acetylene black to the PVDF is 8:1: 1; the size of the carbon felt is 1cm multiplied by 3cm, and the drying temperature is 70 ℃.
In the step (3), the cathode is ultrathin MnO2The loading capacity is 4.2-5.18mg/cm2(ii) a PVA, KOH, deionized water, K3[Fe(CN)6]And C3H8O3The ratio of (A) to (B) is 3 g: 1.52 g: 30g of: 0.329-0.658 g: 3 mL. K3[Fe(CN)6]And C3H8O3As an additive.
In the step (3), after the PVA is stirred in a water bath at 85 ℃ for 1 hour, the KOH solution is added dropwise.
In the step (3), the soaking time is 20-30 min; when assembling the device, the applied pressure is 0.1-0.15 MPa; the maintaining time is 10-15 min.
Therefore, the flexible all-solid-state asymmetric supercapacitor obtained by the invention has the following advantages: (1) the electrochemical performance is excellent: the working voltage is stabilized at 1.3V, the highest energy density reaches 66Wh/kg, the highest power density reaches 11700W/kg, the two devices are connected in series to light the LED bulb, and good practicability is shown. (2) The device is light in weight, has good flexibility and temperature resistance, can reach the ultimate working temperature of-20 ℃ and 40 ℃, and is expected to provide energy support for portable wearing equipment. (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, stable, safe and controllable.
Drawings
FIG. 1 is a schematic diagram of experimental process routes for electrode materials and devices used in the present invention.
FIG. 2 is a scanning electron microscope picture of a NiCo-MOF series composite material selected region prepared by the invention: a. example 1 sample; b. example 2 sample; c. example 4 sample; d. example 3 samples.
FIG. 3 is a scanning electron microscope image of NiCo-MOF composite material prepared in embodiment 3 of the present invention with different magnification in selected regions: a-b.10 μm under a scanning electron microscope; c.2 μm scanning electron micrograph; d.400nm scanning electron micrograph; e.100nm scanning electron micrograph; scanning electron micrograph at 50nm.
FIG. 4 is a curve of flexibility test and temperature resistance test of the assembled flexible asymmetric device of the present invention: a.0 °, 45 °, 90 °, 135 ° test diagram; b.0 DEG, 45 DEG, 90 DEG, 135 DEG V test curve; c.0 °, 45 °, 90 °, 135 ° GCD test curve; d. -20 ℃, 40 ℃ test schematic; e. -20 ℃, CV test curve at 40 ℃; f. GCD test curve at-20 ℃ and 40 ℃.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments.
Example 1:
(1) cleaning and activating the surface of the carbon felt: ultrasonically cleaning a 1cm × 3cm commercial carbon felt by using an ethanol solution with the mass concentration of 95% and deionized water for 15min in sequence; then 3mol/L H are respectively prepared2SO4Solution with 3mol/LHNO3Sequentially weighing 60mL and 20mL of the solution according to the volume ratio of 3:1, and pouring the solution into a beaker filled with a carbon felt; stirring the beaker at room temperature for 20min at constant speed, transferring the beaker to a 70 ℃ water bath kettle, and continuously stirring at constant speed for 20 min; after stirring is finished, taking out the carbon felt and cleaning the carbon felt by using 95% ethanol solution with mass concentration for three times; finally, the carbon felt is placed in a drying oven to be dried for 5 hours at the temperature of 65 ℃, and then taken out to be weighed as the mass M1It was 0.236 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: firstly, 1.5mmol of Ni (NO)3)2·6H2O、1.5mmol Co(NO3)2·6H2O and 1.5mmol H3BTC is dissolved in 60mL DMF solution and stirred at 900rpm/min for 10min at room temperature; then, transferring the mixed solution into a 100mL reaction kettle, heating to 120 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal treatment at the temperature for 15 h; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge, and centrifuging for 3min at the rotating speed of 10000 rpm/min; then washing with DMF, deionized water and 95% ethanol solution with mass concentration for 3 times in sequence; finally, the precipitate obtained is placed in a drying cabinet and dried at 60 ℃ for 24 h. After the drying is finished, an electrochemical test is carried out to obtain the NiCo-MOF specific capacitance of 469F/g.
(3) Preparing an asymmetric device: firstly, sequentially weighing three substances of NiCo-MOF, acetylene black and PVDF according to the mass ratio of 80 wt%, 10 wt% and 10 wt%, and pouring the three substances into a mortar containing an NMP solvent for grinding into slurry; then coating the obtained slurry on a carbon felt of 1cm multiplied by 3cm, and drying for 24 hours at 70 ℃; weighing its mass as M2Is 0.242g. The net loading of the NiCo-MOF sample was M+＝1.95mg/cm2。
According to the positive electrode load capacity and the charge conservation law, the negative electrode load capacity is calculated to be M-＝4.33mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on the carbon felt with the same size as a negative electrode material; subsequently, 3g of PVA, 1.68g of KOH, 3mL of C were weighed3H8O330mL of deionized water, stirring PVA in a water bath at 85 ℃ for 1h, dropwise adding KOH solution, and dropwise adding C3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 20 min; taking out and then aligning and closing the two electrodes; and (3) wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 10min to obtain the all-solid-state supercapacitor. The test shows that the working voltage of the device is 0-1.3V, and the energy density is 39.25 Wh/kg.
Example 2:
(1) cleaning and activating the surface of the carbon felt: this step is the same as the procedure in example 1, and its mass M is weighed3It was 0.225 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: firstly, 1.5mmol of Ni (NO)3)2·6H2O、3mmol Co(NO3)2·6H2O and 1.5mmol H3BTC is dissolved in 60ml DMF solution and stirred at 900rpm/min for 10min at room temperature; then, transferring the mixed solution into a 100mL reaction kettle, heating to 120 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal treatment for 15h at the temperature; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge, and centrifuging for 3min at the rotating speed of 10000 rpm/min; then washing with DMF, deionized water and 95% ethanol solution with mass concentration for 3 times in sequence; finally, the obtained precipitate was put into a drying oven and dried at 60 ℃ for 24 hours. After drying, electrochemical test is carried out to obtain the NiCo-MOF specific capacitance of 532F/g.
(3) Preparing an asymmetric device: the procedure of this step was the same as in example 1, and the total mass of the positive electrode was designated as M4It was 0.232 g. Thereby obtainingThe net loading of the NiCo-MOF sample was M+＝2.26mg/cm2. According to the positive electrode load capacity and the charge conservation law, the negative electrode load capacity is calculated to be M-＝5.02mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on the carbon felt with the same size as a negative electrode material; subsequently, 3g of PVA, 1.68g of KOH, 3mL of C were weighed3H8O330mL of deionized water, after PVA is stirred for 1h in a water bath at 85 ℃, the KOH solution is added dropwise, and then the C solution is added dropwise3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 20 min; taking out and then aligning and closing the two electrodes; and (3) wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 10min to obtain the all-solid-state supercapacitor. The device working voltage is 0-1.3V and the energy density is 47.69Wh/kg through testing.
Example 3:
(1) cleaning and activating the surface of the carbon felt: this step is the same as the procedure in example 1, and its mass M is weighed5It was 0.215 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: firstly 3mmol of Ni (NO)3)2·6H2O、1.5mmol Co(NO3)2·6H2O and 1.5mmol H3BTC is dissolved in 60ml DMF solution and stirred at 900rpm/min for 10min at room temperature; then, transferring the mixed solution into a 100mL reaction kettle, heating to 120 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal treatment at the temperature for 15 h; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge, and centrifuging for 3min at the rotating speed of 10000 rpm/min; then washing with DMF, deionized water and 95% ethanol solution with mass concentration for 3 times in sequence; finally, the precipitate obtained is placed in a drying cabinet and dried at 60 ℃ for 24 h. After drying, electrochemical test is carried out to obtain NiCo-MOF specific capacitance of 639F/g.
(3) Preparing an asymmetric device: the procedure of this step was the same as in example 1, and the total mass of the positive electrode was designated as M6It was 0.222 g. The net loading of the resulting NiCo-MOF sample was M+＝2.19mg/cm2. According to the positive electrode load capacity and the charge conservation law, the negative electrode load capacity is calculated to be M-＝4.87mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on the carbon felt with the same size as a negative electrode material; subsequently, 3g of PVA, 1.68g of KOH, 3mLC were weighed out3H8O330mL of deionized water, after PVA is stirred for 1h in a water bath at 85 ℃, the KOH solution is added dropwise, and then the C solution is added dropwise3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 20 min; taking out and then aligning and closing the two electrodes; and (3) wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 10min to obtain the all-solid-state supercapacitor. The device working voltage is 0-1.3V and the energy density is 58.93Wh/kg through testing.
Example 4:
(1) cleaning and activating the surface of the carbon felt: this step is the same as the procedure in example 1, and its mass M is weighed7It was 0.223 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: firstly, 6mmol of Ni (NO)3)2·6H2O、1.5mmol Co(NO3)2·6H2O and 1.5mmol H3BTC is dissolved in 60mL DMF solution and stirred at 900rpm/min for 10min at room temperature; then, transferring the mixed solution into a 100mL reaction kettle, heating to 120 ℃ at the speed of 5 ℃/min, and carrying out hydrothermal treatment at the temperature for 15 h; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge, and centrifuging for 3min at the rotating speed of 10000 rpm/min; then washing with DMF, deionized water and 95% ethanol solution with mass concentration for 3 times in sequence; finally, the obtained precipitate was put into a drying oven and dried at 60 ℃ for 24 hours. After drying, electrochemical tests are carried out to obtain NiCo-MOF specific capacitance of 639F/g.
(3) Preparing an asymmetric device: the procedure of this step was the same as in example 1, and the total mass of the positive electrode was designated as M8It was 0.229 g. The net load of the NiCo-MOF sample is M+＝2mg/cm2. According to beingCalculating the load of negative electrode as M according to the law of polar load and conservation of charge-＝4.44mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on a carbon felt with the same size as a negative electrode material; subsequently, 3g of PVA, 1.68g of KOH, 3mLC were weighed3H8O330mL of deionized water, after the PVA is stirred for 1 hour in a water bath at 85 ℃, the KOH solution is added dropwise, and then the C solution is added dropwise3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 10 min; taking out and aligning and closing the two poles; and (3) wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 20min to obtain the all-solid-state supercapacitor. The device working voltage is 0-1.3V and the energy density is 35.42Wh/kg after the test.
Examples 1-4 were conducted to compare the effect of different molar ratios of Ni and Co on the electrochemical performance of NiCo-MOF positive electrode materials, and it can be concluded that NiCo-MOF positive electrode materials have the best electrochemical performance when the molar ratio of Ni/Co is 2: 1. Similar to the electrode material, the device exhibits the optimum energy density at the corresponding ratio.
Example 5:
(1) cleaning and activating the surface of the carbon felt: this step is the same as the procedure in example 3, and its mass M is weighed9It was 0.229 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: this procedure was the same as in example 3. After drying, electrochemical tests were carried out to obtain NiCo-MOF specific capacitance of 628F/g.
(3) Preparing an asymmetric device: the procedure of this step is the same as in example 3, and the total mass of the positive electrode is referred to as M10It was 0.235 g. The net load of the NiCo-MOF sample is M+＝2.08mg/cm2. According to the positive electrode load capacity and the charge conservation law, the negative electrode load capacity is calculated to be M-＝4.62mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on a carbon felt with the same size as a negative electrode material; subsequently, 3 is weighedgPVA、1.68gKOH、0.329g K3[Fe(CN)6]、3mLC3H8O330mL of deionized water, after the PVA is stirred for 1 hour in a water bath at the temperature of 85 ℃, the KOH solution is added dropwise, and then the K solution is added dropwise3[Fe(CN)6]Solutions and C3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 20 min; taking out and then aligning and closing the two electrodes; and (3) wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 10min to obtain the all-solid-state supercapacitor. The test shows that the working voltage of the device is 0-1.3V, and the energy density is 61.37 Wh/kg.
Example 6:
(1) cleaning and activating the surface of the carbon felt: this step is the same as the procedure in example 3, and its mass M is weighed11It was 0.237 g.
(2) Preparing a bimetallic NiCo-MOF positive electrode material: this procedure was the same as in example 3. After drying, an electrochemical test is carried out to obtain the NiCo-MOF specific capacitance of 635F/g.
(3) Preparing an asymmetric device: the procedure was the same as in example 3, and the total mass of the positive electrode was designated as M12It was 0.244 g. The net load of the NiCo-MOF sample is M+＝2.33mg/cm2. According to the positive electrode load capacity and the charge conservation law, the negative electrode load capacity is calculated to be M-＝5.18mg/cm2. Similarly, ultra-thin MnO is self-made in a laboratory2The acetylene black and the PVDF are weighed according to the same mass ratio and ground into slurry to be coated on the carbon felt with the same size as a negative electrode material; subsequently, 3g of PVA, 1.68g of KOH, 3mL of C were weighed3H8O3、0.658g K3[Fe(CN)6]30mL of deionized water, stirring PVA in a water bath at 85 ℃ for 1h, then dropwise adding KOH solution, and dropwise adding K3[Fe(CN)6]Solutions and C3H8O3Synthesizing PVA/KOH gel electrolyte; finally, respectively soaking the anode and the cathode in the gel electrolyte for 20 min; taking out and then aligning and closing the two electrodes; wrapping a layer of plastic film on the surface of the electrode, and maintaining the device at 0.1MPa for 10min to obtain the all-solid-state super-capacitorA container. The test results show that the working voltage of the device is 0-1.3V, and the energy density is 66.52 Wh/kg.
Examples 3, 5 and 6 are to investigate the influence of the addition amount of the redox electron pair in the gel electrolyte on the energy density of the device, and it can be concluded that the additional introduction of the redox electron pair in the gel electrolyte plays a role in increasing the energy density of the device, and the energy density of the device is increased with the increase of the addition amount.
Claims (10)
1. The wide-temperature-zone supercapacitor electrode material is characterized in that the electrode material is a NiCo-MOF electrode material with high pseudocapacitance performance, the proportion of Ni and Co main metal ions can be changed, the electrode material is a NiCo-MOF ball similar to a raspberry shape, a large number of ultrathin nanosheets exist on the surface of the NiCo-MOF ball, the electrode material has an ultrahigh specific surface area, certain gaps exist among nanosheet layers, the non-totally-enclosed three-dimensional structure provides a large amount of space for free flow of anions and cations in electrolyte, the anion and cation freely-flowing space is in direct contact with the electrode material, the activity of the electrode material is improved, the electrochemical reaction rate of the electrode material is improved, and the pseudocapacitance effect is more remarkable.
2. A supercapacitor made of the wide temperature zone supercapacitor electrode material according to claim 1 as a positive electrode.
3. The supercapacitor of claim 2, comprising a positive electrode, a negative electrode and a gel electrolyte, wherein the negative electrode is ultra-thin MnO2The gel electrolyte is PVA/KOH gel electrolyte.
4. The preparation method of the wide temperature zone supercapacitor electrode material according to claim 1, characterized by comprising the following specific steps:
(1) cleaning and activating the surface of the carbon felt: ultrasonically cleaning a commercial carbon felt by using an ethanol solution and deionized water in sequence; then separately configure H2SO4Solution with HNO3The solution is poured into the carbon containerIn a beaker of felt; 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 is finished, taking out the carbon felt and cleaning the carbon felt with an ethanol solution for three times; finally, placing the carbon felt in an oven for drying, taking out the carbon felt, and weighing the carbon felt for later use;
(2) preparing a bimetallic NiCo-MOF positive electrode material: firstly, Ni (NO)3)2·6H2O、Co(NO3)2·6H2O and H3BTC is dissolved in DMF solution, the mixed solution is transferred to a reaction kettle after being stirred at room temperature, the mixed solution is heated to 120 ℃ at the speed of 5 ℃/min, and hydrothermal reaction is carried out at the temperature; after the reaction is finished and the temperature is naturally cooled to the room temperature, putting the sample into a centrifuge for centrifugation, and then sequentially washing the sample with DMF, deionized water and ethanol solution; and finally, putting the obtained precipitate into a drying oven for drying to obtain a NiCo-MOF sample.
5. The preparation method of the wide temperature zone supercapacitor electrode material according to claim 4, wherein in the step (1), the ultrasonic cleaning time is controlled to be 15 min; the concentration of the ethanol solution is 95 wt%; said H2SO4Solution and HNO3The concentration of the solution is 3mol/L, H2SO4Solution and HNO3The volume ratio of the solution is 3: 1; the oven temperature was 65 ℃.
6. The method for preparing the wide temperature zone supercapacitor electrode material according to claim 4, wherein in the step (2), the Ni (NO) is added3)2·6H2O、Co(NO3)2·6H2O and H3The molar ratio of BTC is 1: 1:1,1: 2:1,2: 1:1,4: 1: 1; DMF as activating agent, H3BTC is used as an initiator and an inducer, and the stirring speed is 900 rpm/min; controlling the hydrothermal reaction time of the reaction kettle to be 15 h; the rotating speed of the centrifugal machine is 10000rpm/min, and the centrifugal time is 3 min; the concentration of the ethanol solution is 95 wt%; the temperature of the drying oven is 60 ℃, and the drying time is 24 h.
7. As claimed in claim 2The preparation method of the super capacitor is characterized by comprising the following specific steps: firstly, sequentially weighing three substances including NiCo-MOF, acetylene black and PVDF, and pouring the substances into a mortar containing an NMP solvent for grinding into slurry; then coating the obtained slurry on a carbon felt, and drying overnight for later use; similarly, weighing ultrathin MnO2Pouring acetylene black and PVDF into a mortar containing an NMP solvent, grinding into slurry, coating the slurry on a carbon felt, and drying overnight to obtain a negative electrode material; subsequently, PVA, KOH, deionized water, K are weighed3[Fe(CN)6]And C3H8O3Synthesizing PVA/KOH gel electrolyte in water bath at 85 ℃; finally, soaking the positive electrode and the negative electrode in the gel electrolyte respectively; taking out and then aligning and closing the two electrodes; and (3) coating a layer of plastic film on the surface of the electrode, and applying pressure to the device to obtain the all-solid-state supercapacitor.
8. The method for preparing the supercapacitor according to claim 7, wherein the net mass of the NiCo-MOF positive electrode material is 1.89-2.33mg/cm2Ultra-thin MnO of negative electrode2The loading capacity is 4.2-5.18mg/cm2。
9. The method of claim 7, wherein the NiCo-MOF, acetylene black and PVDF are present in a mass ratio of 8:1:1, and the ultra-thin MnO is present2The mass ratio of the acetylene black to the PVDF is 8:1: 1; the size of the carbon felt is 1cm multiplied by 3cm, and the drying temperature is 70 ℃; PVA, KOH, deionized water, K3[Fe(CN)6]And C3H8O3The ratio of (A) to (B) is 3 g: 1.52 g: 30g of: 0.329-0.658 g: 3mL, K3[Fe(CN)6]And C3H8O3As an additive.
10. The method for preparing the supercapacitor according to claim 7, wherein after the PVA is stirred in a water bath at 85 ℃ for 1 hour, the KOH solution is added dropwise; soaking for 20-30 min; when assembling the device, the applied pressure is 0.1-0.15 MPa; the maintaining time is 10-15 min.
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| CN112837943A (en) * | 2021-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Ultrathin two-dimensional nanosheet layer NiCo-MOF material, and preparation method and application thereof |
| CN113517144A (en) * | 2021-03-19 | 2021-10-19 | 江苏大学 | Carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and preparation method thereof |
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| CN111009421A (en) * | 2019-11-22 | 2020-04-14 | 中国矿业大学 | Lamellar bimetallic organic framework compound and preparation method and application thereof |
| CN113517144A (en) * | 2021-03-19 | 2021-10-19 | 江苏大学 | Carbon fiber felt-based flexible all-solid-state asymmetric supercapacitor and preparation method thereof |
| CN112837943A (en) * | 2021-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Ultrathin two-dimensional nanosheet layer NiCo-MOF material, and preparation method and application thereof |
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