CN114420462A - Preparation method of super capacitor with long service life - Google Patents
Preparation method of super capacitor with long service life Download PDFInfo
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- CN114420462A CN114420462A CN202111617691.6A CN202111617691A CN114420462A CN 114420462 A CN114420462 A CN 114420462A CN 202111617691 A CN202111617691 A CN 202111617691A CN 114420462 A CN114420462 A CN 114420462A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000000463 material Substances 0.000 claims abstract description 64
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- -1 polypropylene Polymers 0.000 claims abstract description 11
- 229920001155 polypropylene Polymers 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 30
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 30
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 30
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 description 32
- 238000002474 experimental method Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000007789 sealing Methods 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- 238000005485 electric heating Methods 0.000 description 12
- 239000012286 potassium permanganate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000013112 stability test Methods 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
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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
- H01G11/46—Metal oxides
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
A method for preparing long-service-life super capacitor is characterized by using MnO wrapped by using tough material2@Ni(OH)2The material is prepared by a super capacitor assembly step with the anode of/NF, the cathode of an activated carbon plate, 7mol/L KOH solution as electrolyte and polypropylene as a separator. The specific capacitance of the electrode of the super capacitor reaches 105F/g at 1A, the maximum energy density reaches 47.3Wh/Kg, and MnO is2@Ni(OH)2the/NF electrode is treated by a tough material to enable MnO2@Ni(OH)2the/NF electrode is suitable for the charging and discharging process due to volume change, and can prevent the corrosion of electrolyte, so that the product has good circulation stability, and the specific capacitance is high after charging and discharging 10000 circles under the current of 3A/gThe retention rate is 99.8% of the initial retention rate, the electrochemical energy storage is excellent, and the method is worthy of market popularization.
Description
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a preparation method of a super capacitor with long service life.
Background
The super capacitor is a new type of energy storage device developed in the seventh and eighty years of the last century, and is a power source with special performance between the traditional capacitor and battery, and mainly depends on electric double layer and redox pseudo-capacitor charge to store electric energy, so unlike the traditional chemical power source, it is an electrochemical element, but does not generate chemical reaction in the process of energy storage, and the energy storage process is reversible, and it does not possess dielectric medium like ceramic capacitor and electrolytic capacitor, instead, it uses the state of electric double layer (electric double layer) formed on the interface by solid (electrode) and liquid (electrolyte) to replace the dielectric medium. Compared with the traditional battery, the super capacitor has the advantages of high power density, long quality guarantee period, wider use temperature range, safety, environmental friendliness and the like. In view of the advantages of super capacitors and the continuous improvement of research on their applications, super capacitors are widely used in many fields such as daily life, transportation, industry, renewable energy, military and the like, and exhibit significant advantages.
The electrode material is an important component of the super capacitor, and the performance of the super capacitor mainly depends on the quality of the capacitive performance of the electrode material, so that the electrode material becomes the most critical and most concerned part in the research process of the super capacitor, and through a large amount of research work, factors influencing the capacitance of the electrode material mainly comprise specific surface area, pore structure, conductivity and the like.
Transition metal oxide has high theoretical specific capacitance as a super capacitor electrode material, has abundant earth resources, low cost, does not cause environmental pollution and the like, and is widely concerned, although some transition metal oxides are reported to be used for the electrode material of the super capacitor at present, the conductivity of the transition metal oxide is generally low, the diffusion distance of electrolyte ions to the electrode is short, so that the cycle stability of the transition metal oxide is low and the actual specific capacitance is far lower than the theoretical value; in addition, in the charging and discharging process of the super capacitor, the electrode structure can be damaged due to the volume change of the electrode, the energy storage performance of the super capacitor is reduced after the super capacitor is charged and discharged for many times, the circulation stability is not ideal enough, in addition, the electrode structure can be damaged due to the fact that the electrode is in the electrolyte for a long time, the charging and discharging performance is reduced, and the service life is shortened.
Disclosure of Invention
The invention aims to provide a preparation method of a super capacitor with long service life.
The invention is realized by the following technical scheme:
a method for preparing a super capacitor with long service life is characterized in that MnO wrapped by a tough material is used2@Ni(OH)2The preparation method comprises the following steps of (1) preparing a super capacitor by using/NF as an anode, an activated carbon plate as a cathode, 7mol/L KOH solution as electrolyte and polypropylene as a separation plate; wherein the tough material is prepared from carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water.
In order to fully improve the electrochemical performance of the electrode, the MnO2@Ni(OH)2The preparation method of the/NF electrode comprises the following steps: preparing NF into proper small blocks, immersing the small blocks into a hydrochloric acid solution for ultrasonic treatment, taking out the small blocks, putting the small blocks into water, performing ultrasonic treatment again, drying the small blocks, putting the small blocks into a high-temperature hydrothermal kettle after drying, adding deionized water, sealing the kettle, reacting the mixture for 26 to 30 hours at the temperature of between 140 and 150 ℃, finishing the reaction, naturally cooling the reaction product to room temperature, taking out the reaction product, drying the reaction product, and taking out the reaction product to obtain Ni (OH)2/NF, then adding Ni (OH)2Placing the NF in a potassium permanganate solution, then placing the NF in a hydrothermal reaction kettle, carrying out heat preservation reaction at the temperature of 140-150 ℃ for 24-26 hours, naturally cooling to room temperature after the reaction is finished, removing a reactant, washing with water, drying the reactant after the washing is finished, and drying to obtain MnO2@Ni(OH)2a/NF electrode. The NF is foamNickel.
Super capacitor discovers in the use, and the charge-discharge process of many times can lead to energy storage performance to descend because electrode volume change itself, and on the other hand, electrode contact with electrolyte for a long time, and its surface is easily corroded by electrolyte, can lead to energy storage performance to descend equally for electric capacity life shortens, in order to thoroughly solve this technical problem, above-mentioned MnO2@Ni(OH)2the/NF also needs to be wrapped by a tough material, wherein the tough material comprises carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water in a mass ratio of 0.6-0.8: 3-7: 25-32: 3-5: 30-35, the particle size of the copper powder is 30-80 mu m, and the particle size of the carbon powder is 30-80 mu m.
Further, the MnO mentioned above2@Ni(OH)2the/NF tough material package is prepared by the following steps:
(1) preparing a tough material: heating deionized water to 50-60 ℃, adding sodium carboxymethylcellulose under the stirring condition, uniformly dispersing, and standing for 1-3 hours to obtain a sodium carboxymethylcellulose solution for later use; heating styrene butadiene rubber to 85-90 ℃, adding a sodium carboxymethylcellulose solution under the stirring condition, continuously stirring for 90-120 minutes, sequentially adding carbon powder and copper powder, continuously stirring for 20-30 minutes, and keeping the temperature for later use; the stirring speed is 60-90 r/min.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode into the tough material, standing for 1-2 hours at the temperature of 85-90 ℃, taking out, placing in a blast drying oven, setting the drying temperature to be 40-45 ℃, and drying for 15-24 hours to obtain the NF membrane. The unique bonding property of the sodium carboxymethylcellulose can enable the tough material to firmly cover MnO2@Ni(OH)2The surface of the/NF electrode is matched with styrene butadiene rubber and sodium carboxymethyl cellulose, so that MnO can be ensured on the one hand2@Ni(OH)2the/NF electrode has better toughness, so that the electrode is more suitable for volume change in the charging and discharging process, and the cactus-shaped core-shell structure system is ensured not to be damaged, and on the other hand, the styrene butadiene rubber and the sodium carboxymethylcellulose can be used in MnO2@Ni(OH)2/NF electrode surfaceThe film is formed to prevent the electrolyte from corroding and damaging the electrode, so that the charge and discharge performance is not reduced in the process of charging and discharging for many times, the cycle stability is good, and the carbon powder and the copper powder can provide the conductivity for the tough material.
Further, the assembly of the super capacitor is to treat MnO with the same size after being treated by a tough material2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
The invention has the following beneficial effects:
the invention relates to a preparation method of a super capacitor with long service life, which is MnO2@Ni(OH)2The specific capacitance of the electrode reaches 105F/g and the maximum energy density reaches 47.3Wh/Kg at 1A of the super capacitor made of/NF capacitor electrode, and MnO2@Ni(OH)2the/NF electrode is treated by a tough material to enable MnO2@Ni(OH)2the/NF electrode is suitable for the volume change in the charging and discharging process, and can prevent the corrosion of electrolyte, so that the product has good circulation stability, the specific capacitance retention rate is 99.8% of the initial value after charging and discharging for 10000 circles under the current of 3A/g, the electrochemical energy storage is excellent, and the method is worthy of market popularization.
Drawings
FIG. 1: the charge and discharge curves of the product obtained in example 1 are shown.
FIG. 2: the charge-discharge cycle stability chart of the product obtained in example 1 is shown.
FIG. 3: the charge-discharge curve of the product prepared in comparative experiment 1 is shown.
FIG. 4: a graph comparing the charge and discharge cycle stability of the product prepared in experiment 1.
FIG. 5: the charge-discharge curve of the product prepared in comparative experiment 2 is shown.
FIG. 6: a graph comparing the charge-discharge cycle stability of the product prepared in experiment 2.
FIG. 7: the charge-discharge curve of the product prepared in comparative experiment 3 is shown.
FIG. 8: a graph comparing the charge-discharge cycling stability of the product prepared in experiment 3.
Detailed Description
The present invention will be further specifically described below by way of examples with reference to the accompanying drawings.
Example 1
A preparation method of a super capacitor with long service life is prepared by the following steps:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small blocks of 3.5 multiplied by 1.5 cm, immersing the small blocks in 25ml of hydrochloric acid solution with the volume fraction of 20 percent, carrying out ultrasonic treatment for 25min, taking out, putting the small blocks in 70ml of deionized water, carrying out ultrasonic treatment for 50 min, putting the treated NF in an air-blast drying oven, setting the temperature to be 70 ℃, drying for 14 h, taking out, putting the NF in a high-temperature hydrothermal kettle, adding 45ml of deionized water, sealing, putting the kettle in an electric heating air-blast drying oven at 145 ℃, reacting for 28 h, naturally cooling to room temperature, taking out the reactant, putting the reactant in a constant-temperature drying oven at 45 ℃, drying for 28 h, taking out, putting the reactant in 40ml of potassium permanganate solution with the concentration of 0.02mol/L, putting the potassium permanganate solution in a hydrothermal reaction kettle, sealing, putting the kettle in the electric heating air-blast drying oven at 145 ℃ for heat preservation for 25 h, naturally cooling to room temperature, removing the reactant, repeatedly washing with deionized water for 4 times, after the washing is finished, the reactant is placed in a constant temperature air blast drying oven at 65 ℃ for drying for 25 hours, and MnO is obtained after the drying is finished2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2.MnO2@Ni(OH)2Coating with NF flexible material:
(1) preparing a tough material: heating deionized water to 55 ℃, adding sodium carboxymethylcellulose under the condition of stirring, uniformly dispersing, and standing for 2 hours to obtain sodium carboxymethylcellulose solution for later use; heating styrene butadiene rubber to 87 ℃, adding the sodium carboxymethylcellulose solution under the stirring condition, continuously stirring for 110 minutes, sequentially adding carbon powder and copper powder, continuously stirring for 25 minutes, and keeping the temperature for later use; the stirring speed is 80 r/min. The mass ratio of carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water in the tough material is 0.7: 5: 27: 4: 32, the particle size of the copper powder is 30-80 μm, and the particle size of the carbon powder is 30-80 μm.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode in the tough material, keeping the temperature at 88 ℃, standing for 1.5 hours, taking out, placing in an air-blast drying oven, setting the drying temperature at 42 ℃, and drying for 20 hours to obtain the NF electrode.
3. Assembling the super capacitor:
MnO with the same size after being treated by tough material2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
Experiment one: and (3) measuring mass specific capacitance:
the super capacitor prepared in example 1 is tested under the current density of 1A/g, 1.5A/g, 2A/g, 3A/g and 5A/g to obtain the charge-discharge curve of the electrode, and the experimental result shows that: the specific capacitance of the electrode of the product prepared in the example 1 reaches 102F/g at 1A/g, and the maximum energy density reaches 45.9Wh/Kg, and the specific energy density is shown in figure 2.
Experiment two: charge-discharge cycle stability experiment:
coated MnO2@ Ni (OH) for the tough Material from example 12The electrode material is cut into a square with the length of 1cm multiplied by 1cm as a working electrode after activation, a platinum sheet electrode is used as a counter electrode, a silver chloride electrode is used as a reference electrode, the charging and discharging curve of the electrode is tested under the current density of 3A/g, the electrode is charged and discharged for 10000 circles under the current density of 3A/g, the specific capacity is recorded and calculated once every 500 circles, the experimental result is shown in figure 3, the electrode is charged and discharged for 10000 circles under the current density of 3A/g, the specific capacitance is not attenuated, and the retention rate is 100% of the initial value.
Experiment three: comparative experiment
Comparative experiment 1: a preparation method of a super capacitor with long service life is as the preparation method of example 1, except that the electrode material is not processed by a tough material, the specific steps are as follows:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small blocks of 3.5 multiplied by 1.5 cm, immersing the small blocks in 25ml of hydrochloric acid solution with the volume fraction of 20 percent, carrying out ultrasonic treatment for 25min, taking out, putting the small blocks in 70ml of deionized water, carrying out ultrasonic treatment for 50 min, putting the treated NF in an air-blast drying oven, setting the temperature to be 70 ℃, drying for 14 h, taking out, putting the NF in a high-temperature hydrothermal kettle, adding 45ml of deionized water, sealing, putting the kettle in an electric heating air-blast drying oven at 145 ℃, reacting for 28 h, naturally cooling to room temperature, taking out the reactant, putting the reactant in a constant-temperature drying oven at 45 ℃, drying for 28 h, taking out, putting the reactant in 40ml of potassium permanganate solution with the concentration of 0.02mol/L, putting the potassium permanganate solution in a hydrothermal reaction kettle, sealing, putting the kettle in the electric heating air-blast drying oven at 145 ℃ for heat preservation for 25 h, naturally cooling to room temperature, removing the reactant, repeatedly washing with deionized water for 4 times, after the washing is finished, the reactant is placed in a constant temperature air blast drying oven at 65 ℃ for drying for 25 hours, and MnO is obtained after the drying is finished2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2. Assembling the super capacitor:
MnO of2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
According to the experimental method of the embodiment 1, the mass specific capacitance measurement and the charge-discharge cycle stability test are respectively carried out, and the test result shows that; the specific capacitance of the electrode of the product prepared in the comparative experiment 1 reaches 95F/g at 1A/g, and the energy density is 42.75Wh/Kg at the moment, and the specific figure is shown in figure 4; the result of the charge-discharge cycle stability test shows that after 10000 cycles of charge and discharge under the current of 3A/g, the specific capacitance retention rate is initial 67.2%, and particularly shown in figure 5, the charge-discharge stability of the product is poor under the condition that the electrode is not wrapped by the added tough material.
Comparative experiment 2: according to the preparation method of the embodiment 1, the toughness is still treated by the tough material, only the tough material is not added with sodium carboxymethyl cellulose, and the preparation method comprises the following specific steps:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small blocks of 3.5 multiplied by 1.5 cm, immersing the small blocks in 25ml of hydrochloric acid solution with the volume fraction of 20 percent, carrying out ultrasonic treatment for 25min, taking out, putting the small blocks in 70ml of deionized water, carrying out ultrasonic treatment for 50 min, putting the treated NF in an air-blast drying oven, setting the temperature to be 70 ℃, drying for 14 h, taking out, putting the NF in a high-temperature hydrothermal kettle, adding 45ml of deionized water, sealing, putting the kettle in an electric heating air-blast drying oven at 145 ℃, reacting for 28 h, naturally cooling to room temperature, taking out the reactant, putting the reactant in a constant-temperature drying oven at 45 ℃, drying for 28 h, taking out, putting the reactant in 40ml of potassium permanganate solution with the concentration of 0.02mol/L, putting the potassium permanganate solution in a hydrothermal reaction kettle, sealing, putting the kettle in the electric heating air-blast drying oven at 145 ℃ for heat preservation for 25 h, naturally cooling to room temperature, removing the reactant, repeatedly washing with deionized water for 4 times, after the washing is finished, the reactant is placed in a constant temperature air blast drying oven at 65 ℃ for drying for 25 hours, and MnO is obtained after the drying is finished2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2.MnO2@Ni(OH)2Coating with NF flexible material:
(1) preparing a tough material: taking butadiene styrene rubber, heating to 87 ℃, sequentially adding carbon powder and copper powder under the stirring condition, continuing stirring for 25 minutes, and keeping the temperature for later use; the stirring speed is 80 r/min. The mass ratio of carbon powder, butadiene styrene rubber, copper powder and deionized water in the tough material is 0.7: 27: 4: 32, the particle size of the copper powder is 30-80 μm, and the particle size of the carbon powder is 30-80 μm.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode in the tough material, keeping the temperature at 88 ℃, standing for 1.5 hours, taking out, placing in an air-blast drying oven, setting the drying temperature at 42 ℃, and drying for 20 hours to obtain the NF electrode.
3. Assembling the super capacitor:
MnO with the same size after being treated by tough material2@Ni(OH)2the/NF electrode, polypropylene, activated carbon plate are pressed together, thenAnd (3) curling into a cylinder shape, placing the cylinder shape into a sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
According to the experimental method of the embodiment 1, the mass specific capacitance measurement and the charge-discharge cycle stability test are respectively carried out, and the test result shows that; the specific capacitance of the electrode of the product prepared in the comparative experiment 2 reaches 93F/g at 1A/g, and the energy density is 41.85Wh/Kg at the time, specifically shown in FIG. 6; the result of the charge-discharge cycle stability test shows that after 10000 cycles of charge and discharge under the current of 3A/g, the specific capacitance retention rate is 75.2% of the initial value, and particularly shown in figure 7, the charge-discharge stability of the product is poor under the condition that the electrode is wrapped by the ductile material.
Comparative experiment 3: according to the preparation method of the embodiment 1, the toughness is still treated by the tough material, only the styrene butadiene rubber is not added into the tough material, and the preparation method comprises the following specific steps:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small blocks of 3.5 multiplied by 1.5 cm, immersing the small blocks in 25ml of hydrochloric acid solution with the volume fraction of 20 percent, carrying out ultrasonic treatment for 25min, taking out, putting the small blocks in 70ml of deionized water, carrying out ultrasonic treatment for 50 min, putting the treated NF in an air-blast drying oven, setting the temperature to be 70 ℃, drying for 14 h, taking out, putting the NF in a high-temperature hydrothermal kettle, adding 45ml of deionized water, sealing, putting the kettle in an electric heating air-blast drying oven at 145 ℃, reacting for 28 h, naturally cooling to room temperature, taking out the reactant, putting the reactant in a constant-temperature drying oven at 45 ℃, drying for 28 h, taking out, putting the reactant in 40ml of potassium permanganate solution with the concentration of 0.02mol/L, putting the potassium permanganate solution in a hydrothermal reaction kettle, sealing, putting the kettle in the electric heating air-blast drying oven at 145 ℃ for heat preservation for 25 h, naturally cooling to room temperature, removing the reactant, repeatedly washing with deionized water for 4 times, after the washing is finished, the reactant is placed in a constant temperature air blast drying oven at 65 ℃ for drying for 25 hours, and MnO is obtained after the drying is finished2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2.MnO2@Ni(OH)2Coating with NF flexible material:
(1) preparing a tough material: heating deionized water to 55 ℃, adding sodium carboxymethylcellulose under the stirring condition, standing for 2 hours after uniform dispersion to obtain a sodium carboxymethylcellulose solution, sequentially adding carbon powder and copper powder into the sodium carboxymethylcellulose solution under the stirring condition, continuing stirring for 25 minutes, and keeping the temperature for later use; the stirring speed is 80 r/min. The mass ratio of carbon powder, sodium carboxymethylcellulose, copper powder and deionized water in the tough material is 0.7: 5: 4: 32, the particle size of the copper powder is 30-80 μm, and the particle size of the carbon powder is 30-80 μm.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode in the tough material, keeping the temperature at 88 ℃, standing for 1.5 hours, taking out, placing in an air-blast drying oven, setting the drying temperature at 42 ℃, and drying for 20 hours to obtain the NF electrode.
3. Assembling the super capacitor:
MnO with the same size after being treated by tough material2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
According to the experimental method of the embodiment 1, the mass specific capacitance measurement and the charge-discharge cycle stability test are respectively carried out, and the test result shows that; the specific capacitance of the electrode of the product prepared in the comparative experiment 3 reaches 91F/g at 1A/g, and the energy density is 41Wh/Kg at the moment, specifically shown in FIG. 7; the result of the charge-discharge cycle stability test shows that after 10000 cycles of charge and discharge under the current of 3A/g, the specific capacitance retention rate is 81.3% of the initial value, and particularly shown in figure 8, the charge-discharge stability of the product is poor under the condition that the electrode is wrapped by the ductile material.
Example 2
A preparation method of a super capacitor with long service life is prepared by the following steps:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small pieces of 3.5 × 1.5 cm, soaking in 30ml hydrochloric acid solution with volume fraction of 18%, ultrasonic treating for 30min, taking out, and placing in 80mlPerforming ultrasonic treatment for 60 minutes in ionized water, then placing the treated NF in an air-blowing drying oven, setting the temperature to be 75 ℃, drying for 12 hours, taking out, placing in a high-temperature hydrothermal kettle, adding 42ml of deionized water, sealing, placing in an electric heating air-blowing drying oven at 150 ℃, reacting for 26 hours, finishing the reaction, naturally cooling to room temperature, taking out the reactant, placing in a constant-temperature drying oven at 50 ℃, drying for 30 hours, taking out, placing in 50ml of 0.03mol/L potassium permanganate solution, placing in a hydrothermal reaction kettle, sealing, placing in an electric heating air-blowing drying oven at 150 ℃, preserving heat for reacting for 26 hours, finishing the reaction, naturally cooling to room temperature, removing the reactant, repeatedly washing for 5 times by using deionized water, finishing the washing, placing the reactant in a constant-temperature air-blowing drying oven at 70 ℃ for drying for 26 hours, and finishing the drying to obtain MnO2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2.MnO2@Ni(OH)2Coating with NF flexible material:
(1) preparing a tough material: heating deionized water to 60 ℃, adding sodium carboxymethylcellulose under the condition of stirring, uniformly dispersing, and standing for 3 hours to obtain sodium carboxymethylcellulose solution for later use; heating styrene butadiene rubber to 90 ℃, adding the sodium carboxymethylcellulose solution under the stirring condition, continuously stirring for 120 minutes, sequentially adding carbon powder and copper powder, continuously stirring for 30 minutes, and keeping the temperature for later use; the stirring speed is 90 r/min. The MnO2@Ni(OH)2the/NF also needs to be wrapped by a tough material, wherein the tough material comprises carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water in a mass ratio of 0.8: 7: 32: 5: 35, the particle size of the copper powder is 30-80 μm, and the particle size of the carbon powder is 30-80 μm.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode in the tough material, keeping the temperature at 90 ℃, standing for 2 hours, taking out, placing in an air-blast drying oven, setting the drying temperature at 45 ℃, and drying for 24 hours to obtain the NF electrode.
3. Assembling the super capacitor:
of the same size after treatment with a ductile materialMnO2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
According to the experimental method of the embodiment 1, the mass specific capacitance measurement and the charge-discharge cycle stability test are respectively carried out, and the test result shows that; the specific capacitance of the electrode of the product prepared in the example 2 reaches 105F/g at 1A/g, and the maximum energy density reaches 47.3 Wh/Kg; the charge-discharge cycle stability test result shows that after 10000 cycles of charge-discharge under the current of 3A/g, the specific capacitance retention rate is 99.8% of the initial specific capacitance retention rate.
Example 3
A preparation method of a super capacitor with long service life is prepared by the following steps:
1.MnO2@Ni(OH)2preparation of/NF electrode
Cutting NF into rectangular small blocks of 3.5 multiplied by 1.5 cm, immersing the small blocks in 20ml hydrochloric acid solution with the volume fraction of 25 percent for ultrasonic treatment for 20min, taking out the small blocks, putting the small blocks in 50ml deionized water for ultrasonic treatment for 30min, putting the treated NF in an air-blast drying oven, setting the temperature to 65 ℃, drying the small blocks for 15 h, taking out the small blocks, putting the small blocks in a high-temperature hydrothermal kettle, adding 40ml deionized water, sealing the kettle, putting the kettle in an electric heating air-blast drying oven at 150 ℃, reacting for 26 h, naturally cooling to room temperature, taking out the reactant, putting the reactant in a constant-temperature drying oven at 40 ℃, drying for 30 h, taking out the reactant, putting the reactant in 35ml potassium permanganate solution with the concentration of 0.02mol/L, putting the potassium permanganate solution in a hydrothermal reaction kettle, sealing the kettle, putting the kettle in an electric heating air-blast drying oven at 140 ℃ for heat preservation and reacting for 26 h, naturally cooling to the room temperature, removing the reactant, repeatedly washing the reactant by deionized water for 3 times, after the washing is finished, the reactant is placed in a constant temperature air blast drying oven at 60 ℃ for drying for 26 hours, and MnO is obtained after the drying is finished2@Ni(OH)2a/NF electrode. The NF is foamed nickel.
2.MnO2@Ni(OH)2Coating with NF flexible material:
(1) preparing a tough material: heating deionized water to 50 deg.C, adding sodium carboxymethylcellulose under stirring, dispersing uniformly, and standing 1Obtaining sodium carboxymethyl cellulose solution for later use; heating styrene butadiene rubber to 85 ℃, adding the sodium carboxymethylcellulose solution under the stirring condition, continuously stirring for 90 minutes, sequentially adding carbon powder and copper powder, continuously stirring for 20 minutes, and keeping the temperature for later use; the stirring speed is 60 r/min. The MnO2@Ni(OH)2the/NF also needs to be wrapped by a tough material, wherein the tough material comprises carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water in a mass ratio of 0.6: 3: 25: 3: 30, the particle size of the copper powder is 30-80 mu m, and the particle size of the carbon powder is 30-80 mu m.
（2）MnO2@Ni(OH)2Coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode in the tough material, keeping the temperature at 85 ℃, standing for 2 hours, taking out, placing in an air-blast drying oven, setting the drying temperature at 40 ℃, and drying for 24 hours to obtain the NF electrode.
3. Assembling the super capacitor:
MnO with the same size after being treated by tough material2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
According to the experimental method of the embodiment 1, the mass specific capacitance measurement and the charge-discharge cycle stability test are respectively carried out, and the test result shows that; the specific capacitance of the electrode of the product prepared in the example 3 reaches 103F/g at 1A/g, and the maximum energy density reaches 46.4 Wh/Kg; the charge-discharge cycle stability test result shows that after 10000 cycles of charge-discharge under the current of 3A/g, the specific capacitance retention rate is 99.7 percent of the initial specific capacitance retention rate.
Claims (4)
1. A method for preparing a super capacitor with long service life is characterized in that MnO wrapped by a tough material is used2@Ni(OH)2The preparation method comprises the following steps of (1) preparing a super capacitor by using/NF as an anode, an activated carbon plate as a cathode, 7mol/L KOH solution as electrolyte and polypropylene as a separation plate; wherein the tough material is prepared from carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized waterAnd (5) obtaining the product.
2. The method of claim 1, wherein said MnO is selected from the group consisting of2@Ni(OH)2the/NF also needs to be wrapped by a tough material, wherein the tough material comprises carbon powder, sodium carboxymethylcellulose, styrene butadiene rubber, copper powder and deionized water in a mass ratio of 0.6-0.8: 3-7: 25-32: 3-5: 30-35, the particle size of the copper powder is 30-80 mu m, and the particle size of the carbon powder is 30-80 mu m.
3. The method of claim 2, wherein said MnO is selected from the group consisting of2@Ni(OH)2the/NF tough material package is prepared by the following steps:
(1) preparing a tough material: heating deionized water to 50-60 ℃, adding sodium carboxymethylcellulose under the stirring condition, uniformly dispersing, and standing for 1-3 hours to obtain a sodium carboxymethylcellulose solution for later use; heating styrene butadiene rubber to 85-90 ℃, adding a sodium carboxymethylcellulose solution under the stirring condition, continuously stirring for 90-120 minutes, sequentially adding carbon powder and copper powder, continuously stirring for 20-30 minutes, and keeping the temperature for later use; the stirring speed is 60-90 r/min;
（2）MnO2@Ni(OH)2coating with NF flexible material: MnO of2@Ni(OH)2Immersing the NF electrode into the tough material, standing for 1-2 hours at the temperature of 85-90 ℃, taking out, placing in a blast drying oven, setting the drying temperature to be 40-45 ℃, and drying for 15-24 hours to obtain the NF membrane.
4. The method of claim 3, wherein the supercapacitor is assembled by treating the supercapacitor with a tough material to form MnO of the same size2@Ni(OH)2Pressing the NF electrode, the polypropylene and the activated carbon plate together, then curling into a cylinder shape, placing the cylinder shape into the sleeve, and then injecting 7mol/L KOH solution into the sleeve to obtain the super capacitor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109243839A (en) * | 2018-09-30 | 2019-01-18 | 湖南大学 | A kind of electrode material for super capacitor and preparation method with big work potential window |
| CN113421779A (en) * | 2021-06-22 | 2021-09-21 | 重庆文理学院 | Preparation method of super capacitor with good circulation stability |
| CN113421775A (en) * | 2021-06-22 | 2021-09-21 | 重庆文理学院 | NiO @ CoMoO4Preparation method of/NF capacitance electrode |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109243839A (en) * | 2018-09-30 | 2019-01-18 | 湖南大学 | A kind of electrode material for super capacitor and preparation method with big work potential window |
| CN113421779A (en) * | 2021-06-22 | 2021-09-21 | 重庆文理学院 | Preparation method of super capacitor with good circulation stability |
| CN113421775A (en) * | 2021-06-22 | 2021-09-21 | 重庆文理学院 | NiO @ CoMoO4Preparation method of/NF capacitance electrode |
Non-Patent Citations (1)
| Title |
|---|
| LIANGLIANG TIAN等: "Rationally design of 2D branched Ni(OH)2/MnO2 hybrid hierarchical architecture on Ni foam for high performance supercapacitors", 《ELECTROCHIMICA ACTA》 * |
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