CN112735843A - Method for improving manganese dioxide super-capacity by hierarchically assembling nano-electrodes - Google Patents

Method for improving manganese dioxide super-capacity by hierarchically assembling nano-electrodes Download PDF

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CN112735843A
CN112735843A CN202011541781.7A CN202011541781A CN112735843A CN 112735843 A CN112735843 A CN 112735843A CN 202011541781 A CN202011541781 A CN 202011541781A CN 112735843 A CN112735843 A CN 112735843A
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manganese dioxide
hours
solution
graphite felt
temperature
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王连卫
曲艺鸿
严晨欢
徐少辉
熊大元
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East China Normal University
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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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a method for improving the ultra-compatibility of manganese dioxide by a nano electrode assembled in layers. The invention aims to solve the problem that the performance of manganese dioxide as a super capacitor is poor. The manganese dioxide of the present invention is grown on a graphite felt material on which titanium nitride has been induced to grow. The preparation method of the layered assembled nano electrode comprises the following steps: firstly, weighing and mixing raw materials in proportion; secondly, soaking the substrate material to prepare seeds; thirdly, washing and vacuum drying; fourthly, carrying out hydrothermal reaction; fifthly, nitriding in a tube furnace; sixthly, carrying out hydrothermal reaction; and seventhly, washing and vacuum drying. The invention has the advantages that: the titanium dioxide generated by seed induction can completely and uniformly coat the graphite felt, the titanium nitride generated after nitridation keeps the appearance of the titanium dioxide, the titanium nitride nano array provides a proper environment for the subsequent growth of manganese dioxide, and the surface of the titanium nitride is uniformly covered by the grown manganese dioxide nano sheet, so that the specific surface area of the material is increased.

Description

Method for improving manganese dioxide super-capacity by hierarchically assembling nano-electrodes
Technical Field
The invention belongs to the field of energy storage of manganese dioxide super capacitors, and relates to a method for planting seeds on a graphite felt, a method for preparing nano-wire titanium dioxide, a method for generating titanium nitride by nitriding titanium dioxide and a method for preparing nano-sheet manganese dioxide.
Background
Although manganese dioxide has attracted considerable attention as an electrode material in supercapacitors, its further development is hampered by poor electrical conductivity. Herein we describe a simple method to deposit manganese dioxide nanoplates onto an array of highly conductive long tapered titanium nitride nanofibers grown on a seed graphite felt to improve electrochemical performance. MnO2the/TiN/SGF electrode showed a high area capacitance of 425.5F/g after 1A/g and 10,000 test cycles, with almost no change in capacitance, indicating excellent cycling stability and good reversibility. MnO2The area capacitance of/TiN/SGF is far superior to MnO2/TiO2/SGF, TiN/SGF and TiO2The enhanced performance of the/SGF electrode can be attributed to the unique nanostructure and the apparent synergy between titanium nitride and manganese dioxide. The strong nanofibrous scaffold produced by the simple and efficient seed hydrothermal synthesis method contributes to achieving good cycle performance. The resulting nanocomposites are promising candidates for high performance energy storage systems.
Disclosure of Invention
The invention aims to provide a method for improving the super-capacity performance of manganese dioxide by a layered assembly nano electrode, so as to solve the problem of low super-capacity performance of manganese dioxide caused by poor conductivity of manganese dioxide in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for improving the ultra-capacitive performance of manganese dioxide by a layered assembly nano electrode comprises the following steps:
firstly, cutting a graphite felt into graphite felts of 1cm multiplied by 1cm as a base material, ultrasonically cleaning the graphite felts in ethanol and deionized water, and then drying the graphite felts for 24 hours at the temperature of 60 ℃;
secondly, preparing a solution containing 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid; mixing with graphite felt for 30min to form titanium dioxide seed crystals on the graphite felt to produce graphite felt containing seeds, and then drying at 60 ℃;
step three, soaking the graphite felt cleaned in the step one in the solution prepared in the step two for 30 minutes, then cleaning with deionized water, and then drying at 60 ℃ for 24 hours to obtain the graphite felt with the seeds;
step four, preparing a mixed solution containing 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate;
fifthly, sealing the graphite felt with the seeds prepared in the third step and the solution prepared in the fourth step in a hydrothermal reaction kettle, carrying out solvothermal reaction for 5 hours at the temperature of 150 ℃, and naturally cooling to room temperature;
sixthly, cleaning the composite material obtained in the fifth step, and drying for 24 hours at the temperature of 60 ℃;
step seven, mixing the composite material obtained in the step six with 4g of urea, putting the mixture into a quartz boat, putting the quartz boat into a tube furnace, starting a mechanical pump, and vacuumizing;
eighthly, after the vacuum pumping in the seventh step is carried out to a preset value, opening an air inlet, introducing nitrogen, and adjusting the gas introduction speed;
step nine, setting the nitriding time to be 3 hours, the temperature to be 800 ℃ and the like;
tenth, cleaning the composite material obtained in the ninth step, and drying for 24 hours at 60 ℃;
step eleven, respectively preparing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L, and mixing the potassium permanganate solution and the manganese sulfate solution in a ratio of 1:1 to obtain a mixed solution;
step ten, sealing the composite material obtained in the step ten and the mixed solution prepared in the step eleventh in a hydrothermal reaction kettle, carrying out solvothermal reaction for 12 hours at the temperature of 140 ℃, and naturally cooling to room temperature;
and step three, cleaning the composite material obtained in the step two, and drying at 60 ℃ for 24 hours to obtain a sample.
The prepared graphite felt as the electrode substrate material is completely coated by titanium nitride, manganese dioxide growing on the titanium nitride after hydrothermal treatment is more and is in a nanometer flake shape, the length and the width are about 250nm, and the thickness is less than 30 nm. The energy storage performance of the prepared electrode, manganese dioxide, is greatly improved, the high-area capacitance of 425.5F/g is almost unchanged after 1A/g and 10,000 test cycles, and in addition, the contact resistance of the solution is very small.
In the first step, the dispersing agent is absolute ethyl alcohol and deionized water.
In the second step and the third step, the seed solution is a solution of 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid, and the soaking time is 30 min.
In the fourth step, the solution for growing titanium dioxide is a mixed solution of 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate.
In the fifth step, the hydrothermal time is 5 hours, and the temperature is 150 ℃.
In the ninth step, the nitrogen nitriding time is 3 hours, and the temperature is 800 ℃.
In the eleventh step, the solution for growing manganese dioxide is a mixed solution generated by mixing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L in a ratio of 1: 1.
In the thirteenth step, the duration of the hydrothermal growth of manganese dioxide is 12 hours, and the temperature is 140 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the hydrothermal method adopted by the invention for synthesizing titanium dioxide and manganese dioxide is simple in operation, low in cost and good in reproducibility.
(2) The method for nitriding titanium dioxide by nitrogen is convenient to operate and uniform in nitridation.
(3) According to the manganese dioxide composite electrode based on the graphite felt material with the titanium nitride grown by induction, titanium dioxide generated by seed induction is nitrided to generate titanium nitride, so that the titanium nitride can completely coat the graphite felt fiber, a solid growth framework is provided for manganese dioxide, the manganese dioxide material grown by hydrothermal growth is fluffier, and the surface active area is increased. In addition, the introduction of nitrogen is helpful for increasing the active sites of the material, thereby being helpful for improving the super capacity energy storage performance of the material.
Drawings
FIG. 1 is an SEM image of a layered assembled nanoelectrode composite;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is an XRD pattern of the original graphite felt and layered assembly nanoelectrode composite;
FIG. 4 is an XPS spectrum of individual elements of a layered assembly nanoelectrode composite
FIG. 5 shows MnO2/TiN/SGF、MnO2/TiO2(iii) SGF, TiN/SGF and TiO2Cyclic voltammograms of/SGF electrodes;
FIG. 6 shows MnO2A current-time curve diagram of the/TiN/SGF electrode under different charge and discharge rates;
FIG. 7 shows MnO2/TiN/SGF、MnO2/TiO2(iii) SGF, TiN/SGF and TiO2Nyquist plot for/SGF electrodes;
FIG. 8 shows MnO2the/TiN/SGF retained the image over 10,000 cycles of charge and discharge.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
In the steps of the invention, the quantity proportion of reactants must be strictly controlled, the concentration deviation of the reactants is overlarge, and the product is not easy to form.
The gas flow rate must be strictly controlled in the steps of the invention, and the gas flow rate is too fast and the nitridation is not complete.
The reaction time must be strictly controlled in the steps of the invention, the reactant dosage is changed by changing the reaction time, and the capacitance performance is firstly increased and then reduced along with the increase of the reaction time and the reactant dosage.
Example 1
The steps of improving the manganese dioxide super-capacity by the layered assembly of the nano-electrode are as follows:
1. cutting the graphite felt into graphite felt of 1cm multiplied by 1cm as a base material, ultrasonically cleaning the graphite felt in ethanol and deionized water, and then drying the graphite felt for 24 hours at the temperature of 60 ℃;
2. a solution containing 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid was prepared; mixing with graphite felt for 30min to form titanium dioxide seed crystals on the graphite felt to produce graphite felt containing seeds, and then drying at 60 ℃;
3. soaking the graphite felt cleaned in the first step in the solution prepared in the second step for 30min, then cleaning with deionized water, and then drying at 60 ℃ for 24h to obtain a seeded graphite felt;
4. preparing a mixed solution containing 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate;
5. sealing the graphite felt with the seeds prepared in the third step and the solution prepared in the fourth step in a hydrothermal reaction kettle, carrying out solvothermal reaction for 5 hours at the temperature of 150 ℃, and naturally cooling to room temperature;
6. cleaning the composite material obtained in the fifth step, and drying for 24 hours at 60 ℃;
7. mixing the composite material obtained in the sixth step with 4g of urea, putting the mixture into a quartz boat, putting the quartz boat into a tube furnace, starting a mechanical pump, and vacuumizing;
8. after the vacuum pumping in the seventh step reaches a preset value, opening an air inlet, introducing nitrogen, and adjusting the gas introduction speed;
9. setting the nitriding time to be 3h, the temperature to be 800 ℃ and the like;
10. cleaning the composite material obtained in the ninth step, and drying for 24 hours at 60 ℃;
11. respectively preparing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L, and mixing the potassium permanganate solution and the manganese sulfate solution by a ratio of 1:1 to obtain a mixed solution;
12. sealing the composite material obtained in the tenth step and the mixed solution prepared in the eleventh step in a hydrothermal reaction kettle, carrying out solvothermal reaction for 12 hours at the temperature of 140 ℃, and naturally cooling to room temperature;
13. and (4) cleaning the composite material obtained in the twelfth step, and drying at 60 ℃ for 24h to obtain a sample.
Example 2
The steps of improving the manganese dioxide super-capacity by the layered assembly of the nano-electrode are as follows:
firstly, cutting a graphite felt into graphite felts of 1cm multiplied by 1cm as a base material, ultrasonically cleaning the graphite felts in ethanol and deionized water, and then drying the graphite felts for 24 hours at the temperature of 60 ℃;
secondly, preparing a solution containing 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid; mixing with graphite felt for 30min to form titanium dioxide seed crystals on the graphite felt to produce graphite felt containing seeds, and then drying at 60 ℃;
step three, soaking the graphite felt cleaned in the step one in the solution prepared in the step two for 30min, then cleaning with deionized water, and then drying at 60 ℃ for 24h to obtain the graphite felt with the seeds;
step four, preparing a mixed solution containing 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate;
fifthly, sealing the graphite felt with the seeds prepared in the third step and the solution prepared in the fourth step in a hydrothermal reaction kettle, carrying out solvothermal reaction for 5 hours at the temperature of 150 ℃, and naturally cooling to room temperature;
sixthly, cleaning the composite material obtained in the fifth step, and drying for 24 hours at the temperature of 60 ℃;
step seven, mixing the composite material obtained in the step six with 4g of urea, putting the mixture into a quartz boat, putting the quartz boat into a tube furnace, starting a mechanical pump, and vacuumizing;
eighthly, after the vacuum pumping in the seventh step is carried out to a preset value, opening an air inlet, introducing nitrogen, and adjusting the gas introduction speed;
step nine, setting the nitriding time to be 3 hours, the temperature to be 800 ℃ and the like;
tenth, cleaning the composite material obtained in the ninth step, and drying for 24 hours at 60 ℃;
step eleven, respectively preparing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L, and mixing the potassium permanganate solution and the manganese sulfate solution in a ratio of 1:1 to obtain a mixed solution;
step ten, sealing the composite material obtained in the step ten and the mixed solution prepared in the step eleventh in a hydrothermal reaction kettle, carrying out solvothermal reaction for 12 hours at the temperature of 140 ℃, and naturally cooling to room temperature;
and step three, cleaning the composite material obtained in the step two, and drying at 60 ℃ for 24 hours to obtain a sample.
The prepared graphite felt as the electrode substrate material is completely coated by titanium nitride, manganese dioxide growing on the titanium nitride after hydrothermal treatment is more and is in a nanometer flake shape, the length and the width are about 250nm, and the thickness is less than 30 nm. The energy storage performance of the prepared electrode, manganese dioxide, is greatly improved, the high-area capacitance of 425.5F/g is almost unchanged after 1A/g and 10,000 test cycles, and in addition, the contact resistance of the solution is very small.
Various test patterns for examples 1-2 are shown in FIGS. 1-8:
FIG. 1 depicts manganese dioxide grown as nanoplatelets on titanium nitride nanorods;
FIG. 2 can be seen as a close-up view of a layered assembled nanoelectrode composite;
FIG. 3 shows the XRD diffraction patterns of the original and nitrogen-doped molybdenum disulfide, consistent with standard card;
FIG. 4 shows XPS spectra of the layered assembly nano-electrode composite material, in which elements such as Ti, N, Mn, O, etc. can be observed;
FIG. 5 depicts a cyclic voltammogram comparison of a layered assembly nanoelectrode composite with other electrode materials produced during the preparation process, and it can be seen that MnO was prepared2the/TiN/SGF electrode has the largest closed area, which means MnO is prepared2the/TiN/SGF electrode can storeMore energy is stored;
the MnO prepared can be seen in FIG. 62the/TiN/SGF electrode can maintain a triangular charge-discharge shape under different charge-discharge rates, and the excellent redox reversibility is represented;
FIG. 7 is a Nyquist plot of the layered assembly nanoelectrode composite as compared to other electrode materials produced during the fabrication process, and it can be seen that the composite has a lower contact resistance;
fig. 8 shows that the layered assembly nano-electrode composite is more stable under long-term cycling, and the discharge time length after 10,000 cycles has no obvious change.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (8)

1. A method for improving the ultra-capacitive performance of manganese dioxide by a layered assembly nano electrode is characterized by comprising the following steps: the method comprises the following steps:
firstly, cutting a graphite felt into graphite felts of 1cm multiplied by 1cm as a base material, ultrasonically cleaning the graphite felts in ethanol and deionized water, and then drying the graphite felts for 24 hours at the temperature of 60 ℃;
secondly, preparing a solution containing 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid; mixing with graphite felt for 30min to form titanium dioxide seed crystals on the graphite felt to produce graphite felt containing seeds, and then drying at 60 ℃;
step three, soaking the graphite felt cleaned in the step one in the solution prepared in the step two for 30 minutes, then cleaning with deionized water, and then drying at 60 ℃ for 24 hours to obtain the graphite felt with the seeds;
step four, preparing a mixed solution containing 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate;
fifthly, sealing the graphite felt with the seeds prepared in the third step and the solution prepared in the fourth step in a hydrothermal reaction kettle, carrying out solvothermal reaction for 5 hours at the temperature of 150 ℃, and naturally cooling to room temperature;
sixthly, cleaning the composite material obtained in the fifth step, and drying for 24 hours at the temperature of 60 ℃;
step seven, mixing the composite material obtained in the step six with 4g of urea, putting the mixture into a quartz boat, putting the quartz boat into a tube furnace, starting a mechanical pump, and vacuumizing;
eighthly, after the vacuum pumping in the seventh step is carried out to a preset value, opening an air inlet, introducing nitrogen, and adjusting the gas introduction speed;
step nine, setting the nitriding time to be 3 hours, the temperature to be 800 ℃ and the like;
tenth, cleaning the composite material obtained in the ninth step, and drying for 24 hours at 60 ℃;
step eleven, respectively preparing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L, and mixing the potassium permanganate solution and the manganese sulfate solution in a ratio of 1:1 to obtain a mixed solution;
step ten, sealing the composite material obtained in the step ten and the mixed solution prepared in the step eleventh in a hydrothermal reaction kettle, carrying out solvothermal reaction for 12 hours at the temperature of 140 ℃, and naturally cooling to room temperature;
and step three, cleaning the composite material obtained in the step two, and drying at 60 ℃ for 24 hours to obtain a sample.
2. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the first step, the dispersing agent is absolute ethyl alcohol and deionized water.
3. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the second step and the third step, the seed solution is a solution of 1.10mL of titanium tetrachloride and 48.90mL of concentrated hydrochloric acid, and the soaking time is 30 min.
4. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the fourth step, the solution for growing titanium dioxide is a mixed solution of 24.25mL of concentrated hydrochloric acid, 24.25mL of deionized water and 1.5mL of tetrabutyl titanate.
5. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the fifth step, the hydrothermal time is 5 hours, and the temperature is 150 ℃.
6. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the ninth step, the nitrogen nitriding time is 3 hours, and the temperature is 800 ℃.
7. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the eleventh step, the solution for growing manganese dioxide is a mixed solution generated by mixing a potassium permanganate solution with the concentration of 0.024mol/L and a manganese sulfate solution with the concentration of 0.01mol/L in a ratio of 1: 1.
8. The method for improving the manganese dioxide ultra-capacity of the layered assembled nano-electrode according to claim 1, wherein the method comprises the following steps: in the thirteenth step, the duration of the hydrothermal growth of manganese dioxide is 12 hours, and the temperature is 140 ℃.
CN202011541781.7A 2020-12-23 2020-12-23 Method for improving manganese dioxide super-capacity by hierarchically assembling nano-electrodes Pending CN112735843A (en)

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CN104240967A (en) * 2014-09-26 2014-12-24 东南大学 Polyaniline-manganese dioxide-titanium nitride nanowire array composite material and preparation method and application thereof
DE102017204622A1 (en) * 2017-03-20 2018-09-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing a hybrid capacitor and hybrid capacitor
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Application publication date: 20210430