CN111223683A - Method for preparing carbon/nano manganese dioxide composite electrode material - Google Patents
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 132
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 abstract description 8
- 238000002791 soaking Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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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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- 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
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Abstract
The invention relates to a method for preparing a carbon/nano manganese dioxide composite electrode material, which comprises the steps of soaking an electrode covered by a carbon material or a carbon electrode in a potassium permanganate aqueous solution at the temperature of 10-40 ℃, and then irradiating the potassium permanganate aqueous solution by adopting ultraviolet light to grow nano manganese dioxide on the surface of the carbon material in situ to obtain the carbon/nano manganese dioxide composite electrode material.
Description
Technical Field
The invention relates to a method for rapidly preparing a carbon/nano manganese dioxide composite electrode material, in particular to a method for rapidly preparing a carbon/nano manganese dioxide composite electrode material at room temperature, and belongs to the technical field of functional material preparation.
Background
With the rapid development of economic society and the rapid increase of population density, the world energy crisis problem is more and more severe. Whether it be traditional or new renewable energy sources, efficient energy storage is important for a safe, stable and sustained supply of energy. A supercapacitor is a device that relies primarily on electric double layers and faraday capacitance to store energy. Compared with the traditional power supply, the super capacitor has high power density, short charge-discharge time and long cycle life, and related material research and development work is widely concerned by people.
Manganese dioxide is a cheap, easily available and environment-friendly transition metal oxide material. The manganese dioxide with the nano structure has the characteristics of large specific surface area, more redox active sites, exchangeable interlayer cations and the like, and has a good application prospect in energy storage systems such as super capacitors, batteries and the like. However, manganese dioxide has poor conductivity (10)-5～10-6S/cm) limits the transfer rate of ions and electrons in the manganese dioxide electrode, so that the specific capacitance value of manganese dioxide in practical application is far lower than the theoretical value (1370F/g). Although the capacitance of a carbonaceous material such as carbon nanotube or graphene is lower than that of a metal oxide material having a faraday capacitance characteristic such as manganese dioxide, the carbonaceous material has excellent conductivity. In order to improve the electrochemical performance of the nano manganese dioxide electrode material, researchers usually modify manganese dioxide on the surface of a conductive material such as a carbonaceous material to exert the synergistic effect of the two materials, so as to reduce the interface charge transfer resistance and improve the energy storage efficiency.
The existing carbon/manganese dioxide composite material is prepared by electrochemical deposition, hydrothermal method and the like, the preparation process is complex or the synthesis temperature is high, the conditions are relatively harsh, the energy consumption is high, and the wide application of the carbon/manganese dioxide composite material is limited to a certain extent. Therefore, a method for rapidly growing nano manganese dioxide on the surface of a carbon material in situ at room temperature is provided. The specific capacitance of the carbon/nano manganese dioxide composite electrode material quickly obtained by reacting for 2 hours at room temperature reaches 277g/F, is superior to that of a carbon/nano manganese dioxide composite electrode material prepared by a general high-temperature and time-consuming hydrothermal reaction (J.Mater.chem.,2012 and 22,8634), and can be used for basic research and technical development of a super capacitor.
Disclosure of Invention
In order to solve the problems, the invention provides a method for rapidly preparing a carbon/nano manganese dioxide composite electrode material, which comprises the steps of soaking an electrode covered by a carbon material or a carbon electrode in a potassium permanganate aqueous solution at the temperature of 10-40 ℃, and then irradiating the potassium permanganate aqueous solution by ultraviolet light to grow nano manganese dioxide on the surface of the carbon material in situ to obtain the carbon/nano manganese dioxide composite electrode material.
In the method, an electrode covered by a carbon material or a carbon electrode is soaked in a potassium permanganate aqueous solution, and ultraviolet light (with the wavelength of 0.01-0.40 micrometer) is adopted to irradiate the potassium permanganate aqueous solution. The ultraviolet photoelectron can reduce the activation energy required by the potassium permanganate reaction and promote the potassium permanganate and the carbon material to generate the oxidation reduction reaction, so that the nano manganese dioxide can be grown in situ on the surface of the carbon material at the temperature of 10-40 ℃ to obtain the carbon/nano manganese dioxide composite electrode material.
Preferably, the material of the carbon material or the carbon electrode is selected from at least one of amorphous carbon, carbon nanotube, graphene and graphene oxide; preferably, the carbon material covers the surface of the substrate; more preferably, the substrate is a metal electrode material.
Preferably, the concentration of the potassium permanganate aqueous solution is 0.001-0.1 mol/L. Too low a concentration of potassium permanganate can limit the rapid growth of manganese dioxide. The raw material utilization rate of the potassium permanganate aqueous solution with too high concentration is lower.
In addition, the volume of the potassium permanganate solution is preferably 10-100 mL.
Preferably, the temperature of the potassium permanganate aqueous solution is 20-40 ℃; preferably, the temperature of the aqueous potassium permanganate solution is about 25 ℃ at room temperature.
Preferably, the irradiation power of the ultraviolet light is not more than 100W, and the irradiation time is not more than 24 hours; preferably, the irradiation power of the ultraviolet light is 10-100W, and the irradiation time is 1-24 hours. Under the illumination of a certain power, manganese dioxide can be rapidly generated on the surface of the carbon material. The growth of manganese dioxide is facilitated by increasing the ultraviolet irradiation time, but the growth efficiency gradually decreases as the irradiation time is prolonged.
Preferably, the light source of the ultraviolet light is an ultraviolet lamp, and the distance between the ultraviolet lamp and the liquid level of the potassium permanganate aqueous solution is 2-10 cm.
On the other hand, the invention also provides the carbon/nano manganese dioxide composite electrode material prepared by the method, and nano manganese dioxide in the carbon/nano manganese dioxide composite electrode material is birnessite type manganese dioxide nanosheets.
In still another aspect, the invention provides a super capacitor containing the carbon/nano manganese dioxide composite electrode material.
In the invention, the used raw materials are cheap, the equipment and the preparation process are simple, and the material preparation cost is low. The carbon/nano manganese dioxide composite electrode material obtained by reacting for 2 hours at room temperature has specific capacitance of 277g/F, is superior to the specific capacitance of the carbon/nano manganese dioxide composite electrode material prepared by general hydrothermal reaction which needs high temperature and consumes time, and can be used for basic research and technical development of super capacitors.
Compared with the prior electrochemical deposition, hydrothermal technology and the like, the invention provides a method for rapidly preparing the carbon/nano manganese dioxide composite electrode material at room temperature. The potassium permanganate is the only manganese source, under the excitation of ultraviolet electrons, the activation energy required by the potassium permanganate reaction is reduced, the potassium permanganate and the carbon material are promoted to generate manganese dioxide through oxidation-reduction reaction, and other oxidizing agents or reducing agents are not added into the potassium permanganate aqueous solution. The method has the advantages of cheap and easily obtained raw materials, no need of special equipment and convenient operation, and the electrochemical performance of the obtained carbon/nano manganese dioxide composite electrode material can be regulated and controlled by ultraviolet illumination time, thereby having good application prospect.
Drawings
FIG. 1 is a Raman spectrum of a carbon-containing electrode material (carbon film) and a carbon/nano manganese dioxide composite electrode material prepared by respectively irradiating ultraviolet light for 2h and 8h in example 1;
FIG. 2 is a scanning electron microscope image of the carbon-containing electrode material (a) and the carbon/nano manganese dioxide composite electrode material prepared by respectively irradiating 2h (b) and 8h (c) with ultraviolet light in example 1;
fig. 3 is a cyclic voltammetry curve (a) and a constant current charging and discharging curve (b) of the carbon/nano manganese dioxide composite electrode material prepared in example 1 by respectively irradiating ultraviolet light for 2h and 8 h.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the method, an electrode covered by a carbon material or the carbon material electrode is soaked in a potassium permanganate aqueous solution, and nano manganese dioxide is grown in situ on the surface of the carbon material at 10-40 ℃ by adopting an ultraviolet illumination reduction method. The carbon/nano manganese dioxide composite electrode material prepared by the method can be used for basic research and technical development of super capacitors.
In alternative embodiments, the material of the carbon material or the carbon electrode may be various types of carbonaceous materials such as amorphous carbon, carbon nanotubes, graphene oxide, and the like.
In an optional embodiment, the volume of the potassium permanganate aqueous solution is 10-100 mL, and the concentration of potassium permanganate is 0.001-0.1 mol/L.
In an alternative embodiment, ultraviolet light reduction is performed using an ultraviolet lamp. The irradiation power of the ultraviolet lamp can be 10-100W, and the irradiation time can be 1-24 hours. The distance between the ultraviolet lamp (lamp source) and the liquid level of the potassium permanganate aqueous solution is about 2-10 cm.
In the present disclosure, the manganese dioxide in the prepared carbon/nano manganese dioxide composite electrode material is birnessite type manganese dioxide nanosheets.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
A: preparation of carbon/manganese dioxide composite electrode material by ultraviolet illumination reduction method
And preparing a carbon film on the surface of the titanium sheet electrode by using a hydrothermal carbonization reaction method by taking a glucose aqueous solution as a precursor. Soaking the titanium sheet electrode material covered by the carbon film in a potassium permanganate aqueous solution at the room temperature of about 25 ℃, placing the titanium sheet electrode material under ultraviolet light for a period of time, and growing nano manganese dioxide on the surface of the carbon film. Wherein the volume of the glucose aqueous solution is 40mL, and the mass fraction of glucose is 5%. The reaction temperature of the hydrothermal carbonization reaction method is 190 ℃, and the reaction time is 5 h. The volume of the potassium permanganate aqueous solution is 20mL, and the concentration is 0.01 mol/L. The power of an ultraviolet lamp is 48W, the distance between a lamp source and the liquid level of the potassium permanganate aqueous solution is about 5cm, and the ultraviolet irradiation time is 2h and 8 h.
Raman spectrum tests of the carbon-containing electrode material and the carbon/nano manganese dioxide composite electrode material prepared by irradiating the carbon-containing electrode material in the embodiment 1 for 2 hours and 8 hours under ultraviolet light showed that birnessite type manganese dioxide grows on the surface of the carbon film after the carbon-containing electrode material is irradiated for 2 hours and 8 hours under ultraviolet light as shown in fig. 1.
SEM tests were performed on the carbon-containing electrode material of example 1 and the carbon/nano manganese dioxide composite electrode material prepared by irradiating under uv light for 2h and 8h, and the results are shown in fig. 2(a), fig. 2(b) and fig. 2(c), respectively. The result shows that a large number of nano-sheets with similar shapes are grown on the surface of the carbon film after the carbon film is irradiated by ultraviolet light for 2 hours and 8 hours. And as the irradiation time of the purple light is prolonged from 2h to 8h, the diameter of the carbon sphere covered by the nano sheet is increased.
The results of EDS tests performed on the surface of the carbon/nano manganese dioxide composite electrode material prepared in example 1 by irradiating with ultraviolet light for 2 hours and 8 hours are shown in table 1, and the results show that as the irradiation time is increased from 2 hours to 8 hours, the relative contents of the corresponding K and Mn elements in the non-spherical region (region i and region iii) and the spherical region (region ii and region iv) are increased, but the mass ratios of the K/Mn elements are substantially the same.
Table 1 shows the relative contents of the elements and the mass ratio of K/Mn elements in the carbon/nano manganese dioxide composite electrode material prepared in example 1:
b: and (3) testing the electrochemical performance of the carbon/nano manganese dioxide composite electrode material:
and testing the electrochemical performance of the carbon/nano manganese dioxide composite electrode material in a sodium sulfate solution of 0.5mol/L by adopting a common three-electrode system. The voltage window measured by the cyclic voltammetry characteristic curve is 0-0.8V, and the scanning rate is 20 mV/s. The current density used in the constant current charge-discharge curve test is 0.2A/g. The voltages involved in the present invention are relative to a saturated calomel electrode.
Cyclic voltammetry and constant current charge and discharge tests were performed on the carbon/nano manganese dioxide composite electrode material prepared by ultraviolet irradiation for 2 hours and 8 hours, and the results are shown in fig. 3 (a) and fig. 3 (b), respectively. The result shows that the specific capacitance of the carbon/nano manganese dioxide electrode material prepared by ultraviolet 2h under the same test condition is better, and the value is 277F/g. And the specific capacitance of the carbon/nano manganese dioxide electrode material is 236F/g when the ultraviolet time is prolonged to 8 hours.
Claims (9)
1. A method for preparing a carbon/nano manganese dioxide composite electrode material is characterized in that an electrode covered by a carbon material or a carbon electrode is soaked in a potassium permanganate aqueous solution at the temperature of 10-40 ℃, and then the potassium permanganate aqueous solution is irradiated by ultraviolet light, so that nano manganese dioxide grows in situ on the surface of the carbon material, and the carbon/nano manganese dioxide composite electrode material is obtained.
2. The method according to claim 1, wherein the carbon material or the material of the carbon electrode is selected from at least one of amorphous carbon, carbon nanotubes, graphene, and graphene oxide; preferably, the carbon material covers the surface of the electrode, and the electrode is made of a metal electrode material.
3. The method according to claim 1 or 2, wherein the concentration of the aqueous solution of potassium permanganate is 0.001 to 0.1 mol/L.
4. The method according to claim 3, wherein the volume of the aqueous potassium permanganate solution is 10-100 mL.
5. The method according to any one of claims 1 to 4, wherein the temperature of the aqueous potassium permanganate solution is 20 to 40 ℃; preferably, the temperature of the aqueous potassium permanganate solution is 25 ℃ at room temperature.
6. The method according to any one of claims 1 to 5, wherein the irradiation power of the ultraviolet light is not more than 100W, and the irradiation time is not more than 24 hours; preferably, the irradiation power of the ultraviolet light is 10-100W, and the irradiation time is 1-24 hours.
7. The method according to any one of claims 1 to 6, wherein the light source of the ultraviolet light is an ultraviolet lamp, and the ultraviolet lamp is 2-10 cm away from the liquid level of the potassium permanganate aqueous solution.
8. A carbon/nano manganese dioxide composite electrode material prepared according to the method of any one of claims 1 to 7, wherein nano manganese dioxide in the carbon/nano manganese dioxide composite electrode material is birnessite type manganese dioxide nanosheets.
9. A supercapacitor containing the carbon/nano manganese dioxide composite electrode material according to claim 8.
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| CN115433475A (en) * | 2021-06-03 | 2022-12-06 | 中国科学院上海硅酸盐研究所 | Photoelectric response type manganese oxide-carbon composite coating, preparation method thereof and application thereof in nerve and bone tissue repair |
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| CN115433475A (en) * | 2021-06-03 | 2022-12-06 | 中国科学院上海硅酸盐研究所 | Photoelectric response type manganese oxide-carbon composite coating, preparation method thereof and application thereof in nerve and bone tissue repair |
| CN114613610A (en) * | 2022-02-25 | 2022-06-10 | 中国科学院宁波材料技术与工程研究所 | Adhesive-free supercapacitor electrode based on basic manganese oxide nano material modified carbon fiber and preparation and application thereof |
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