CN113113239B - Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof - Google Patents

Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof Download PDF

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CN113113239B
CN113113239B CN202011176464.XA CN202011176464A CN113113239B CN 113113239 B CN113113239 B CN 113113239B CN 202011176464 A CN202011176464 A CN 202011176464A CN 113113239 B CN113113239 B CN 113113239B
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CN113113239A (en
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盖利刚
王家钰
姜海辉
刘利彬
班青
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Qilu University of Technology
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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
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    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
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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
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Abstract

The invention belongs to the technical field of electrochemical energy storage, and relates to a supercapacitor electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) carrying out surface treatment on the carbon cloth to obtain carbon cloth A; 2) placing the carbon cloth A in a gallium trichloride-benzene solution, repeatedly dipping and lifting for several times to obtain carbon cloth B, placing the carbon cloth B in a fume hood, placing in room-temperature ambient air for 6-12h to obtain carbon cloth C, and then placing the carbon cloth C in an oven to dry at 50-70 ℃ for 6-12h to obtain carbon cloth D; 3) and placing the carbon cloth D in a tube furnace, and carrying out nitridation treatment in an ammonia atmosphere to obtain the carbon cloth/gallium oxynitride. The invention also provides the carbon cloth/gallium oxynitride prepared by the method and application thereof. The preparation method of the carbon cloth/gallium oxynitride composite material can realize effective regulation and control of the band structure, the N/O ratio and the particle size by changing the nitridation temperature; the obtained carbon cloth/gallium oxynitride has excellent electrochemical performance.

Description

Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof
Technical Field
The invention relates to a super capacitor electrode material and a preparation method thereof, belonging to the technical field of electrochemical energy storage.
Background
Gallium oxynitrides are widely used in the fields of cracking water, decomposing nitrogen oxides and gas sensing (adv. mater. interfaces2019,6,1900659; nanoscales 2018,10, 1837-. The structure, composition and morphology of gallium oxynitride are closely related to the preparation method thereof. To date, researchers have developed a variety of methods for preparing gallium oxynitrides, including solvothermal methods (Nano Energy2018,44,23-33), plasma assisted atomic layer deposition (Nano Energy2019,66,104089), magnetron sputtering (j.solid State chem.2020,282,121066), chemical vapor deposition (Energy environ.sci.2014,7, 1693-. The ammonitriding process is considered to be a simple and efficient method for preparing gallium oxynitride since it allows many gallium-containing compounds to be directly nitrided into gallium oxynitride.
The properties of gallium oxynitrides depend on their structure, composition and morphology. In the preparation process of the gallium oxynitride, how to realize the control synthesis of the band structure, the N/O ratio and the particle size of the gallium oxynitride is crucial to the exertion of the performance of the gallium oxynitride. However, so far, no reports on the synthesis of gallium oxynitride band structure, N/O ratio and particle size control have been found.
Recently, researchers have found that gallium nitride exhibits excellent rate performance when used as an electrode material for a supercapacitor, but has a disadvantage of relatively low specific capacity (adv. mater.2016,28, 3768-3776).
The supercapacitor electrode material needs to have good electrical conductivity. Gallium oxynitride is a semiconductor material, but its conductivity is not high, which affects its rate capability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof.
The invention provides a carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof.
A carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof comprise the following steps:
1) carrying out surface treatment on the carbon cloth to obtain carbon cloth A;
2) placing the carbon cloth A in a gallium trichloride-benzene solution, repeatedly dipping and lifting for several times to obtain carbon cloth B, placing the carbon cloth B in a fume hood, placing in room-temperature ambient air for 6-12h to obtain carbon cloth C, and then placing the carbon cloth C in an oven to dry at 50-70 ℃ for 6-12h to obtain carbon cloth D;
3) and placing the carbon cloth D in a tube furnace, and carrying out nitridation treatment in an ammonia atmosphere to obtain the carbon cloth/gallium oxynitride.
Performing surface treatment on the carbon cloth in the step 1), wherein the surface treatment is air plasma treatment or ultrasonic treatment; wherein, the air plasma treatment time is 60-120s, and the power is 90-110W; the ultrasonic treatment comprises the following steps: placing the carbon cloth in 3-8mol L-1Performing ultrasonic treatment for 1-3h at room temperature in the acid solution, and drying for use. Preferably, the acid is nitric acid or hydrochloric acid. More preferably, the acid is 5 to 7mol L-1Nitric acid of (2). More preferred sonications are: carbon cloth was placed at 6mol L-1The mixture was sonicated at room temperature for 2 hours in a nitric acid solution, and dried for use.
The gallium trichloride-benzene solution in the step 2), wherein the concentration of the gallium trichloride is 1-2mol L-1The purity of the benzene was analytical.
Repeating the dipping and pulling for several times in the step 2), wherein the dipping and pulling times are 6-12 times, and the time interval between two adjacent dipping and pulling times is 4-6 min. Preferably, the time interval between two adjacent dipping and pulling processes is 5 min.
The ammonia atmosphere in the step 3), wherein the flow rate of ammonia gas is 32-48mL min-1Before entering the tube furnace, the ammonia gas passes through a gas washing bottle filled with 25-28% strong ammonia water.
The nitriding treatment in the step 3), wherein the temperature of the nitriding treatment is 750--1The nitriding time is 8-12 h. More preferably, the nitriding treatment is carried out at 800 ℃ for 10 h.
The invention also provides carbon cloth/gallium oxynitride, prepared by any one of the above methods. More preferably, the carbon cloth/gallium oxynitride, gallium oxynitride nanoparticles are supported on a carbon cloth fiber. The size of the gallium oxynitride nanoparticles is 10-70nm, preferably, the size of the gallium oxynitride nanoparticles is 10-25 nm.
The invention also provides application of the carbon cloth/gallium oxynitride to a working electrode of a super capacitor.
Advantageous effects
1. The preparation method of the carbon cloth/gallium oxynitride composite material provided by the invention can realize effective regulation and control of the band structure, the N/O ratio and the particle size by changing the nitridation temperature.
2. The carbon cloth/gallium oxynitride provided by the invention has higher area specific capacity and better rate capability, and is suitable for being used as a working electrode of a super capacitor.
Drawings
Fig. 1 is an XRD pattern of the sample.
FIG. 2 is an XPS valence spectrum of a sample.
Fig. 3 is a Ga 3d spectrum of the sample.
Fig. 4 is an argon ion-thinned Ga 3d spectrum of the sample.
Fig. 5 is a diffuse reflection uv-vis absorption spectrum of the sample.
FIG. 6 is a plot of samples based on the Kubelka-Munk equation.
Fig. 7 is an SEM image of sample S1.
FIG. 8 is a high power SEM image of sample S1, where the scale lines correspond to 500 nm.
Fig. 9 is an SEM image of sample S2.
FIG. 10 is a high power SEM image of sample S2, where the scale lines correspond to 500 nm.
Fig. 11 is an SEM image of sample S3.
FIG. 12 is a high power SEM image of sample S3, with the scale lines corresponding to 500 nm.
FIG. 13 shows the sample at 10mV s-1Cyclic voltammograms below.
FIG. 14 shows the samples at 0.5mA cm-2And (5) a constant current charging and discharging curve diagram.
FIG. 15 is a graph of rate capability of samples.
FIG. 16 shows sample S2 at 10mA cm-2Lower cycle curve and coulombic efficiency plot.
Detailed Description
The technical solutions of the present invention are further described below by using specific examples and referring to the drawings, and these examples are only for illustrating the technical solutions of the present invention and should not be construed as limiting the contents of the claims of the present invention.
In the examples, nitric acid was obtained from Tianjin metallocene chemical reagent, benzene was obtained from Shanghai, a national medicine group, carbon cloth was obtained from Taiwan carbon technology, and gallium trichloride was obtained by combustion reaction of gallium metal and chlorine.
Air plasma treatment of carbon cloth was performed in an SPV-5L type plasma cleaning machine, a precision instruments ltd, sandingand, guan, dong.
An X-ray powder diffraction (XRD) pattern is obtained by detecting a German Bruker D8 advanced X-ray powder diffractometer; scanning Electron Microscope (SEM) pictures are obtained by detection of a Hitachi Regulus8220 Japanese field emission scanning electron microscope; the CHNO element analysis is obtained by detecting with an ElementarUnicube element analyzer in Germany; an X-ray photoelectron spectroscopy (XPS) graph is obtained by detection of a Thermo Fisher Scientific ESCALAB 250Xi X-ray photoelectron spectrometer; detecting the diffuse reflection ultraviolet-visible absorption spectrogram by using a Shimadzu UV-2600 diffuse reflection ultraviolet-visible spectrophotometer in Japan; the electrochemical performance of the sample is detected by an electrochemical analyzer of Shanghai Chenghua CHI 660E.
Example 1
A carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof comprise the following steps:
(1) carbon cloth was placed at 6mol L-1Then sonicated for 2h at room temperature in nitric acid solution, and dried.
(2) Cutting the carbon cloth into rectangular strips of 1cm multiplied by 4cm, and placing the carbon cloth strips in 1mol L-1Dipping and pulling the gallium trichloride-benzene solution for 12 times, wherein the time interval between two adjacent dipping and pulling processes is 5 min.
(3) Placing the impregnated and pulled carbon cloth in a fume hood, placing in room temperature ambient air for 12h, placing the carbon cloth in a 60 ℃ oven for drying for 6h, placing the carbon cloth in a tubular furnace, opening an ammonia cylinder, and setting the flow rate of ammonia gas to 48mL min-1The ammonia gas flows through 25-28% strong ammonia water and then enters the tube furnace.
(4) Temperature programming is carried out, and the heating rate is 10 ℃ for min-1And when the temperature reaches 750 ℃, preserving the heat for 10 hours.
(5) And cooling and naturally cooling to room temperature to obtain the carbon cloth/gallium oxynitride which is marked as S1.
Example 2
The temperature of 750 ℃ in step (4) of example 1 was changed to 800 ℃ and the remaining conditions were not changed. The resulting carbon cloth/gallium oxynitride was designated as S2.
Example 3
The temperature of 750 ℃ in step (4) of example 1 was changed to 850 ℃ and the remaining conditions were not changed. The resulting carbon cloth/gallium oxynitride was designated as S3.
Analysis of results
Fig. 1 is an XRD pattern of samples S1, S2, and S3. Two weak peaks at 24.2 ° and 43.6 ° in the figure are derived from carbon cloth, and the positions of the remaining diffraction peaks correspond to the (100), (002), (101), (102), (110), (103) and (112) crystal planes of hexagonal sphalerite-type structure GaN (JCPDS 50-0792). The diffraction peak width of the S3 spectrum corresponding to the (100)/(002)/(101) crystal plane is narrow and significant splitting occurs, compared to S1 and S2. This indicates that an increase in the nitriding temperature is advantageous for increasing the crystallinity of the sample particles.
Structural information of the sample can be obtained using Rietveld fitting. Table 1 gives the unit cell parameters for the different samples. As can be seen from table 1, the cell volume of the samples gradually decreased with increasing nitridation temperature, but were all larger than the cell volume of GaN. This is due to the gradual increase in the N/O ratio in samples S1-S3. Theoretical calculation results show that O atoms replace N atoms in GaN, the Ga-N bond length is lengthened, and the Ga-O bond length is larger than the Ga-N bond length. Thus, as the nitridation temperature increases, the N/O ratio in the sample increases and the cell volume becomes larger.
Table 1 Rietveld fit results for different samples.
Figure BDA0002748828530000041
The CHNO elemental analysis result shows that the chemical formulas of the samples S1, S2 and S3 are GaO respectively0.20N0.81、GaO0.20N0.90And GaO0.20N0.96. Thus, the N/O ratios of samples S1, S2, and S3 were 4.05, 4.50, and 4.80, respectively.
FIG. 2 shows the XPS values of the samplesA state spectrum. The peaks near 4.8, 7.6 and 10.7eV in FIG. 2 correspond to Ga, respectively4p-N2p、Ga4s-N2pAnd Ga4sO2p. This result indicates that orbital hybridization of Ga with N, O occurs in gallium oxynitride.
The hybridization of Ga with N, O is confirmed by the Ga 3d spectrum (fig. 3). The peaks at 19.6 and 20.6eV in FIG. 3 correspond to Ga-N and Ga-O, respectively. It is noted that the content of the Ga-O component in the sample gradually decreased and the content of the Ga-N component gradually increased as the nitriding temperature increased (FIGS. 2 and 3). This shows that the N/O ratio of the sample can be controlled by changing the nitriding temperature.
To further obtain structural information of the sample, the sample was characterized using argon ion thinning XPS technique. The argon ion thinning Ga 3d spectrum (FIG. 4) shows that the content of Ga-O component is gradually increased and the content of Ga-N component is gradually reduced with the increase of the ion thinning times. The results of the gradients exhibited by the Ga-O and Ga-N compositions as the number of thinnings increased indicate that samples S1-S3 are gallium oxynitride, not a mixture of gallium oxide and gallium nitride.
The change of the nitriding temperature not only can regulate and control the unit cell parameters and the N/O ratio of the sample, but also can regulate and control the energy band structure and the particle morphology of the sample.
FIG. 5 is a graph of the diffuse reflectance UV-VIS absorption spectrum of a sample. The energy band width of the sample can be estimated using diffuse reflectance uv-vis absorption spectroscopy data according to the Kubelka-Munk equation (fig. 6). As can be seen from fig. 6, the energy band widths of the samples S1, S2, and S3 are 2.92, 3.03, and 3.28eV, respectively.
Fig. 7-12 are topographical maps of the samples. As can be seen from the topography of the sample, the gallium oxynitride nanoparticles are supported on the carbon cloth fiber. The size of gallium oxynitride nanoparticles in the S1 sample was 20-40nm (FIG. 8), and the size of gallium oxynitride nanoparticles in the S2 sample was 10-25nm (FIG. 10); whereas the gallium oxynitride nanoparticles in the S3 sample were 40-70nm in size (fig. 12), but the particles were superficially ground into finer nanoparticles.
Example 4
The carbon cloth/gallium oxynitride is used for a super capacitor working electrode, and the electrochemical performance evaluation steps are as follows:
cutting a rectangular strip of S1 sample into electrode sheets of 1cm × 1cm, fixing the electrode sheets on a working electrode clamp, and measuring Hg/Hg2SO4As a reference electrode, a 1.5cm × 1.5cm platinum sheet as a counter electrode, 1mol L-1H2SO4The solution is electrolyte, and a cyclic volt-ampere (CV) curve, a constant current charge-discharge (GCD) curve, an alternating current impedance spectrum and cyclic stability of the electrode slice are respectively tested.
Example 5
S1 in example 4 was changed to S2, and the rest was unchanged.
Example 6
S1 in example 4 was changed to S3, and the rest was unchanged.
Analysis of results
FIG. 13 shows the sample at a sweep rate of 10mV s-1CV diagram below. As can be seen from fig. 13, the CV curve of the sample is almost a regular rectangle, and represents a more typical electrochemical double-layer capacitive energy storage characteristic.
FIG. 14 shows the samples at 0.5mA cm-2Constant current charge and discharge curve under current density. From FIG. 14, it can be calculated that the specific discharge capacities of the samples S1, S2 and S3 were 114, 863 and 766mF cm, respectively-2。
The sample S2 has not only higher specific area capacity under the same current density, but also better rate performance (figure 15), and the specific area capacity is 100mA cm-2Under the current density, the specific discharge capacity of the sample S2 reaches 285mF cm-2Much higher than 30mF cm for sample S1-2And 120mF cm of sample S3-2. At 10mA cm-2For 1 ten thousand cycles, sample S2 has nearly 100% capacity retention and maintains nearly 100% coulombic efficiency during cycling (fig. 16), showing excellent electrochemical performance.
Example 7
A carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof comprise the following steps:
(1) carbon cloth was placed at 6mol L-1Then sonicated for 2h at room temperature in nitric acid solution, and dried.
(2) Will be provided withCutting the carbon cloth into rectangular strips of 1cm multiplied by 4cm, and placing the carbon cloth strips in 2mol L-1Dipping and pulling 6 times in the gallium trichloride-benzene solution, wherein the time interval of dipping and pulling is 4 min.
(3) Placing the impregnated and pulled carbon cloth in a fume hood, placing in ambient air at room temperature for 6h, drying in an oven at 50 deg.C for 12h, placing the carbon cloth in a tubular furnace, opening an ammonia cylinder, and setting the flow rate of ammonia gas at 32mL min-1The ammonia gas flows through 25-28% strong ammonia water and then enters the tube furnace.
(4) Temperature programming is carried out, and the heating rate is 10 ℃ for min-1And when the temperature reaches 800 ℃, keeping the temperature for 12 hours.
(5) And cooling and naturally cooling to room temperature to obtain the carbon cloth/gallium oxynitride which is marked as S4.
The specific discharge capacity of the sample S4 at different current densities is shown in Table 2.
TABLE 2 specific discharge capacities of samples S4 and S5 at different current densities.
Figure BDA0002748828530000061
Example 8
A carbon cloth/gallium oxynitride supercapacitor electrode material and a preparation method thereof comprise the following steps:
(1) the carbon cloth was treated with air plasma at 100W power for 60 s.
(2) Cutting the carbon cloth into rectangular strips of 1cm multiplied by 4cm, and placing the carbon cloth strips in 1mol L-1The gallium trichloride-benzene solution is dipped and pulled for 10 times, and the time interval between two adjacent dipping and pulling is 6 min.
(3) Placing the impregnated and pulled carbon cloth in a fume hood, placing in room temperature ambient air for 8h, drying the carbon cloth in a 70 ℃ oven for 10h, placing the carbon cloth in a tubular furnace, opening an ammonia cylinder, and setting the flow rate of ammonia gas to be 40mL min-1The ammonia gas flows through 25-28% strong ammonia water and then enters the tube furnace.
(4) Temperature programming is carried out, and the heating rate is 10 ℃ for min-1And when the temperature reaches 800 ℃, preserving the heat for 8 hours.
(5) And cooling and naturally cooling to room temperature to obtain the carbon cloth/gallium oxynitride which is marked as S5.
The specific discharge capacity of the sample S5 at different current densities is shown in Table 2.
As can be seen from Table 2, no matter the carbon cloth is treated by acid or air plasma, the carbon cloth/gallium oxynitride composite electrode material with excellent electrochemical performance can be obtained at 800 ℃ by adopting ammonia water assisted ammonia nitridation method.

Claims (13)

1. A preparation method of a carbon cloth/gallium oxynitride supercapacitor electrode material comprises the following steps:
1) carrying out surface treatment on the carbon cloth to obtain carbon cloth A;
2) placing the carbon cloth A in a gallium trichloride-benzene solution, repeatedly dipping and lifting for several times to obtain carbon cloth B, placing the carbon cloth B in a fume hood, placing in room-temperature ambient air for 6-12h to obtain carbon cloth C, and then placing the carbon cloth C in an oven to dry at 50-70 ℃ for 6-12h to obtain carbon cloth D;
3) and placing the carbon cloth D in a tube furnace, and carrying out nitridation treatment in an ammonia atmosphere to obtain the carbon cloth/gallium oxynitride.
2. The method of claim 1, wherein: performing surface treatment on the carbon cloth in the step 1), wherein the surface treatment is air plasma treatment or ultrasonic treatment.
3. The method of claim 2, wherein: the air plasma treatment time is 60-120s, and the power is 90-110W; the ultrasonic treatment comprises the following steps: placing the carbon cloth in 3-8mol L-1Performing ultrasonic treatment for 1-3h at room temperature in the acid solution, and drying for use.
4. The method of claim 3, wherein: the ultrasonic treatment comprises the following steps: carbon cloth was placed at 6mol L-1In nitric acid solution, ultrasonic treating at room temperature for 2 hr, drying, and collecting the filtrateThe preparation is used.
5. The method of claim 3, wherein: the acid is 5-7mol L-1Nitric acid of (2).
6. The production method according to any one of claims 1 to 5, characterized in that: the gallium trichloride-benzene solution in the step 2), wherein the concentration of the gallium trichloride is 1-2mol L-1。
7. The production method according to any one of claims 1 to 5, characterized in that: repeating the dipping and pulling for several times in the step 2), wherein the dipping and pulling times are 6-12 times, and the time interval between two adjacent dipping and pulling times is 4-6 min.
8. The production method according to any one of claims 1 to 5, characterized in that: the ammonia atmosphere in the step 3) has the ammonia gas flow rate of 32-48mL min-1Before entering the tube furnace, the ammonia gas passes through a gas washing bottle filled with 25-28% strong ammonia water.
9. The production method according to any one of claims 1 to 5, characterized in that: the nitriding treatment in the step 3), wherein the temperature of the nitriding treatment is 750--1The nitriding time is 8-12 h.
10. A carbon cloth/gallium oxynitride produced by the method of any one of claims 1 to 9.
11. The carbon cloth/gallium oxynitride of claim 10 wherein the gallium oxynitride nanoparticles are supported on a carbon cloth fiber; the gallium oxynitride nanoparticles have a size of 10-70 nm.
12. The carbon cloth/gallium oxynitride of claim 11 wherein the gallium oxynitride nanoparticles have a size of 10 nm to 25 nm.
13. Use of a carbon cloth/gallium oxynitride according to any one of claims 10 to 12 or prepared by a process according to any one of claims 1 to 9 for a working electrode of a supercapacitor.
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CN105779954A (en) * 2016-03-02 2016-07-20 三峡大学 Method for preparing GaN/electric conducting substrate composite material by magnetron sputtering method and application thereof to sodium ion battery

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CN104134546A (en) * 2013-05-02 2014-11-05 中国科学院大连化学物理研究所 Photoelectrode using metal nitride as conductive substrate and preparation method thereof
CN105779954A (en) * 2016-03-02 2016-07-20 三峡大学 Method for preparing GaN/electric conducting substrate composite material by magnetron sputtering method and application thereof to sodium ion battery

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金属氮氧化物复合材料的制备及其超级电容器性能研究;王守志;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20190915(第2019/09期);全文 *

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