CN108110246A - A kind of extra small VS4/ Super P composite nano-powders and preparation method and application - Google Patents
A kind of extra small VS4/ Super P composite nano-powders and preparation method and application Download PDFInfo
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- CN108110246A CN108110246A CN201711403838.5A CN201711403838A CN108110246A CN 108110246 A CN108110246 A CN 108110246A CN 201711403838 A CN201711403838 A CN 201711403838A CN 108110246 A CN108110246 A CN 108110246A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- Y02E60/10—Energy storage using batteries
Abstract
A kind of extra small VS4Sodium metavanadate, thioacetamide and Super P are added in and solution A are obtained in deionized water by the preparation method and application of/Super P composite nano-powders；Then ammonium hydroxide is added dropwise into solution A and obtains the solution B that pH value is 9.8~10.2；Sealing carries out hydro-thermal reaction after solution B is poured into reaction liner；By reaction product, drying obtains extra small VS after water and alcohol alternately clean4/ Super P composite nano-powders.VS4/ Super P composite nano-powders are by VS4Uniformly interaction is distributed for nanosphere and Super P nanospheres, VS4The consistent appearance of nanosphere, size uniform a diameter of 50~80nm, VS4Nanosphere is the monocrystalline VS that edge (110) high preferred orientation that length is 60~100nm is grown by a diameter of 20nm4Flexible nano stick is entwined.VS4/ Super P composite nano-powders show excellent chemical property and catalytic performance in the application of lithium/sodium-ion battery and optical electrical catalytic field.
Description
Technical field
The present invention relates to a kind of VS4A kind of preparation method of/Super P composite granules, and in particular to extra small VS4/SuperP
Composite nano-powder and its preparation method and application.
Background technology
VS4In V valence states, high sulfur content, one-dimensional chain crystal structure, the connection of weak interchain and big chain spacing for enriching etc. it is special
Property, make it that there is high application prospect [Xu X, Jeong S, Rout CS, Oh P, KoM, Kim in electrochemistry and catalytic field
H,et al.Lithium reaction mechanism and high rate capability of VS4-graphene
nanocomposite as an anode material for lithium batteries.J Mater Chem A.2014；
2:10847-53.].Meanwhile with regard to patronite (VS present in nature4) abundant reserves and its potential low cost and
Speech, VS4There is huge commercial value in commercial application.However, pure phase VS4Synthesis need to the local pressure of sulphur into
The accurate control of row, and the vanadic sulfide interference phase of various non-stoichiometrics is easily generated, along with the oxyphie characteristic of vanadium so that
VS4Since 1970 by since reporting for the first time, the report during which on its synthesis and application is very few.In recent years, with section
The development of technology, synthetic technology have important breakthrough and progress, make VS4Start the visual field for slowly entering researcher again, and
VS is successfully synthesized by hydro-thermal reaction there has also been some4Report.However, in these hydro-thermal reactions, template includes graphite
Alkene, carbon nanotubes, conducting polymer (polythiophene, polypyrrole and polyaniline) and tetracarboxylic dianhydride etc. usually require to be introduced into,
It has higher cost, the VS of synthesis4Also it is mostly one-dimentional structure [Rout CS, Kim B-H, Xu X, Yang J, Jeong
HY,Odkhuu D,etal.Synthesis and characterization of patronite form of vanadium
sulfide on graphitic layer.JAm Chem Soc.2013；135:8720-5.].Moreover it has been reported that pure phase
VS4It is mostly micro-meter scale, results in its smaller specific surface area.It is well known that high specific surface area will greatly improve electricity
Chemistry and catalytic reaction area, and then electrochemistry and catalytic performance can be obviously improved.On the other hand, three-dimensional self-assembled structures are only
Special physics confinement effect can effectively inhibit the volume change in reaction process, and then can significantly increase the stabilization of material
Property.Therefore, three-dimensional self assembly VS of the synthesis with extra small scale4And it is compound with the progress of inexpensive carbon material, for VS4's
Practical application has great importance.
The content of the invention
It is an object of the invention to provide a kind of reaction process is simple, temperature is low, easily-controllable and large scale equipment and severe is not required
Carve the extra small VS of reaction condition4/ Super P composite nano-powders and its preparation method and application.
In order to achieve the above objectives, preparation method of the invention comprises the following steps：
Step 1：Take 0.8~1.2g sodium metavanadates, 3.4~3.8g thioacetamides and 0.2~0.4g Super P simultaneously
It is added in 55~65ml deionized waters, half settled solution A is obtained after magnetic agitation or ultrasonic disperse；
Step 2：Then the ammonia spirit of 1.0~1.2mol/L is added dropwise dropwise into solution A, until solution ph reaches
9.8~10.2, obtain solution B；
Step 3：It is sealed after solution B is poured into reaction liner by 55~65% packing ratio, by liner loaded on solid in outer kettle
Surely it is placed in homogeneous reaction instrument, reaction kettle is heated to 175~185 DEG C of progress hydro-thermal reactions by room temperature under rotation status；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, production is collected after water and alcohol alternately clean
Object, and dried under the conditions of 60~80 DEG C, you can obtain extra small VS4/ Super P composite nano-powders.
The step 1 magnetic agitation rotating speed is 800~1000r/min, and mixing time is 55~65min.
The step 1 ultrasonic disperse time is 30~45min.
The adjusting process of pH is in the step 2, under the conditions of continuous magnetic agitation, by the ammonia of 1.0~1.2mol/L
Aqueous solution is added drop-wise in solution A dropwise, and the rate of addition of ammonia spirit is controlled to drip a drop ammonia for 0.03~0.05ml/min
Aqueous solution, stirring is after solution ph is stablized, then instills next drop ammonia spirit, until reacting liquid pH value is adjusted to 9.8
~10.2.
The rotary rpm of the step 3 is 5~10r/min, 23.5~24.5h of hydro-thermal reaction.
The cleaning of the step 4 is carried out 3~6 times using suction filtration or centrifugation.
The collection of the step 4 is carried out using suction filtration or centrifugation.
The drying of the step 4 carries out 10~14h in vacuum drying chamber.
The extra small VS synthesized by the preparation method of the present invention4/ Super P composite nano-powders are by VS4Nanosphere and SuperP
Uniformly interaction is distributed nanosphere, VS4The consistent appearance of nanosphere, size uniform a diameter of 50~80nm, VS4Nanosphere is
By a diameter of 20nm, the monocrystalline VS for edge (110) high preferred orientation growth that length is 60~100nm4Flexible nano stick is entwined.
VS4/ Super P composite nano-powders lithium/sodium-ion battery and optical electrical catalytic field application, using for sodium/
When lithium ion battery negative material and optical electrical catalyst, excellent chemical property and catalytic performance are shown.
Specifically have the beneficial effect that：
(1) present invention using a step hydro-thermal reaction due to directly synthesizing final product, thus has low synthesis temperature
Large scale equipment and harsh reaction condition is not required in degree, simple synthesis path；
(2) vanadium source used in the present invention is sodium metavanadate, sulphur source is thioacetamide, carbon source is Super P, these three raw materials
It is Common materials, cheap and easy to get, at low cost, synthesis composite granule yield is high, reaction is easily-controllable, without post-processing, environment friend
It is good, it can be suitble to mass produce；
(3) present invention is synthesizing extra small three-dimensional self assembly VS4During/Super P composite nano-powders, do not introduce and appoint
What template or surfactant, entire self assembling process are the self-template effect control by reaction raw materials, thus entire anti-
It should be simple, easily-controllable, efficient and inexpensive；
(4) present invention prepare product chemistry composition it is homogeneous, purity is high, pattern is uniform, born as sodium/lithium ion battery
Excellent performance can be shown when pole material and optical electrical catalyst；
(5) present invention in Super P addition for extra small self assembly VS4Formation play conclusive effect.Super
The addition of P affects VS4Nucleation rate and the speed of growth, make VS4It is easy to be nucleated, it is difficult to it grows, it is substantial amounts of super so as to generate
Small VS4Flexible rod, while VS4The one-dimensional chain crystal structure of rotation makes these flexible rod self assemblies be entwined nanosphere；
(6) present invention in pH value regulation and control for extra small VS4Formation also play crucial effect, excessively high pH is easy to make
Reaction generation VS2Rather than VS4, too low pH be then easy to promote VS4Grow into the self-assembly of large scale；
(7) process that pH of the present invention is adjusted is for pure phase VS4Formation play an important role.Inappropriate ammonium hydroxide is dense
Degree, the selection of rate of addition and strong base solution all easily causes the generation of local reaction, and then generates VOxOr S simple substance is miscellaneous
Phase；
(8) present invention in packing ratio regulation and control for pure phase VS4Formation equally play an important role.Higher filling
Than S can be promoted2-Oxygen in ion exchange vanadic acid root, so as to produce VS2.Relatively low packing ratio is unfavorable for S2 2-It replaces in vanadium oxygen root
Oxygen, so as to cause VOxGeneration；
(9) VS extra small in the VS4/Super P composite nano-powders prepared by the present invention4Nanometer rods can not only produce
Raw larger specific surface area, but also more surface-active sites can be provided, and then chemical property can be promoted and urged
Change performance.In addition, this extra small scale can not only shorten charge transfer path, but also it can be the storage of sodium/lithium ion
More active sites are provided, so as to promote the specific capacity of material and high rate performance；
(10) VS prepared by the present invention4Nanometer rods are wound in the structure of nanosphere and exist in/Super P composite nano-powders
It can play the role of good physics confinement in charge and discharge process.On the one hand good restraining function can be played, on the other hand
Also the expansion and contraction to nanometer rods provide cushion space, so as to greatly alleviate the volume change of nanometer rods, finally
Significantly improve its cyclical stability；
(11) VS prepared by the present invention4VS in/Super P composite nano-powders4Nanometer rods are given birth to along (110) high preferred orientation
Long single crystal characteristics, as the entrance of charge disengaging lattice, larger interplanar distance is conducive to the transmission of charge, thus for
The promotion of electrochemistry and catalytic performance will play an important role.Meanwhile single crystal characteristics improve the structural stability of material, into
And be conducive to the stability of charge deintercalation and catalytic process, so as to extend its working life；
(12) VS prepared by the present invention4Equally distributed Super P not only can be with in/Super P composite nano-powders
The electric conductivity of material is promoted, fixed VS can also be played4Alleviate the effect of its volume change, so as to cooperate with promotion electrochemistry
Reaction power and stability.
Description of the drawings
Fig. 1 is the low power scanning figure that the embodiment of the present invention 1 prepares product.
Fig. 2 is the high power scanning figure that the embodiment of the present invention 1 prepares product.
Fig. 3 is the super-high power scanning figure that the embodiment of the present invention 1 prepares product.
Fig. 4 is the high-resolution-ration transmission electric-lens figure that the embodiment of the present invention 1 prepares product.
After raw material Super P in the embodiment of the present invention 1 is are removed by Fig. 5, the scanning electron microscope (SEM) photograph of products therefrom.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1：
Step 1：Take 1.0g sodium metavanadates, 3.6g thioacetamides and 0.3g Super P be added to simultaneously 60ml go from
In sub- water, half settled solution A is obtained in 800r/min magnetic agitations 65min；
Step 2：Then the ammonia spirit of 1.0mol/L is added dropwise dropwise into solution A under magnetic stirring, control ammonium hydroxide is molten
The rate of addition of liquid is 0.03ml/min, drips a drop ammonia spirit, stirring is after solution ph is stablized, then instills next
Ammonia spirit is dripped, until reacting liquid pH value is adjusted to 10, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 60% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 180 DEG C of hydro-thermal reactions for 24 hours by room temperature under 8r/min；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, after water and alcohol alternately filter 3 times, is adopted
With collected by suction product, 12h drying are carried out with 60 DEG C, you can obtain extra small VS in vacuum drying chamber4/ SuperP is nano combined
Powder.
From figure 1 it appears that VS4/ Super P composite nano-powders are by VS4Nanosphere and Super P nanospheres are equal
Even interaction is distributed.
From figure 2 it can be seen that VS4The pattern of nanosphere is more consistent, size more uniformly, in 50~80nm.
From figure 3, it can be seen that VS4It by diameter is about 20nm, the VS that length is about 60~100nm that nanosphere, which is,4Flexibility is received
Rice stick is entwined.
Figure 4, it is seen that VS4Nanometer rods present the mono-crystalline structures along the growth of (110) high preferred orientation.
From figure 5 it can be seen that when not introducing Super P in the reaction, the VS of synthesis4Flexible rod and by its winding and
The scale of balling-up all becomes larger.
Embodiment 2：
Step 1：Take 0.8g sodium metavanadates, 3.5g thioacetamides and 0.2g Super P be added to simultaneously 58ml go from
In sub- water, half settled solution A is obtained in 1000r/min magnetic agitations 55min；
Step 2：Then the ammonia spirit of 1.15mol/L is added dropwise dropwise into solution A under magnetic stirring, controls ammonium hydroxide
The rate of addition of solution is 0.04ml/min, drips a drop ammonia spirit, stirring is after solution ph is stablized, then instills down
One drop ammonia spirit, until reacting liquid pH value is adjusted to 9.9, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 55% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 178 DEG C of hydro-thermal reaction 24.5h by room temperature under 5r/min；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, after water and alcohol alternating centrifugal 5 times, is adopted
With product is collected by centrifugation, with 65 DEG C of progress 10h drying in vacuum drying chamber, you can obtain extra small VS4/ SuperP is nano combined
Powder.
Embodiment 3：
Step 1：Take 1.1g sodium metavanadates, 3.7g thioacetamides and 0.4g Super P be added to simultaneously 63ml go from
In sub- water, half settled solution A is obtained in 900r/min magnetic agitations 60min；
Step 2：Then the ammonia spirit of 1.1mol/L is added dropwise dropwise into solution A under magnetic stirring, control ammonium hydroxide is molten
The rate of addition of liquid is 0.05ml/min, drips a drop ammonia spirit, stirring is after solution ph is stablized, then instills next
Ammonia spirit is dripped, until reacting liquid pH value is adjusted to 10.1, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 58% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 185 DEG C of hydro-thermal reaction 23.5h by room temperature under 10r/min；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, after water and alcohol alternately filter 6 times, is adopted
With collected by suction product, 13h drying are carried out with 75 DEG C, you can obtain extra small VS in vacuum drying chamber4/ SuperP is nano combined
Powder.
Embodiment 4：
Step 1：Take 0.9g sodium metavanadates, 3.8g thioacetamides and 0.25g Super P be added to simultaneously 65ml go from
In sub- water, half settled solution A is obtained after ultrasonic disperse 45min；
Step 2：Then the ammonia spirit of 1.05mol/L is added dropwise dropwise into solution A under magnetic stirring, controls ammonium hydroxide
The rate of addition of solution is 0.045ml/min, drips a drop ammonia spirit, stirring is after solution ph is stablized, then instills
Next drop ammonia spirit until reacting liquid pH value is adjusted to 10.2, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 65% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 183 DEG C of hydro-thermal reactions for 24 hours by room temperature under 9r/min；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, after water and alcohol alternating centrifugal 4 times, is adopted
With product is collected by centrifugation, with 80 DEG C of progress 11h drying in vacuum drying chamber, you can obtain extra small VS4P nanometers of/Super is multiple
Close powder.
Embodiment 5：
Step 1：Take 1.2g sodium metavanadates, 3.4g thioacetamides and 0.35g Super P be added to simultaneously 55ml go from
In sub- water, half settled solution A is obtained after ultrasonic disperse 45min；
Step 2：Then the ammonia spirit of 1.2mol/L is added dropwise dropwise into solution A under magnetic stirring, control ammonium hydroxide is molten
The rate of addition of liquid is 0.035ml/min, drips a drop ammonia spirit, stirring is after solution ph is stablized, then instills down
One drop ammonia spirit, until reacting liquid pH value is adjusted to 9.8, obtains solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 63% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 175 DEG C of hydro-thermal reaction 24.5h by room temperature under 7r/min；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, after water and alcohol alternately filter 5 times, is adopted
With product is collected by centrifugation, with 70 DEG C of progress 14h drying in vacuum drying chamber, you can obtain extra small VS4/ SuperP is nano combined
Powder.
Claims (10)
1. a kind of extra small VS4The preparation method of/Super P composite nano-powders, it is characterised in that：
Step 1：0.8~1.2g sodium metavanadates, 3.4~3.8g thioacetamides and 0.2~0.4g Super P is taken to add in simultaneously
Into 55~65ml deionized waters, half settled solution A is obtained after magnetic agitation or ultrasonic disperse；
Step 2：Then the ammonia spirit of 1.0~1.2mol/L is added dropwise dropwise into solution A, until solution ph reach 9.8~
10.2, obtain solution B；
Step 3：It seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 55~65% packing ratio
It is placed in homogeneous reaction instrument, reaction kettle is heated to 175~185 DEG C of progress hydro-thermal reactions by room temperature under rotation status；
Step 4：Reaction kettle is naturally cooled into room temperature after hydro-thermal reaction, product is collected after water and alcohol alternately clean, and
It is dried under the conditions of 60~80 DEG C, you can obtain extra small VS4/ Super P composite nano-powders.
2. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
Step 1 magnetic agitation rotating speed is 800~1000r/min, and mixing time is 55~65min.
3. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The step 1 ultrasonic disperse time is 30~45min.
4. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The adjusting process of pH is in step 2, and under the conditions of continuous magnetic agitation, the ammonia spirit of 1.0~1.2mol/L is dripped dropwise
It is added in solution A, the rate of addition of ammonia spirit is controlled to drip a drop ammonia spirit for 0.03~0.05ml/min, is stirred
Until after solution ph is stablized, then next drop ammonia spirit is instilled, until reacting liquid pH value is adjusted to 9.8~10.2.
5. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The rotary rpm of step 3 is 5~10r/min, 23.5~24.5h of hydro-thermal reaction.
6. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The cleaning of step 4 is carried out 3~6 times using suction filtration or centrifugation.
7. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The collection of step 4 is carried out using suction filtration or centrifugation.
8. extra small VS according to claim 14The preparation method of/Super P composite nano-powders, it is characterised in that：It is described
The drying of step 4 carries out 10~14h in vacuum drying chamber.
9. a kind of extra small VS of preparation method synthesis as described in claim 14/ Super P composite nano-powders, feature exist
In：VS4/ Super P composite nano-powders are by VS4Uniformly interaction is distributed for nanosphere and Super P nanospheres, VS4Nanometer
The consistent appearance of ball, size uniform a diameter of 50~80nm, VS4Nanosphere is by a diameter of 20nm, and length is 60~100nm's
Along the monocrystalline VS of (110) high preferred orientation growth4Flexible nano stick is entwined.
10. a kind of VS as claimed in claim 94/ Super P composite nano-powders are catalyzed in lithium/sodium-ion battery and optical electrical
The application in field.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109748319A (en) * | 2019-02-26 | 2019-05-14 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@carbon nano-tube composite powder |
| CN109904422A (en) * | 2019-02-26 | 2019-06-18 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@Super P composite granule |
| CN112490438A (en) * | 2020-11-27 | 2021-03-12 | 青岛科技大学 | Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof |
| CN112786845A (en) * | 2019-11-07 | 2021-05-11 | 广州汽车集团股份有限公司 | VS4Hierarchical pore graphitized carbon composite material, preparation method thereof, positive electrode material, positive plate, lithium-sulfur battery cell and lithium-sulfur battery pack |
| CN113130863A (en) * | 2021-03-22 | 2021-07-16 | 郑州大学 | VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748319A (en) * | 2019-02-26 | 2019-05-14 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@carbon nano-tube composite powder |
| CN109904422A (en) * | 2019-02-26 | 2019-06-18 | 陕西科技大学 | A kind of preparation method and application of four vanadic sulfides@Super P composite granule |
| CN109904422B (en) * | 2019-02-26 | 2022-05-20 | 陕西科技大学 | Preparation method and application of vanadium tetrasulfide @ Super P composite powder |
| CN112786845A (en) * | 2019-11-07 | 2021-05-11 | 广州汽车集团股份有限公司 | VS4Hierarchical pore graphitized carbon composite material, preparation method thereof, positive electrode material, positive plate, lithium-sulfur battery cell and lithium-sulfur battery pack |
| CN112490438A (en) * | 2020-11-27 | 2021-03-12 | 青岛科技大学 | Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof |
| CN113130863A (en) * | 2021-03-22 | 2021-07-16 | 郑州大学 | VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery |
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| CN108110246B (en) | 2020-07-10 |
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