CN108649190B - Vertical graphene/titanium niobium oxide/sulfur carbon composite material with three-dimensional porous array structure and preparation method and application thereof - Google Patents
Vertical graphene/titanium niobium oxide/sulfur carbon composite material with three-dimensional porous array structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a vertical graphene/titanium niobium oxygen/sulfur carbon composite material with a three-dimensional porous array structure, a preparation method and application thereof, wherein the preparation method comprises the following steps: graphene nanosheets vertically and crossly grown on the substrate; TiNb coated on the graphene nanosheet2O7Form VG/TiNb2O7Nanosheets; and coating the VG/TiNb2O7A sulfur-doped carbon layer on the nanosheets to form VG/TiNb2O7@ S-C three-dimensional porous arrays. The invention synthesizes VG/TiNb reversely2O7The nano array is used as a carrier, and the composite material is prepared by constant current anodic deposition. The composite material has the characteristics of high cycle stability, high rate performance, coulombic efficiency and the like, and can obviously improve the energy density/power density and cycle stability of the full battery when being matched with lithium iron phosphate or a ternary material. The novel composite material is suitable for serving as a lithium ion battery cathode material, and can be applied to various electronic equipment, electric automobiles, hybrid electric automobiles and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion secondary battery cathode materials, in particular to a vertical graphene/titanium niobium oxygen/sulfur carbon composite material with a three-dimensional porous array structure, a preparation method thereof and application of the composite material as a lithium ion battery cathode material.
Background
Lithium ion batteries are currently widely used in the fields of transportation, information electronics, and the like as the most important electric energy storage devices. Lithium ion sourceThe rapid development of ion batteries is mainly dependent on the innovation of positive and negative electrode materials. However, the most widely commercialized negative electrode active graphite material is prone to form dendrites, silicon and tin-based compounds have a serious volume expansion problem, and a Solid Electrolyte Interface (SEI) film is prone to be formed, which is poor in safety. Lithium titanate does not form SEI film, but has low theoretical capacity, and titanium niobate compound (TiNb)xO2+2.5x) There is no SEI film formed during the cycle and the theoretical capacity is relatively high, which has attracted great attention. In the titanium niobate compound, TiNb is widely applied2O7And Ti2Nb10O29Theoretical capacities of 388 and 396mAh g, respectively-1. Wherein, TiNb2O7First, the problem group of Goodenough suggests that there is no SEI film formation in the operating voltage range, and that the theoretical capacity is high and slightly higher than that of graphite. However, the intrinsic electron/ion conductivity of the titanium niobate material is low, which limits the high-rate electrochemical performance. Therefore, in order to design the titanium niobate material into a high-performance lithium ion battery electrode, the titanium niobate material needs to be modified.
In order to solve the above problems, researchers at home and abroad usually optimize the electrochemical lithium storage performance by using the following modification modes: mainly comprises three modes of nanocrystallization, metal ion doping, surface coating and the like. The electrode material is designed and synthesized into nano-tubes, nano-wires, nano-particles and other nano-structures, so that the transmission path of electrons/lithium ions is reduced, and the transmission speed is increased, thereby improving the transmission efficiency of electrons/ions; using Ru4+，Cu2+，Mo6+Metal ions are doped, so that more vacancies are provided for facilitating ion transmission, and the high-rate electrochemical performance of the composite material is improved; the high-conductivity coating layers such as Ag, CNTs (carbon nanotubes), graphene (graphene) and the like are adopted to improve the contact interface between the electrode and the electrolyte, reduce the electrochemical impedance of the interface and improve the electronic conductivity. However, most of the above modifications are based on powder materials. The presence of binders and additives in the powder electrode limits further improvement of its electrochemical performance. The film composite does not need a binder/additive and is suitable as a powder materialA substitute for (1). Therefore, the search for a substrate material with high specific surface area and high conductivity is very urgent and is also the first choice for constructing a high-performance titanium-based lithium ion niobate battery. However, in the array structure, the electrode material TiNb2O7Will be in direct contact with the electrolyte and will lack a rapid electron transport path. The highly efficient surface conductive coating layer can provide channels for the surface conductive coating layer and further improve the electrochemical performance. VG/TiNb synthesized as described above2O7The @ S-C composite porous array electrode has high rate capability, circulation stability and coulombic efficiency and is expected to become a lithium ion battery anode material with high power density and energy density capable of being commercially applied.
Disclosure of Invention
Against the problems of the background art, the invention aims to synthesize VG/TiNb with high specific surface area2O7The @ S-C composite porous array electrode is used for carrying out cooperative optimization through a three-dimensional nano porous array substrate and a surface coating carbon layer, and the problem of low intrinsic electron/ion mobility is solved.
The invention provides a vertical graphene/titanium niobium oxide/sulfur carbon composite material with a three-dimensional porous array structure, a preparation method thereof and application of the composite material as a lithium ion battery cathode material, and VG/TiNb with a core-shell structure2O7The @ S-C composite porous array electrode comprises a VG nano porous array substrate and TiNb2O7An active material and an S-C amorphous surface-coated carbon layer. VG/TiNb2O7The @ S-C composite porous array electrode is prepared by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD), a solvothermal method and a constant-current anodic deposition method, and the VG/TiNb is2O7The thickness of the nano-sheet is 20-50nm, VG/TiNb2O7The thickness of the @ S-C core-shell array is 50-120 nm.
The vertical graphene/titanium niobium oxide/sulfur carbon composite material with a three-dimensional porous array structure comprises:
vertically and crossly growing graphene nanosheets (VG) on the substrate to form a three-dimensional nano porous structure;
TiNb coated on the graphene nanosheet2O7(i.e., TNO) to form VG/TiNb2O7Nanosheets;
and coating the VG/TiNb2O7A sulfur-doped carbon layer (S-C) on the nanosheets to form VG/TiNb2O7@ S-C three-dimensional porous arrays.
The thickness of the graphene nano-sheet is 5-8nm, and the VG/TiNb is2O7The thickness of the nano-sheet is 20-50nm, and finally the obtained VG/TiNb2O7Thickness of the @ S-C three-dimensional porous array (i.e., VG/TiNb)2O7@ S-C core-shell array nanosheet thickness) is 50-120 nm.
The material is composed of a three-dimensional nano porous array substrate and a surface coated carbon layer and is cooperatively optimized.
The composite VG/TiNb2O7The @ S-C three-dimensional porous array is formed by taking a nanoporous array formed by interlaced and grown vertical graphene nano sheets (VG-5-8 nm) as a conductive substrate, and thermally growing and coating TNO in a solvent to form (VG/TiNb)2O7) Coating amorphous sulfur-doped carbon layer (S-C) after core, and preparing VG/TiNb2O7The thickness of the nano-sheet is 20-50nm, VG/TiNb2O7The thickness of the @ S-C core-shell array nanosheet is 50-120 nm.
A preparation method of a vertical graphene/titanium niobium oxygen/sulfur carbon composite material with a three-dimensional porous array structure comprises the following steps:
(1) the preparation method of the Vertical Graphene (VG) comprises the following steps: sequentially depositing the graphene array on carbon cloth by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to obtain a vertical graphene nanosheet (VG);
(2)VG/TiNb2O7the preparation method comprises the following steps: drying the vertical graphene nano-sheets, taking the vertical graphene nano-sheets as a growth substrate, and utilizing isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) Performing solvent thermal reaction as precursor, and cleaning after the reactionWashing, drying, heat treating and calcining to obtain VG/TiNb2O7Nanosheets;
(3)VG/TiNb2O7the preparation method of @ S-C comprises the following steps: 3, 4-Ethylenedioxythiophene (EDOT) and LiClO4Dissolving in acetonitrile, and depositing in constant-current anode to obtain VG/TiNb2O7And (3) depositing PEDOT (polymer of EDOT) on the nano-sheet, and calcining to obtain the vertical graphene/titanium niobium oxide/sulfur carbon composite material with a three-dimensional porous array structure.
In the step (1), in the plasma enhanced chemical vapor deposition method, the microwave frequency is 2.2 to 2.6GHz and the microwave power is 1.5kW to 2.5kW, and further preferably, the microwave frequency is 2.45GHz and the microwave power is 2 kW.
The method specifically comprises the following steps:
firstly, arranging carbon in a cavity and enabling the air pressure of the carbon to reach 10 mTorr;
secondly, after the temperature of the cavity is raised to 400 ℃, hydrogen plasma is generated in the cavity, and the hydrogen plasma passes through 500W microwave plasma at the flow rate of 90sccm H2Generating gas flow and simultaneously introducing methane, wherein in the whole reaction process, the volume ratio of hydrogen to methane is 3:2, and the reaction time is kept to be 2 h;
and finally, cooling to obtain the graphene nanosheets vertically grown on the carbon cloth, namely vertical graphene nanosheets (VGs).
In the step (2), the isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) The mass ratio of (1): 1.5 to 2.5, and more preferably, 0.5684 g: 1.08 g.
The reaction conditions of the solvothermal reaction are as follows: reacting at 180-220 ℃ for 4-8 h, preferably at 200 ℃ for 6 h.
The conditions of the heat treatment calcination are as follows: calcining for 1 to 3 hours by heat treatment at 600 to 800 ℃, and preferably for 2 hours by heat treatment at 700 ℃.
The heat treatment calcination is carried out under the protection atmosphere of argon.
In the step (3), the 3, 4-Ethylenedioxythiophene (EDOT) and LiClO4The mixture ratio of the acetonitrile and the glycerol is 0.3mL &0.7 mL: 0.5 g-1.5 g: 80mL to 120mL, more preferably 0.5 mL: 1 g: 100 ml.
The calcining conditions are as follows: calcining for 1 to 3 hours at the temperature of between 600 and 800 ℃, and further preferably calcining for 2 hours at the temperature of 700 ℃.
The calcination is carried out under the protection atmosphere of argon.
The vertical graphene/titanium niobium oxide/sulfur carbon composite material with the three-dimensional porous array structure has the three-dimensional porous array structure and is very suitable for serving as a lithium ion battery cathode material.
Compared with the prior art, the invention has the following advantages and outstanding effects:
in the invention, VG/TiNb2O7The @ S-C composite porous array is a film material, does not contain additives and binders, and has excellent cycle stability and high rate performance; the VG porous conductive substrate has a three-dimensional nano porous structure, so that the contact area of an electrode/electrolyte is increased, and a lithium ion transmission path is shortened; the sulfur-doped carbon layer coating provides a fast channel for electron transmission between the electrolyte and the electrode, improves the interface, and reduces the interface transfer resistance, thereby improving the electron conductivity and reducing the influence of the intrinsic low electron/ion conductivity of the material. The composite cathode improves the safety performance and the cycle performance of the lithium ion battery, and is beneficial to promoting the development of the lithium metal secondary battery with high energy density and high stability.
Drawings
FIG. 1 shows VG/TiNb prepared in example 22O7Scanning electron micrographs of the array;
FIG. 2 is a VG/TiNb sample prepared in example 22O7Transmission electron microscopy images of the array;
in FIG. 3, a is VG/TiNb prepared in example 22O7Scanning Electron micrograph of @ S-C, and b in FIG. 3 is VG/TiNb prepared in example 22O7The Ti element distribution spectrum of @ S-C, C in FIG. 3 is VG/TiNb prepared in example 22O7The distribution spectrum of the Nb element of @ S-C, d in FIG. 3 is VG/TiNb prepared in example 22O7O element distribution spectrogram of @ S-C, and e in FIG. 3 is VG/TiNb prepared in example 22O7The C element distribution spectrogram of @ S-C, f in FIG. 3 is VG/TiNb prepared in example 22O7S element distribution spectrogram of @ S-C;
FIG. 4 is a VG/TiNb graph obtained in example 22O7Scanning electron microscope image of @ S-C composite nanoporous array.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
(1) The preparation method of the Vertical Graphene (VG) comprises the following steps: the VG array was deposited on the carbon cloth by Plasma Enhanced Chemical Vapor Deposition (PECVD) (microwave frequency 2.45GHz and microwave power 2kW) in order. Firstly, carbon is distributed in a cavity and the air pressure of the carbon is 10mTorr, secondly, after the temperature of the cavity is raised to 400 ℃, hydrogen plasma is generated in the cavity, and the hydrogen plasma passes through 500W microwave plasma and H with the flow rate of 90sccm2Gas flow is generated while methane is introduced. In the whole reaction process, the ratio of hydrogen to methane is 3:2, the reaction time is kept for 2h, and finally, the reaction is cooled to room temperature of 25 ℃, and the preparation of the VG sample is finished.
(2)VG/TiNb2O7The preparation method comprises the following steps: drying the VG substrate in an oven for 12h, weighing, taking the Vertical Graphene (VG) as a growth substrate after weighing, and utilizing isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) And performing solvent thermal reaction as a precursor. Get 0.5684g C12H28O4Ti and 1.08g NbCl5Stirring in a beaker for 15 minutes, transferring to a hydrothermal kettle for reaction at 200 ℃ for 6 hours, and cooling along with the furnace. Then cleaning the sample with deionized water and absolute ethyl alcohol for several times, drying, calcining the sample in a tubular furnace for 2 hours at 700 ℃ under the protection of argon gas, and heating at the speed of 5 ℃/min to obtain VG/TiNb2O7Film samples.
(3)VG/TiNb2O7The preparation method of @ S-C comprises the following steps: 0.5ml EDOT and 1g LiClO4Dissolved in 100ml of acetonitrile and deposited by galvanostatic anodic deposition (1mA cm)-2) In the preparation of VG/TiNb2O7After PEDOT deposition on the filmCalcining the mixture for 2h (Ar atmosphere) in a tube furnace at the high temperature of 700 ℃, wherein the heating rate is 5 ℃/min to obtain VG/TiNb2O7@ S-C three-dimensional porous arrays.
Example 1
The VG substrate was dried in a vacuum oven. Using isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) The precursor is used for carrying out solvothermal reaction for 6h at 200 ℃ and is cooled along with the furnace. Washing the obtained sample with deionized water and absolute ethyl alcohol for several times, drying, calcining at 700 ℃ for 2h under the protection of argon gas at the heating rate of 5 ℃/min to obtain VG/TiNb2O7Film samples. With VG/TiNb2O7As core, in EDOT and LiClO4In acetonitrile solution, constant current anode deposition is carried out. After about 10s, PEDOT polymer will be deposited homogeneously on VG/TiNb2O7Array, forming a core-shell structure, and then calcining in a tube furnace at 700 ℃ for 2h (Ar atmosphere) to obtain VG/TiNb2O7@ S-C three-dimensional porous arrays.
Example 2
The VG substrate was dried in a vacuum oven. Using isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) The precursor is used for carrying out solvothermal reaction for 6h at 200 ℃ and is cooled along with the furnace. Washing the obtained sample with deionized water and absolute ethyl alcohol for several times, drying, calcining at 700 ℃ for 2h under the protection of argon gas at the heating rate of 5 ℃/min to obtain VG/TiNb2O7Film samples. With VG/TiNb2O7As core, in EDOT and LiClO4In acetonitrile solution, constant current anode deposition is carried out. After a period of about 20s, the reaction mixture,
PEDOT polymer will be uniformly deposited on VG/TiNb2O7Array, forming a core-shell structure, and then calcining in a tube furnace at 700 ℃ for 2h (Ar atmosphere) to obtain VG/TiNb2O7@ S-C three-dimensional porous arrays.
VG/TiNb prepared in example 22O7The scanning electron micrograph of the array is shown in FIG. 1; VG/TiNb prepared in example 22O7Transmission electron microscopy of arraysAs shown in fig. 2; in FIG. 3, a is VG/TiNb prepared in example 22O7Scanning Electron micrograph of @ S-C, and b in FIG. 3 is VG/TiNb prepared in example 22O7The Ti element distribution spectrum of @ S-C, C in FIG. 3 is VG/TiNb prepared in example 22O7The distribution spectrum of the Nb element of @ S-C, d in FIG. 3 is VG/TiNb prepared in example 22O7O element distribution spectrogram of @ S-C, and e in FIG. 3 is VG/TiNb prepared in example 22O7The C element distribution spectrogram of @ S-C, f in FIG. 3 is VG/TiNb prepared in example 22O7S element distribution spectrogram of @ S-C; FIG. 4 is a VG/TiNb graph obtained in example 22O7Scanning electron microscope image of @ S-C composite nanoporous array.
As can be seen from the figure, the vertical graphene/titanium niobium oxide/sulfur carbon composite material with the three-dimensional porous array structure comprises: vertically and crossly growing graphene nanosheets (VG) on the substrate to form a three-dimensional nano porous structure; TiNb coated on the graphene nanosheet2O7(i.e., TNO) to form VG/TiNb2O7Nanosheets; and coating the VG/TiNb2O7A sulfur-doped carbon layer (S-C) on the nanosheets to form VG/TiNb2O7@ S-C three-dimensional porous arrays. The thickness of the graphene nano-sheet is 5-8nm, and the VG/TiNb is2O7The thickness of the nano-sheet is 20-50nm, and finally the obtained VG/TiNb2O7Thickness of the @ S-C three-dimensional porous array (i.e., VG/TiNb)2O7@ S-C core-shell array nanosheet thickness) is 50-120 nm.
Example 3
The VG substrate was dried in a vacuum oven. Using isopropyl titanate (C)12H28O4Ti) and niobium pentachloride (NbCl)5) The precursor is used for carrying out solvothermal reaction for 6h at 200 ℃ and is cooled along with the furnace. Washing the obtained sample with deionized water and absolute ethyl alcohol for several times, drying, calcining at 700 ℃ for 2h under the protection of argon gas at the heating rate of 5 ℃/min to obtain VG/TiNb2O7Film samples. With VG/TiNb2O7As core, in EDOT and LiClO4Acetonitrile ofIn the solution, constant current anodic deposition is carried out. After about 40s, PEDOT polymer will be deposited homogeneously on VG/TiNb2O7Array, forming a core-shell structure, and then calcining in a tube furnace at 700 ℃ for 2h (Ar atmosphere) to obtain VG/TiNb2O7@ S-C three-dimensional porous arrays.
Performance testing
VG/TiNb prepared in examples 1 to 32O7The @ S-C three-dimensional porous electrode material is respectively used as a counter electrode and a working electrode of the button cell, the metal lithium wafer is used as the counter electrode, and 1M LiPF6+ EC/DMC (1:1) is the electrolyte. And sequentially adding the negative pole piece, the electrolyte, the diaphragm and the counter electrode piece into a battery shell for battery assembly, pressing and sealing the battery in a full-automatic packaging machine after the battery is assembled, and standing for more than 12 hours for electrochemical test. The charging and discharging test is carried out at room temperature, the instrument is a blue battery test system, and the test mainly adopts constant current charging and discharging test and cyclic voltammetry test. The constant current charge and discharge test is a very important electrochemical test means, and the indexes mainly comprise: specific capacity, rate capability, cycle capability, coulombic efficiency. Test voltage range is relative to Li/Li+1.0-2.5V, multiplying power test current of 1C,2C,5C,10C,20C,40C,80C and 160C, and circulating test current of 10C.
The performance test results are as follows:
VG/TiNb for example 1, example 2 and example 32O7The discharge specific capacitance of the @ S-C three-dimensional porous electrode at a current density of 10C is 134mAh/g, 182mAh/g and 165mAh/g respectively. In addition, after 10000 cycles of circulation, the discharge specific capacity retention rate reaches more than 65%, and the coulombic efficiency reaches more than 95%. It can be seen that VG/TiNb prepared as described above2O7The battery assembled by the @ S-C three-dimensional porous electrode has good cycling stability and high coulombic efficiency. VG/TiNb for example 1, example 2 and example 32O7The specific discharge capacitance of the @ S-C three-dimensional porous electrode at the current density of 160C is 145mAh/g, 225mAh/g and 180mAh/g respectively. It can be seen that VG/TiNb prepared as described above2O7The @ S-C three-dimensional porous electrode material has good high rate performance.
The VG conductive substrate has a three-dimensional nano porous structure, nanocrystallization is carried out on electrons and lithium ions, the contact area of the electrodes/electrolyte is increased, and the lithium ion transmission path is shortened; on the other hand, the three-dimensional porous VG substrate and the sulfur-doped carbon layer have higher electronic conductivity, and can promote electronic conduction between particles, so that the electronic/ionic conductivity of the particles is improved.
Therefore, the VG/TiNb of the invention2O7The @ S-C three-dimensional porous electrode has the characteristics of high cycle stability, high rate performance, coulombic efficiency and the like, and is expected to become a lithium ion battery cathode material with high power density and energy density, which can be commercially applied.
Claims (10)
1. A vertical graphene/titanium niobium oxygen/sulfur carbon composite material with a three-dimensional porous array structure is characterized by comprising:
graphene nanosheets vertically and crossly grown on the substrate;
TiNb coated on the graphene nanosheet2O7Form VG/TiNb2O7Nanosheets;
and coating the VG/TiNb2O7A sulfur-doped carbon layer on the nanosheets to form VG/TiNb2O7@ S-C three-dimensional porous arrays.
2. The vertical graphene/niobium titanium oxide/sulfur carbon composite material with a three-dimensional porous array structure as claimed in claim 1, wherein the thickness of the graphene nanosheet is 5-8nm, and the VG/TiNb is2O7The thickness of the nano-sheet is 20-50nm, and finally the obtained VG/TiNb2O7Thickness of the three-dimensional porous array of @ S-C, i.e. VG/TiNb2O7The thickness of the @ S-C core-shell array nanosheet is 50-120 nm.
3. The preparation method of the vertical graphene/niobium titanium oxygen/sulfur-carbon composite material with the three-dimensional porous array structure as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) sequentially depositing the graphene array on carbon cloth by a plasma enhanced chemical vapor deposition method to obtain a vertical graphene nanosheet;
(2) drying the vertical graphene nanosheet, taking the vertical graphene nanosheet as a growth substrate, carrying out solvothermal reaction by using isopropyl titanate and niobium pentachloride as precursors, cleaning, drying, carrying out heat treatment and calcining after the reaction is finished, thus obtaining VG/TiNb2O7Nanosheets;
(3) 3, 4-ethylenedioxythiophene and LiClO4Dissolving in acetonitrile, and depositing in constant-current anode to obtain VG/TiNb2O7And after PEDOT is deposited on the nano-sheet, calcining the nano-sheet to obtain the vertical graphene/titanium niobium oxide/sulfur carbon composite material with the three-dimensional porous array structure.
4. The method according to claim 3, wherein in the step (1), the microwave frequency is 2.2 to 2.6GHz and the microwave power is 1.5kW to 2.5kW in the plasma enhanced chemical vapor deposition method.
5. The preparation method according to claim 3, wherein in the step (2), the mass ratio of isopropyl titanate to niobium pentachloride is 1: 1.5 to 2.5.
6. The method according to claim 3, wherein in the step (2), the reaction conditions of the solvothermal reaction are as follows: reacting for 4-8 h at 180-220 ℃.
7. The method according to claim 3, wherein in the step (2), the conditions for the heat treatment calcination are as follows: calcining for 1 to 3 hours by heat treatment at the temperature of 600 to 800 ℃;
the heat treatment calcination is carried out under the protection atmosphere of argon.
8. The method according to claim 3, wherein in the step (3), the 3, 4-ethylenedioxythiophene and LiClO are used4The mixture ratio of the acetonitrile to the acetonitrile is 0.3 mL-0.7 mL: 0.5 g-1.5 g: 80mL to 120 mL.
9. The method according to claim 3, wherein in the step (3), the calcination is carried out under the following conditions: calcining for 1 to 3 hours at the temperature of 600 to 800 ℃;
the calcination is carried out under the protection atmosphere of argon.
10. The application of the vertical graphene/titanium niobium oxide/sulfur carbon composite material with the three-dimensional porous array structure according to claim 1 as a lithium ion battery anode material.
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| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| CN111403718B (en) * | 2020-03-31 | 2021-06-15 | 浙江大学 | Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof |
| KR20230029836A (en) | 2020-06-25 | 2023-03-03 | 6케이 인크. | Microcomposite alloy structure |
| AU2021349358A1 (en) | 2020-09-24 | 2023-02-09 | 6K Inc. | Systems, devices, and methods for starting plasma |
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| KR20230095080A (en) | 2020-10-30 | 2023-06-28 | 6케이 인크. | Systems and methods for synthesizing spheroidized metal powders |
| CN113921826B (en) * | 2021-10-09 | 2023-08-04 | 深圳石墨烯创新中心有限公司 | Upright graphene/nano silver composite material and preparation method and application thereof |
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