CN113921826B - Upright graphene/nano silver composite material and preparation method and application thereof - Google Patents
Upright graphene/nano silver composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113921826B CN113921826B CN202111177924.5A CN202111177924A CN113921826B CN 113921826 B CN113921826 B CN 113921826B CN 202111177924 A CN202111177924 A CN 202111177924A CN 113921826 B CN113921826 B CN 113921826B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nano
- upright
- composite material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
The invention discloses a preparation method of an upright graphene/nano silver composite material, which comprises the following steps: s1, spraying a graphene oxide solution on a substrate to form a horizontal graphene arrangement layer; s2, spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer simultaneously to obtain a precursor; s3, performing heat treatment on the precursor material, and then cleaning and drying to form an upright graphene array layer, thereby obtaining a columnar upright graphene array material; s4, dipping the columnar upright graphene array material into a nano silver solution, and then drying to remove the solvent; and S5, performing heat treatment on the columnar upright graphene array material impregnated with the nano silver in an inert atmosphere to obtain the upright graphene/nano silver composite material. The invention also discloses the upright graphene/nano silver composite material prepared by the method and application thereof, wherein the application comprises the following two aspects: as a current collector material and in the production of batteries.
Description
Technical Field
The invention relates to the technical field, in particular to an upright graphene/nano silver composite material, and a preparation method and application thereof.
Background
With the rapid development of mobile electronic devices and electric vehicles, high energy density rechargeable battery systems have received extensive attention and research interest from researchers. In many battery systems, lithium metal is considered to be the most ideal battery system because it has the lowest reduction potential (-3.04V compared with a standard hydrogen electrode), extremely high theoretical specific capacity (3860 mAhg-1) and lower density (0.54 g cm-3), and can be used as a negative electrode to be matched with high-energy positive electrode materials (such as a sulfur positive electrode, an oxygen positive electrode and a layered oxide positive electrode) to construct a lithium metal battery system with high-quality energy density. However, there are a number of problems with metallic lithium anodes that prevent their practical application and further commercialization. For example, the unstable electrode/electrolyte interface state due to the high reactivity and infinite volume change of metallic lithium is liable to cause the formation of lithium dendrites with serious damage, and also reduces the cycle life and reversibility, and brings about a certain potential safety hazard.
By designing and constructing the three-dimensional structure material and simultaneously using the three-dimensional structure material for the carrier and the current collector of the metal lithium, the deposition of the metal lithium and the volume expansion/contraction of the metal lithium can be accommodated, and meanwhile, the local current density is reduced, more uniform deposition is formed, and the growth of lithium dendrites is inhibited. Meanwhile, researches show that the low electrode tortuosity (namely an array structure) can form more uniform ion distribution, and is more beneficial to adjusting the deposition morphology of the metallic lithium; while high electrode tortuosity tends to cause metallic lithium to deposit on the surface, further impeding ion transport. However, the electrode carrier having low tortuosity and sufficient mechanical strength generally has a large weight and a complicated production process, not only reduces the energy density of the battery as a whole, but also is not suitable for practical production. The upright graphene array has low microstructure tortuosity and smaller mass, is an ideal direct-current fluid material, but is usually prepared by a chemical vapor deposition method, and has complex preparation process and harsh preparation conditions; moreover, the vertical graphene is too compact in arrangement, small in array pitch and limited in growth in size in the vertical direction. Because the metal silver and the metal lithium can form a micro alloy phase, the nano silver can reduce the nucleation overpotential of lithium in the electrochemical process, thereby inducing the stable nucleation and uniform deposition of lithium metal.
In summary, a simple, low-cost and process-controllable method is developed to prepare the vertical graphene array material with high mechanical strength, low tortuosity and large vertical dimension, and the characteristics of the carbon material and the metallic silver are combined to prepare the nano silver/vertical graphene composite material with controllable microstructure, and the nano silver/vertical graphene composite material is applied to the fields of energy storage, thermal management and the like, so that the structural and performance advantages of the nano silver/vertical graphene composite material are fully exerted, and the method has very important significance.
Disclosure of Invention
Therefore, the embodiment of the invention provides an upright graphene/nano silver composite material, and a preparation method and application thereof, so as to solve the problems in the prior art.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
in a first aspect, an embodiment of the present invention provides a method for preparing a graphene/nano-silver composite material, including the following steps:
s1, preparing graphene oxide solution with the concentration of 0.1-5mg/mL, and spraying the graphene oxide solution on a substrate in an electrostatic spraying manner to form a horizontal graphene arrangement layer;
s2, preparing a template solution with the concentration of 1-30mg/mL, and simultaneously spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer in an electrostatic spraying manner to obtain a precursor;
s3, carrying out heat treatment on the precursor material in an inert atmosphere, wherein the heat treatment condition is that the temperature is more than 150 ℃ and the time is more than 1h; after heat treatment, cleaning with water, removing a template solution, and then drying to form an upright graphene array layer to obtain a columnar upright graphene array material;
s4, preparing a nano silver solution with the concentration of 0.5-5mg/mL, dipping the columnar upright graphene array material into the nano silver solution, taking out, and drying to remove a solvent of the nano silver solution to obtain the columnar upright graphene array material dipped with nano silver;
s5, carrying out heat treatment on the columnar upright graphene array material impregnated with the nano silver in an inert atmosphere, wherein the heat treatment condition is that the temperature is 150-300 ℃ and the time is 1-5 hours, and obtaining the upright graphene/nano silver composite material.
Preferably, the substrate is one of a metal foil, a ceramic substrate or a polymeric substrate.
Preferably, the solvent of the graphene oxide solution is one of absolute ethyl alcohol or a mixed solvent formed by mixing water and ethyl alcohol; in the mixed solvent formed by mixing water and ethanol, the volume ratio of water to ethanol is 0.01:1-1:1.
Preferably, in the step S1, the electric field voltage is 10-50kV, the receiving distance is 5-30cm, and the spraying speed is 1-10mL/h when the graphene oxide solution is sprayed electrostatically.
Preferably, the solute of the template solution is inorganic metal salt, the solvent is a mixture of water and absolute ethyl alcohol, and the volume ratio of water to absolute ethyl alcohol in the mixture of water and absolute ethyl alcohol is 1:10-1:1.
Preferably, in the step S2, the electric field voltage is 10-50kV, the receiving distance is 5-30cm, and the spraying speed is 1-10mL/h when the graphene oxide solution and the template solution are sprayed electrostatically.
Preferably, in the step S3, when the water is used for cleaning after the heat treatment, the water temperature is 20-80 ℃ and the cleaning time is 0.1-1h; the drying temperature is 50-100deg.C, and the drying time is 1-10 hr.
Preferably, in the step S4, the solvent of the nano silver solution is a mixture of water and absolute ethyl alcohol according to the volume ratio of 1:10-1:1.
Preferably, in step S4, the drying temperature is 50-100deg.C and the drying time is 1-10h.
In a second aspect, the embodiment of the invention provides the upright graphene/nano-silver composite material prepared by the preparation method.
In a third aspect, the present invention provides an application of the above-mentioned graphene/nano-silver composite material as a current collector material.
In a fourth aspect, the embodiment of the invention provides an application of the upright graphene/nano-silver composite material in preparing a battery.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the preparation method of the vertical graphene/nano silver composite material, provided by the invention, the hollow vertical graphene array is obtained through the template-assisted electrostatic spraying method which is simple in process, low in cost and easy to operate, meanwhile, the structural parameters such as the size, the distance and the height of columnar vertical graphene can be accurately regulated and controlled, and nano silver particles are loaded on the surface of graphene through the nano silver dipping method, so that the vertical graphene/nano silver composite material is obtained, and has larger specific surface area and lithium volume, smaller lithium nucleation overpotential, excellent conductivity and convenient ion transmission channel when being used as a negative electrode current collector of a lithium metal battery, and can meet the requirements of containing metal lithium, homogenizing lithium deposition and eliminating lithium dendrites, so that the lithium metal battery can exert higher and more stable coulomb efficiency and longer cycle life.
(2) The vertical graphene/nano silver composite material provided by the invention has the advantages of compact arrangement, large specific surface area, large accommodation volume, good conductivity and strong decoration property, so that the vertical graphene/nano silver composite material has very good application prospects in the fields of heat conduction and radiation, sensors and the like.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings that are required to be used in the description of the embodiments of the present invention will be briefly described below. It will be apparent to those skilled in the art that the drawings in the following description are merely exemplary and that other drawings may be derived from the drawings provided without the inventive effort to those skilled in the art.
The following drawings are provided to enable those skilled in the art to understand and read the disclosure, and are not intended to limit the applicable scope of the present invention, and any modifications may be made without affecting the efficacy or reach of the invention.
FIG. 1 is a front scanning electron microscope image of a columnar upright graphene array material obtained in comparative example 1 of the present invention;
FIG. 2 is a side scanning electron microscope image of the columnar upright graphene array material obtained in comparative example 1 of the present invention;
FIG. 3 is a front scanning electron microscope image of the standing graphene/nano-silver composite material obtained in the embodiment of the present invention;
FIG. 4 is a side scanning electron microscope image of the upright graphene/nano-silver composite material obtained by the embodiment of the invention;
fig. 5 is a partial enlarged view of a side scanning electron microscope of the upright graphene/nano-silver composite material obtained in the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, the terms "comprises," "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements but may include other steps or elements not expressly listed but inherent to such process, method, article, or apparatus or steps or elements added based on further optimization of the inventive concept.
Comparative example 1
The comparative example provides a preparation method of a columnar upright graphene array material and application of the columnar upright graphene array material as a lithium metal battery negative electrode current collector, and the preparation method comprises the following steps:
in the first step, commercially available graphene oxide is ultrasonically dispersed in a mixed solvent of deionized water and absolute ethyl alcohol, wherein the volume ratio of water to ethyl alcohol is 1:3, preparing to obtain the concentration of 0.5mgmL -1 Is a graphene oxide solution;
secondly, the graphene oxide solution obtained in the first step is electrostatically sprayed on a metal copper foil under a high-voltage electric field of 25kV, wherein the spraying speed is 5mL h -1 The distance between the nozzle and the copper foil is 10cm, the spraying time is 2 hours, and a layer of graphene oxide film which is arranged in parallel, namely a horizontal graphene arrangement layer, is obtained on the copper foil;
thirdly, dissolving a certain amount of potassium chloride particles into a mixed solution of water and absolute ethyl alcohol (the mixing ratio of water to absolute ethyl alcohol is 1:4), wherein the concentration of potassium chloride is 10mgmL -1 ；
Fourth, the graphene oxide solution obtained in the first step and the second stepThe potassium chloride solution obtained in the three steps is sprayed onto the graphene oxide film obtained in the second step from different directions, wherein the spraying speed is 5mL h -1 The electric field voltages are 25kV, the receiving distances are 10cm, and the spraying time is 10 hours;
fifthly, carrying out low-temperature thermal reduction treatment on the material obtained in the fourth step for 2h at 200 ℃ in an argon/hydrogen (the hydrogen content is 4 percent and the oxygen content is less than 0.01 percent) mixed gas;
and step six, washing the material obtained in the step five in deionized water at 50 ℃ for 0.5h, and vacuum drying at 60 ℃ for 8h to obtain an upright graphene array structure, namely an upright graphene array layer, so as to obtain the columnar upright graphene array material.
The comparative example also provides a columnar upright graphene array current collector prepared by the preparation method. The columnar upright graphene array current collector comprises a bottom metal foil, a horizontal graphene arrangement layer and an upright graphene array layer.
Fig. 1 is a front scanning electron microscope image of a columnar upright graphene array material obtained in comparative example 1, and referring to fig. 1, it can be seen that in the columnar upright graphene array material obtained in this comparative example, hollow graphene arrays are uniformly distributed, the diameters are distributed within the range of 5-10 μm, and the internal channels are interconnected and penetrated, and the size is 10-20 μm.
Fig. 2 is a side scanning electron microscope image of the columnar upright graphene array material obtained in comparative example 1, and referring to fig. 2, it can be seen that in the columnar upright graphene array material obtained in this embodiment, the graphene arrays are regularly arranged, and the height is about 20 μm.
The present invention also provides a negative electrode comprising the columnar standing graphene array current collector prepared in example 1 and a negative electrode active material embedded therein.
The present invention comparative example 1 also provides a battery. Which may be a lithium metal battery. The battery includes the negative electrode, a positive electrode, and an electrolyte disposed between the negative electrode and the positive electrode. The columnar upright graphene array material prepared in example 1 was used as a lithium metal negative electrode current collector, and was put in a glove box filled with high-purity argon gasIn the process, a 2032 button cell was assembled by using a lithium sheet as a counter electrode. The coulombic efficiency of the half-cell for lithium intercalation/deintercalation at room temperature was tested using a Land (blue-electric) cell test system, and the charge-discharge test current density was 1mA cm -2 The discharge lithium intercalation capacities are respectively 1mA h cm -2 The lithium removal voltage at the time of charging was set to 0.5V. Coulombic efficiency test results: the coulombic efficiency after 150 cycles was 96.8% and the average coulombic efficiency during 150 cycles was 98%.
Examples
In the production method of this example, the first to sixth steps are substantially the same as comparative example 1, except that:
in the embodiment, the simultaneous spraying time in the fourth step is adjusted to 18 hours;
and, this embodiment further includes:
seventh, mixing commercially available nano silver water solution with absolute ethyl alcohol, wherein the volume ratio of water to ethyl alcohol is 1:3, preparing to obtain the concentration of 2mg mL -1 Is a nano silver solution;
eighth, dipping the columnar upright graphene array material obtained in the sixth step into the nano silver solution obtained in the seventh step, taking out after a moment, and vacuum drying for 5 hours at 60 ℃, wherein nano silver is attached to the surface of graphene, so as to obtain the columnar upright graphene array material dipped with nano silver;
and a ninth step, placing the columnar upright graphene array material impregnated with the nano silver obtained in the eighth step into an argon/hydrogen (the hydrogen content is 4 percent and the oxygen content is less than 0.01 percent) mixed gas, carrying out low-temperature treatment for 2 hours at 200 ℃, and tightly loading the nano silver on the surface of graphene to form the upright graphene/nano silver composite material.
The embodiment also provides the columnar upright graphene array current collector loaded with the nano silver, which is prepared by the preparation method. The columnar upright graphene array current collector loaded with the nano silver comprises a bottom metal foil, a horizontal graphene arrangement layer and an upright graphene array layer loaded with the nano silver.
Fig. 3 is a front scanning electron microscope image of the upright graphene/nano silver composite material obtained in the embodiment of the present invention.
Fig. 4 is a side scanning electron microscope image of an upright graphene/nano silver composite material obtained by the embodiment of the invention, and the height of a graphene array structure is 30 μm.
Fig. 5 is a partial enlarged view of fig. 4, and it can be clearly seen that nano silver is uniformly and tightly adhered to the surface of the graphene material.
The embodiment of the invention also provides a negative electrode, which comprises the columnar upright graphene array current collector loaded with nano silver and the negative electrode active material embedded in the array current collector.
The embodiment also provides a battery. Which may be a lithium metal battery. The battery includes the negative electrode, a positive electrode, and an electrolyte disposed between the negative electrode and the positive electrode. The columnar upright graphene array material loaded with nano silver prepared in the embodiment is used as a lithium metal negative electrode current collector, and a 2032 button cell is assembled by taking a lithium sheet as a counter electrode in a glove box filled with high-purity argon. The coulombic efficiency of the half-cell for lithium intercalation/deintercalation at room temperature was tested using a Land (blue-electric) cell test system, and the charge-discharge test current density was 1mA cm -2 The discharge lithium intercalation capacities are respectively 1mA h cm -2 The lithium removal voltage at the time of charging was set to 0.5V. Coulombic efficiency test results: the coulombic efficiency after 200 cycles was 97.3% and the average coulombic efficiency during 200 cycles was 98.6%.
Comparative example 2
Comparative example 2 used commercial copper foil as current collector directly, and assembled half cell, and the conditions for subsequent assembly and testing of the cell were consistent with example 1. The test results are: the average coulomb efficiency of the first 50 cycles was 95.3%, after 50 cycles, the coulomb efficiency was reduced to below 90%, and significant fluctuations occurred and continued to drop to the point where the cell was inoperable.
Claims (12)
1. The preparation method of the upright graphene/nano silver composite material is characterized by comprising the following steps of:
s1, preparing graphene oxide solution with the concentration of 0.1-5mg/mL, and spraying the graphene oxide solution on a substrate in an electrostatic spraying manner to form a horizontal graphene arrangement layer;
s2, preparing a template solution with the concentration of 1-30mg/mL, and simultaneously spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer in an electrostatic spraying manner to obtain a precursor;
s3, carrying out heat treatment on the precursor material in an inert atmosphere, wherein the heat treatment condition is that the temperature is more than 150 ℃ and the time is more than 1h; after heat treatment, cleaning with water, removing the template solution, and then drying to form an upright graphene array layer to obtain a columnar upright graphene array material;
s4, preparing a nano silver solution with the concentration of 0.5-5mg/mL, immersing the columnar upright graphene array material in the nano silver solution, taking out, and drying to remove a solvent of the nano silver solution to obtain the columnar upright graphene array material immersed with nano silver;
s5, carrying out heat treatment on the columnar upright graphene array material impregnated with the nano silver in an inert atmosphere, wherein the heat treatment condition is that the temperature is 150-300 ℃ and the time is 1-5 hours, and obtaining the upright graphene/nano silver composite material.
2. The method for preparing the standing graphene/nano-silver composite material according to claim 1, wherein the substrate is one of a metal foil, a ceramic substrate or a polymer material substrate.
3. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein the solvent of the graphene oxide solution is one of absolute ethyl alcohol or a mixed solvent formed by mixing water and ethyl alcohol; in the mixed solvent formed by mixing water and ethanol, the volume ratio of water to ethanol is 0.01:1-1:1.
4. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein in the step S1, the electric field voltage is 10-50kV, the receiving distance is 5-30cm, and the spraying speed is 1-10mL/h when the graphene oxide solution is sprayed electrostatically.
5. The preparation method of the upright graphene/nano-silver composite material according to claim 1, wherein the solute of the template solution is inorganic metal salt, the solvent is a mixture of water and absolute ethyl alcohol, and the volume ratio of water to absolute ethyl alcohol in the mixture of water and absolute ethyl alcohol is 1:10-1:1.
6. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein in the step S2, the electric field voltage is 10-50kV, the receiving distance is 5-30cm, and the spraying speed is 1-10mL/h when the graphene oxide solution and the template solution are sprayed electrostatically.
7. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein in the step S3, when the upright graphene/nano-silver composite material is washed with water after heat treatment, the water temperature is 20-80 ℃ and the washing time is 0.1-1h; the drying temperature is 50-100deg.C, and the drying time is 1-10 hr.
8. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein in the step S4, the solvent of the nano-silver solution is a mixture of water and absolute ethyl alcohol according to a volume ratio of 1:10-1:1.
9. The method for preparing the upright graphene/nano-silver composite material according to claim 1, wherein in the step S4, the drying temperature is 50-100 ℃ and the drying time is 1-10h.
10. A graphene/nanosilver composite prepared using the graphene/nanosilver composite preparation method of claim 1.
11. Use of the graphene/nano-silver composite material of claim 10 as a current collector material.
12. Use of the graphene/nano-silver composite material of claim 10 for the preparation of a battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111177924.5A CN113921826B (en) | 2021-10-09 | 2021-10-09 | Upright graphene/nano silver composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111177924.5A CN113921826B (en) | 2021-10-09 | 2021-10-09 | Upright graphene/nano silver composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113921826A CN113921826A (en) | 2022-01-11 |
| CN113921826B true CN113921826B (en) | 2023-08-04 |
Family
ID=79238630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111177924.5A Active CN113921826B (en) | 2021-10-09 | 2021-10-09 | Upright graphene/nano silver composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113921826B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269544A (en) * | 2014-10-15 | 2015-01-07 | 南京中储新能源有限公司 | Graphene array composited anode as well as preparation method and application thereof |
| CN106847648A (en) * | 2017-03-01 | 2017-06-13 | 杭州电子科技大学 | A kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure |
| CN107235472A (en) * | 2017-05-24 | 2017-10-10 | 华中科技大学 | Porous vertical graphene nano wall array of N doping and preparation method and application |
| CN108649190A (en) * | 2018-03-28 | 2018-10-12 | 浙江大学 | Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application |
| CN109286011A (en) * | 2018-09-28 | 2019-01-29 | 哈尔滨理工大学 | A kind of preparation method of stannic disulfide/vertical graphene nanometer sheet array electrode |
| CN109449443A (en) * | 2018-09-13 | 2019-03-08 | 安庆师范大学 | A kind of preparation method of porous graphene/Nano silver grain complex lithium metal secondary batteries negative current collector |
| CN110564087A (en) * | 2019-05-24 | 2019-12-13 | 深圳市溢鑫科技研发有限公司 | Vertical graphene-high molecular polymer composite material and preparation method thereof |
| CN110726765A (en) * | 2019-12-17 | 2020-01-24 | 深圳市刷新智能电子有限公司 | Graphene biosensor electrode and preparation process thereof |
| US11063164B1 (en) * | 2020-09-17 | 2021-07-13 | Allen Howard Engel | Method and materials to manufacture heterojunctions, diodes, and solar cells |
| KR20210118318A (en) * | 2020-03-20 | 2021-09-30 | 우석대학교 산학협력단 | Anode material with graphene-agnw-silicon of secondary battery and the method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104700961B (en) * | 2015-03-18 | 2016-10-12 | 上海和伍复合材料有限公司 | A kind of graphene/silver composite material and preparation method thereof |
| US10403894B2 (en) * | 2015-04-23 | 2019-09-03 | William Marsh Rice University | Vertically aligned carbon nanotube arrays as electrodes |
| US10566145B2 (en) * | 2017-03-18 | 2020-02-18 | King Abdulaziz City For Science And Technology—Kacst | TiO2-graphene-silver hybrid nanocomposite and a method of preparation thereof |
-
2021
- 2021-10-09 CN CN202111177924.5A patent/CN113921826B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269544A (en) * | 2014-10-15 | 2015-01-07 | 南京中储新能源有限公司 | Graphene array composited anode as well as preparation method and application thereof |
| CN106847648A (en) * | 2017-03-01 | 2017-06-13 | 杭州电子科技大学 | A kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure |
| CN107235472A (en) * | 2017-05-24 | 2017-10-10 | 华中科技大学 | Porous vertical graphene nano wall array of N doping and preparation method and application |
| CN108649190A (en) * | 2018-03-28 | 2018-10-12 | 浙江大学 | Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application |
| CN109449443A (en) * | 2018-09-13 | 2019-03-08 | 安庆师范大学 | A kind of preparation method of porous graphene/Nano silver grain complex lithium metal secondary batteries negative current collector |
| CN109286011A (en) * | 2018-09-28 | 2019-01-29 | 哈尔滨理工大学 | A kind of preparation method of stannic disulfide/vertical graphene nanometer sheet array electrode |
| CN110564087A (en) * | 2019-05-24 | 2019-12-13 | 深圳市溢鑫科技研发有限公司 | Vertical graphene-high molecular polymer composite material and preparation method thereof |
| CN110726765A (en) * | 2019-12-17 | 2020-01-24 | 深圳市刷新智能电子有限公司 | Graphene biosensor electrode and preparation process thereof |
| KR20210118318A (en) * | 2020-03-20 | 2021-09-30 | 우석대학교 산학협력단 | Anode material with graphene-agnw-silicon of secondary battery and the method thereof |
| US11063164B1 (en) * | 2020-09-17 | 2021-07-13 | Allen Howard Engel | Method and materials to manufacture heterojunctions, diodes, and solar cells |
Non-Patent Citations (1)
| Title |
|---|
| Highly Conductive Graphene Paper with Vertically Aligned Reduced Graphene Oxide Sheets Fabricated by Improved Electrospray Deposition Technique;Jun-Xiang Yan;ACS APPLIED MATERIALS&INTERFACES;第11卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113921826A (en) | 2022-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110676420B (en) | Lithium ion battery's lithium diaphragm of mending | |
| Jiang et al. | Li4. 4Sn encapsulated in hollow graphene spheres for stable Li metal anodes without dendrite formation for long cycle-life of lithium batteries | |
| RU2469442C1 (en) | System for highly efficient conversion and accumulation of energy using carbon nanostructured materials | |
| CN110104630B (en) | Porous carbon composite material for battery diaphragm and preparation method and application thereof | |
| US10727466B2 (en) | Polyethyleneimine-attached carbonaceous material and separator for lithium-sulfur battery coated with the same | |
| CN107681091B (en) | Lithium-sulfur battery functional composite diaphragm and preparation method thereof | |
| CN108565464B (en) | Sulfur-carrying MOF @ conductive polymer material and preparation method and application thereof | |
| CN103053063A (en) | Cathode current collector coated with a primer and magnesium secondary battery including same | |
| EP1825619A2 (en) | High power density supercapacitors with carbon nanotube electrodes | |
| CN112635744B (en) | Carbon-silicon-tin composite cathode material and preparation method thereof | |
| CN105355925B (en) | A kind of preparation method of three-dimensional order nickel skeleton load germanium base lithium cell cathode material | |
| CN110010895A (en) | Carbon fiber loaded magnesium oxide particle crosslinking nano chip arrays composite material and preparation method and application | |
| Wang et al. | Hierarchical porous NiCo 2 O 4 nanograss arrays grown on Ni foam as electrode material for high-performance supercapacitors | |
| Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
| Zhang et al. | In situ constructing lithiophilic and Ion/Electron Dual-Regulated current collector for highly stable lithium metal batteries | |
| Saleem et al. | Coin-cell supercapacitors based on CVD grown and vertically aligned carbon nanofibers (VACNFs) | |
| CN113921826B (en) | Upright graphene/nano silver composite material and preparation method and application thereof | |
| CN111326351A (en) | Cu for capacitor2Preparation method of O/NiO material | |
| CN108565448B (en) | Tin dioxide/graphene composite material and preparation method thereof | |
| CN113328057A (en) | Composite metal lithium cathode and preparation method thereof | |
| CN102593425A (en) | Method for assembling high-performance lithium ion battery based on hollow carbon nanocage cathode material | |
| CN115347140A (en) | Surface-modified composite zinc-based negative electrode, preparation method and battery | |
| Chen et al. | Nanostructured Electrodes via Electrostatic Spray Deposition for Energy Storage System | |
| CN108987694B (en) | Reduced graphene oxide coated Na4MnV(PO4)3@ rGO microsphere nano material and preparation and application thereof | |
| CN113690546A (en) | Lithium-sulfur battery diaphragm and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |