CN113921826A - Vertical graphene/nano-silver composite material and preparation method and application thereof - Google Patents
Vertical graphene/nano-silver composite material and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
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Abstract
The invention discloses a preparation method of a vertical graphene/nano silver composite material, which comprises the following steps: s1, spraying the graphene oxide solution on a substrate to form a horizontal graphene arrangement layer; s2, simultaneously spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer to obtain a precursor; s3, carrying out heat treatment on the precursor material, and then cleaning and drying to form a vertical graphene array layer to obtain a columnar vertical graphene array material; s4, dipping the columnar vertical graphene array material in a nano silver solution, and then drying to remove the solvent; and S5, carrying out heat treatment on the columnar vertical graphene array material impregnated with the nano silver in an inert atmosphere to obtain the vertical graphene/nano silver composite material. The invention also discloses the vertical graphene/nano-silver composite material prepared by the method and application thereof, and the application comprises the following two aspects: as a current collector material and in the manufacture of batteries.
Description
Technical Field
The invention relates to the technical field, and particularly relates to a vertical graphene/nano-silver composite material and a preparation method and application thereof.
Background
With the rapid development of mobile electronic devices and electric vehicles, rechargeable battery systems with high energy density have received much attention and research interest from researchers. Among many battery systems, lithium metal has the lowest reduction potential (-3.04V, compared with a standard hydrogen electrode), the extremely high theoretical specific capacity (3860mAhg < -1 >) and the lower density (0.54g cm < -3 >), and can be used as a negative electrode to be matched with a high-energy positive electrode material (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, so that the lithium metal battery system is considered to be the most ideal battery system. However, the lithium metal negative electrode has a number of problems that prevent its practical application and further commercialization. For example, unstable electrode/electrolyte interface states due to high reactivity and infinite volume change of metallic lithium easily cause formation of lithium dendrites with serious damage, and also reduce cycle life and reversibility, and bring about certain potential safety hazards.
By designing and constructing a three-dimensional structure material and simultaneously using the carrier and the current collector of the metallic lithium, the deposition and volume expansion/contraction of the metallic lithium can be accommodated, and meanwhile, the local current density is favorably reduced, and more uniform deposition is formed, so that the growth of lithium dendrite 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 metal lithium; and the high electrode tortuosity easily causes metallic lithium to be deposited on the surface, and further hinders the transmission of ions. However, electrode carriers having low tortuosity and sufficient mechanical strength generally have a large weight and a complicated production process, not only lowering the energy density of the battery as a whole, but also being unsuitable for practical production. The vertical graphene array has low microstructure tortuosity and smaller mass, is an ideal direct-current material, but is usually prepared by a chemical vapor deposition method, and has a complex preparation process and harsh preparation conditions; and moreover, the vertical graphene is over-compact in arrangement, the array pitch is small, and the size growth in the vertical direction is limited. Because the metal silver and the metal lithium can form a microscopic alloy phase, the nano silver can reduce the nucleation overpotential of the lithium in the electrochemical process, thereby inducing the stable nucleation and uniform deposition of the lithium metal.
In conclusion, 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, the respective characteristics of the carbon material and the metallic silver are combined to prepare the nano silver/vertical graphene composite material with controllable microstructure, the nano silver/vertical graphene composite material is applied to the fields of energy storage, thermal management and the like, 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 a vertical 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 embodiments of the present invention provide the following technical solutions:
in a first aspect, an embodiment of the present invention provides a method for preparing a vertical graphene/nano silver composite material, including the following steps:
s1, preparing a 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 spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer simultaneously in an electrostatic spraying manner to obtain a precursor;
s3, carrying out constant-temperature heat treatment on the precursor material in an inert atmosphere, wherein the heat treatment condition is that the temperature is higher than 150 ℃ and the time is longer than 1 h; after heat treatment, washing with water, removing the template solution, and then drying to form a vertical graphene array layer to obtain a columnar vertical graphene array material;
s4, preparing a nano silver solution with the concentration of 0.5-5mg/mL, dipping the columnar vertical graphene array material into the nano silver solution, taking out, drying and removing the solvent of the nano silver solution to obtain the columnar vertical graphene array material dipped with nano silver;
s5, carrying out heat treatment on the columnar vertical graphene array material impregnated with the nano silver in an inert atmosphere, wherein the heat treatment condition is that the temperature is 150-.
Preferably, the substrate is one of a metal foil, a ceramic substrate or a polymer material 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; the volume ratio of water to ethanol in a mixed solvent formed by mixing water and ethanol is 0.01:1-1: 1.
Preferably, in step S1, the electric field voltage is 10 to 50kV, the receiving distance is 5 to 30cm, and the spraying speed is 1 to 10mL/h when the graphene oxide solution is electrostatically sprayed.
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 the water to the absolute ethyl alcohol in the mixture of the water and the absolute ethyl alcohol is 1:10-1: 1.
Preferably, in step S2, the electric field voltage is 10 to 50kV, the receiving distance is 5 to 30cm, and the spraying speed is 1 to 10mL/h when the graphene oxide solution and the template solution are electrostatically sprayed.
Preferably, in step S3, when the substrate is washed with water after heat treatment, the water temperature is 20-80 ℃, and the washing time is 0.1-1 h; the drying temperature is 50-100 deg.C, and the drying time is 1-10 hr.
Preferably, in step S4, the solvent of the nano-silver solution is a mixture of water and absolute ethyl alcohol in a volume ratio of 1:10 to 1: 1.
Preferably, in the step S4, the drying temperature is 50-100 ℃ and the drying time is 1-10 h.
In a second aspect, the embodiment of the invention provides a vertical graphene/nano silver composite material prepared by the preparation method.
In a third aspect, the embodiment of the invention provides an application of the vertical graphene/nano silver composite material as a current collector material.
In a fourth aspect, the embodiment of the invention provides an application of the vertical graphene/nano silver composite material in preparing a battery.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a preparation method of a vertical graphene/nano silver composite material, the hollow upright graphene array is obtained by a template-assisted electrostatic spraying method with simple process, low cost and easy operation, meanwhile, the structural parameters of the columnar vertical graphene, such as size, spacing, height and the like, can be accurately regulated and controlled, and then through a nano silver impregnation method, the nano silver particles are loaded on the surface of the graphene to obtain the vertical graphene/nano silver composite material which has larger specific surface area and volume lithium volume and smaller lithium nucleation overpotential when being used as a negative current collector of a lithium metal battery, and excellent conductivity and convenient ion transmission channel, can meet the requirements of accommodating metallic lithium, homogenizing lithium deposition and eliminating lithium dendrite, thereby enabling the lithium metal battery to exert higher and more stable coulombic 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 modifiability, so that the vertical graphene/nano silver composite material also has a very good application prospect in the fields of heat conduction and heat dissipation, sensors and the like.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments of the present invention will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other drawings may be derived from the provided drawings by those of ordinary skill in the art without inventive effort.
The drawings are only for purposes of illustration and description, and are not intended to limit the scope of the invention, which is defined by the claims, which follow.
Fig. 1 is a front scanning electron microscope image of a columnar vertical graphene array material obtained in comparative example 1 of the present invention;
FIG. 2 is a side scanning electron microscope image of a columnar vertical graphene array material obtained in comparative example 1 of the present invention;
fig. 3 is a front scanning electron microscope image of the vertical graphene/nano silver composite material obtained in the embodiment of the present invention;
fig. 4 is a side scanning electron microscope image of the vertical graphene/nano silver composite material obtained in the embodiment of the present invention;
fig. 5 is a partial enlarged view of a lateral scanning electron microscope of the vertical 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 is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, the terms "comprises," "comprising," and any other 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 specifically listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus or additional steps or elements based on further optimization of the inventive concepts.
Comparative example 1
The comparative example provides a preparation method of a columnar vertical graphene array material and application of the columnar vertical graphene array material as a negative current collector of a lithium metal battery, and the preparation method comprises the following steps:
firstly, ultrasonically dispersing commercially available graphene oxide 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 solution with the concentration of 0.5mgmL-1The graphene oxide solution of (a);
and step two, electrostatically spraying the graphene oxide solution obtained in the step one onto a metal copper foil in a high-voltage electric field of 25kV at a spraying speed of 5mL h-1The distance between the nozzle and the copper foil is 10cm, the spraying time is 2 hours, and a layer of graphene oxide thin 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 the water to the absolute ethyl alcohol is 1: 4), wherein the concentration of the potassium chloride is 10mgmL-1；
Fourthly, respectively spraying the graphene oxide solution obtained in the first step and the potassium chloride solution obtained in the third step onto the graphene oxide film obtained in the second step from different directions at the spraying speed of 5mL h-1The voltage of the electric field is 25kV, the receiving distance is 10cm, and the spraying time is 10 h;
fifthly, carrying out low-temperature thermal reduction treatment on the material obtained in the fourth step in an argon/hydrogen (hydrogen content is 4%, oxygen content is less than 0.01%) mixed gas at 200 ℃ for 2 h;
and sixthly, washing the material obtained in the fifth step in deionized water at 50 ℃ for 0.5h, and drying the material at 60 ℃ in vacuum for 8h to obtain a vertical graphene array structure, namely a vertical graphene array layer, so as to obtain the columnar vertical graphene array material.
The comparative example also provides a columnar vertical graphene array current collector prepared by the preparation method. The columnar vertical graphene array current collector comprises a bottom metal foil, a horizontal graphene arrangement layer and a vertical graphene array layer.
Fig. 1 is a front scanning electron microscope image of a cylindrical vertical graphene array material obtained in comparative example 1 of the present invention, and referring to fig. 1, it can be seen that in the cylindrical vertical graphene array material prepared in the present comparative example, hollow graphene arrays are uniformly distributed, the diameter is distributed within a range of 5 to 10 μm, internal channels are interconnected and run through, and the size is 10 to 20 μm.
Fig. 2 is a side scanning electron microscope image of the columnar vertical graphene array material obtained in comparative example 1 of the present invention, and referring to fig. 2, it can be seen that in the columnar vertical graphene array material prepared in this embodiment, the graphene array is regularly arranged, and the height is about 20 μm.
Comparative example 1 of the present invention also provides a negative electrode including the pillar-shaped upright graphene array current collector prepared in example 1 and a negative active material embedded therein.
Comparative example 1 of the present invention also provides a battery. It may be a lithium metal battery. The battery includes the negative electrode, the positive electrode, and an electrolyte disposed between the negative electrode and the positive electrode. The columnar vertical graphene array material prepared in the example 1 is used as a lithium metal negative electrode current collector, and a 2032 button cell is assembled in a glove box filled with high-purity argon by taking a lithium sheet as a counter electrode. Testing the coulombic efficiency of lithium intercalation/deintercalation of the half cell at room temperature by using a Land (blue electricity) cell testing system, wherein the charge-discharge testing current density is 1mA cm-2The lithium intercalation capacity during discharging is 1mA h cm-2And the voltage of the lithium removal battery is set to 0.5V during charging. Coulomb 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 in comparative example 1 except that:
in this embodiment, the simultaneous spraying time in the fourth step is adjusted to 18 h;
furthermore, the present embodiment further includes:
and a seventh step of mixing the commercially available nano-silver aqueous solution with absolute ethanol, wherein the volume ratio of water to ethanol is 1: 3, preparing to obtain the solution with the concentration of 2mg mL-1The nano silver solution of (1);
step eight, dipping the columnar vertical graphene array material obtained in the step six into the nano-silver solution obtained in the step seven, taking out after a moment, drying in vacuum at 60 ℃ for 5 hours, and attaching nano-silver to the surface of graphene to obtain the columnar vertical graphene array material dipped with the nano-silver;
and a ninth step of placing the columnar vertical graphene array material impregnated with nano-silver obtained in the eighth step in an argon/hydrogen (hydrogen content is 4%, oxygen content is less than 0.01%) mixed gas, performing low-temperature heat treatment at 200 ℃ for 2 hours, and tightly loading the nano-silver on the surface of the graphene to form the vertical graphene/nano-silver composite material.
The embodiment also provides a cylindrical vertical graphene array current collector loaded with nano silver prepared by the preparation method. The cylindrical vertical graphene array current collector loaded with nano-silver comprises a bottom metal foil, a horizontal graphene arrangement layer and a vertical graphene array layer loaded with nano-silver.
Fig. 3 is a front scanning electron microscope image of the vertical graphene/nano silver composite material obtained in the embodiment of the present invention.
Fig. 4 is a side scanning electron microscope image of the vertical graphene/nano silver composite material obtained in the embodiment of the present invention, and the height of the graphene array structure is 30 μm.
Fig. 5 is a partially enlarged view of fig. 4, and it can be clearly seen that the 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 cylindrical vertical graphene array current collector loaded with the nano silver prepared in the embodiment and a negative active material embedded in the array current collector.
The embodiment also provides a battery. It may be a lithium metal battery. The battery includes the negative electrode, the positive electrode, and an electrolyte disposed between the negative electrode and the positive electrode. The cylindrical vertical graphene array material loaded with nano silver prepared in the embodiment is used as a lithium metal negative current collector, and a 2032 button cell is assembled in a glove box filled with high-purity argon by taking a lithium sheet as a counter electrode. Testing the coulombic efficiency of lithium intercalation/deintercalation of the half cell at room temperature by using a Land (blue electricity) cell testing system, wherein the charge-discharge testing current density is 1mA cm-2The lithium intercalation capacity during discharging is 1mA h cm-2And the voltage of the lithium removal battery is set to 0.5V during charging. Coulomb 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 was conducted using a commercial copper foil directly as a current collector, and the assembly of half cells was conducted, and the conditions of the subsequent assembly and test cells were kept consistent with those of example 1. The test results are: the average coulombic efficiency in the first 50 cycles is 95.3%, and after 50 cycles, the coulombic efficiency is reduced to below 90%, obvious fluctuation occurs, and the coulombic efficiency is continuously reduced until the battery cannot operate.
Claims (12)
1. A preparation method of a vertical graphene/nano silver composite material is characterized by comprising the following steps:
s1, preparing a 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 spraying the template solution and the graphene oxide solution on the horizontal graphene arrangement layer simultaneously in an electrostatic spraying manner to obtain a precursor;
s3, carrying out constant-temperature 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 1 h; after heat treatment, washing with water, removing the template solution, and then drying to form a vertical graphene array layer to obtain a columnar vertical graphene array material;
s4, preparing a nano silver solution with the concentration of 0.5-5mg/mL, dipping the columnar vertical graphene array material into the nano silver solution, taking out the columnar vertical graphene array material, and drying to remove the solvent of the nano silver solution to obtain the columnar vertical graphene array material dipped with nano silver;
s5, carrying out heat treatment on the columnar vertical graphene array material impregnated with the nano silver in an inert atmosphere, wherein the heat treatment condition is that the temperature is 150-.
2. The method for preparing the 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 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 the water to the ethanol is 0.01:1-1: 1.
4. The method for preparing a graphene/nano silver composite material according to claim 1, wherein in step S1, the voltage of the electric field is 10 to 50kV, the receiving distance is 5 to 30cm, and the spraying speed is 1 to 10mL/h when the graphene oxide solution is electrostatically sprayed.
5. The method for preparing the graphene/nano silver composite material according to claim 1, wherein the solute of the template solution is an inorganic metal salt, the solvent is a mixture of water and absolute ethyl alcohol, and the volume ratio of the water to the absolute ethyl alcohol in the mixture of the water and the absolute ethyl alcohol is 1:10-1: 1.
6. The method for preparing a graphene/nano silver composite material according to claim 1, wherein in step S2, the voltage of the electric field is 10 to 50kV, the receiving distance is 5 to 30cm, and the spraying speed is 1 to 10mL/h when the graphene oxide solution and the template solution are electrostatically sprayed.
7. The method for preparing the graphene/nano silver composite material according to claim 1, wherein in step S3, when the graphene/nano silver composite material is washed with water after the heat treatment, the water temperature is 20 to 80 ℃, and the washing time is 0.1 to 1 hour; the drying temperature is 50-100 deg.C, and the drying time is 1-10 hr.
8. The method for preparing the 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 in a volume ratio of 1:10 to 1: 1.
9. The method for preparing the 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 1-10 h.
10. A graphene/nano-silver composite material prepared by the method for preparing a graphene/nano-silver composite material according to claim 1.
11. Use of the graphene/nanosilver composite material according to claim 10 as a current collector material.
12. Use of the graphene/nanosilver composite material according to claim 10 for the preparation of a battery.
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