CN112234189A - Tin telluride-based electrode material, preparation method thereof and lithium ion battery - Google Patents
Tin telluride-based electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN112234189A CN112234189A CN202011090532.0A CN202011090532A CN112234189A CN 112234189 A CN112234189 A CN 112234189A CN 202011090532 A CN202011090532 A CN 202011090532A CN 112234189 A CN112234189 A CN 112234189A
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
The invention discloses a tin telluride-based electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the electrode material comprises the following steps: using massive tin telluride, graphite and carbon nanotubes as raw materials, mixing the raw materials in a ball milling tank, and adding ball milling beads; and then carrying out ball milling under a protective atmosphere to obtain the electrode material. The SnTe-CNT-G electrode material is prepared by a simple ball milling method, and the material structure is anchored on a three-dimensional layered carbon framework by superfine few-layer SnTe nanosheets, so that the SnTe-CNT-G electrode material not only has higher conductivity and good electrochemical redox activity, but also has excellent electrochemical stability, and is an excellent lithium ion battery cathode material; the performance advantage of the tin telluride is greatly shown due to the structural advantage, good cycle stability is shown, and meanwhile, the conductivity of the material is greatly improved due to the introduction of the carbon frame, and the reaction kinetics is promoted.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a tin telluride-based electrode material, a preparation method thereof and a lithium ion battery.
Background
The development of high capacity density rechargeable batteries is critical to meet the ever-increasing demand for energy systems. Despite the commercial success of lithium ion batteries in the portable electronics market, their use in many areas is still limited due to the low theoretical capacity of the commercial graphite anodes. Therefore, development of a novel anode material having high energy density and long cycle life is urgently required.
The topological insulator SnTe has a narrow band gap (0.18eV), and shows wide application prospects in various electronic devices. In addition, element Te has the largest metallic characteristic (2X 10)-4mS·m-1) So that SnTe has extremely high conductivity. Furthermore, SnTe has a typical layered structure, being Li+Provides excellent structural flexibility. More importantly, the density of SnTe (6.445g cm)-3) Much higher than other Sn-based materials, which allows SnTe to have a large volumetric capacity when used as an electrode in a lithium ion battery. However, similar to other alloy-type anode materials, the practical use of SnTe is still limited by its inherent large volume change, resulting in pulverization of active particles, resulting in an unstable Solid Electrolyte Interface (SEI) layer, and thus poor electrochemical performance. Design with short and efficient Li+Stabilization of ion and electron pathsElectrode structures, large contact areas with the electrolyte and reduced apparent volume changes are key to solving these problems.
So far, there are only a few reports on transition metal telluride electrode materials, and studies on electrochemical properties and reaction mechanisms thereof are less focused. In addition, the problem of electron transport between layers of topological materials still cannot be solved well, which limits the application of such materials in lithium ion batteries.
Accordingly, the prior art remains to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a tin telluride-based electrode material, a preparation method thereof and a lithium ion battery, and aims to solve the problems of insufficient conductivity, agglomeration, expansion and pulverization in the circulation process of the conventional telluride electrode material.
The technical scheme of the invention is as follows:
a preparation method of a tin telluride-based electrode material comprises the following steps:
using massive tin telluride, graphite and carbon nanotubes as raw materials, mixing the raw materials in a ball milling tank, and adding ball milling beads;
and then carrying out ball milling under a protective atmosphere to obtain the electrode material.
Optionally, the mass percentage of the bulk tin telluride in the raw material is 30-60%.
Optionally, the graphite accounts for 30-50% of the raw materials by mass.
Optionally, the carbon nanotubes account for 0-20% of the raw materials by mass.
Optionally, in the ball milling process, the ratio of the mass of the raw materials to the mass of the ball milling beads is 1: (20-40).
Optionally, the rotation speed of the ball milling is 400-600 rpm, and the time of the ball milling is 10-20 h.
Optionally, the protective atmosphere is nitrogen or argon.
The tin telluride-based electrode material is prepared by the preparation method of the tin telluride-based electrode material.
A lithium ion battery comprises a negative electrode, wherein the negative electrode material is the tin telluride-based electrode material.
Has the advantages that: the invention prepares the tin telluride-based electrode material (marked as SnTe-CNT-G) with a three-dimensional layered structure by hybridizing the superfine few-layer SnTe layer, graphite (G) and Carbon Nano Tubes (CNT) through a simple and extensible mechanical ball milling method. The electrode material not only has higher conductivity and high specific capacity, but also has good electrochemical stability, and is an excellent lithium ion battery cathode material. And the unique nano structure of the structurally interconnected porous channel provides a short diffusion distance, promotes ion transmission, improves the interface between an electrode and an electrolyte and is beneficial to improving intercalation pseudocapacitance behavior. In addition, the carbon layer can stabilize and prevent stacking/re-stacking of SnTe, improve electron conductivity, and solve the problem of volume expansion during cycling. In addition, the SnTe-CNT-G electrode material is simple in preparation method and low in cost, and is beneficial to large-scale production and application of the material.
Drawings
FIG. 1 is an SEM image of an SnTe-CNT-G electrode material prepared in example 1 of the present invention.
FIG. 2 is a TEM image of the SnTe-CNT-G electrode material prepared in example 1 of the present invention.
FIG. 3 is an XPS plot of SnTe-CNT-G electrode material prepared in example 1 of the present invention.
FIG. 4 shows that the SnTe-CNT-G electrode material prepared in example 1 of the present invention is at 2000mA G-1Cycling performance plot at current density.
FIG. 5a shows the electrode material of SnTe, SnTe-G, SnTe-CNT-G in example 1 of the present invention at 200mA G-1Comparative plot of cycling performance at current density.
FIG. 5b is a graph comparing the rate capability of the electrode material of SnTe, SnTe-G, SnTe-CNT-G in example 1 of the present invention at different current densities.
FIG. 5c shows the electrode material of SnTe, SnTe-G, SnTe-CNT-G in example 1 of the present invention at 2000mA G-1Comparative plot of cycling performance at current density.
Detailed Description
The invention provides a tin telluride-based electrode material, a preparation method thereof and a lithium ion battery, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, most telluride electrode materials have the problems of complicated preparation method, high cost and the like; in addition, for the use as the negative electrode material of the lithium ion battery, other simpler preparation methods can be limited to the solvothermal method, but the solvothermal method synthesizes a multilayer block material, so that the lithium storage point of the active material is limited, and the utilization rate of the active material is low.
Accordingly, an embodiment of the present invention provides a method for preparing a tin telluride-based electrode material, including the steps of:
using massive tin telluride, graphite and carbon nanotubes as raw materials, mixing the raw materials in a ball milling tank, and adding ball milling beads;
and then carrying out ball milling under a protective atmosphere to obtain the electrode material.
In the embodiment, the layered porous SnTe-CNT-G electrode material is prepared by a simple and extensible mechanical ball milling method. In the electrode material, superfine and few-layer SnTe nanosheets are anchored in a three-dimensional layered carbon skeleton, so that abundant active sites are provided for lithium ion storage, the utilization rate of active substances is improved, and the cycle stability and the specific capacity are obviously improved. Second, the carbon layer can stabilize and prevent stacking/re-stacking of SnTe, not only effectively promoting the transport of ions, but also improving electron conductivity. In addition, the carbon layer can also effectively relieve volume expansion, and the structural characteristics greatly enhance the surface reaction kinetics and promote charge transfer. In addition, the SnTe-CNT-G electrode material is simple in preparation method and low in cost, and is beneficial to large-scale production and application of the material.
According to the method, a novel three-dimensional structure can be prepared by a novel, simple and low-cost preparation method, the performance of tin telluride is greatly shown due to the structural advantage of the novel three-dimensional structure, good circulation stability is shown, and meanwhile, the conductivity of the material is greatly improved due to the introduction of the carbon frame, and the reaction kinetics is promoted.
In one embodiment, the mass percentage of the bulk tin telluride in the raw material is 30-60%.
In one embodiment, the graphite accounts for 30-50% of the raw materials by mass. The graphite can be exfoliated into few-layered graphite during the ball milling process.
In one embodiment, the carbon nanotubes are 0-20% by mass of the raw material.
In one embodiment, the mass percent of the bulk tin telluride is 30-60%, and the mass percent of the carbon nanotubes is 0-20% based on the raw materials.
In one embodiment, the ratio of the mass of the feedstock to the mass of the ball milling beads during ball milling is 1: (20-40).
In one embodiment, the rotation speed of the ball mill is 400-600 rpm, and the ball milling time is 10-20 h.
In one embodiment, the protective atmosphere is nitrogen or argon.
The embodiment of the invention provides a tin telluride-based electrode material, which is prepared by adopting the preparation method of the tin telluride-based electrode material.
The layered porous SnTe-CNT-G electrode material has the structure that the SnTe nanosheets with a few superfine layers are anchored on the three-dimensional layered carbon framework, so that the layered porous SnTe-CNT-G electrode material has high conductivity, good electrochemical redox activity and excellent electrochemical stability, and is an excellent lithium ion battery cathode material; the unique nano structure of the structurally interconnected porous channels provides short diffusion distance, promotes ion transmission, improves the interface of an electrode and an electrolyte, and is beneficial to improving intercalation pseudocapacitance behavior.
The embodiment of the invention provides a lithium ion battery, which comprises a negative electrode, wherein the negative electrode material is the tin telluride-based electrode material.
The invention is further illustrated by the following specific examples.
Example 1
Weighing a certain mass of raw materials, weighing a certain amount of ball milling beads, wherein the mass of the blocky SnTe is 1.0g, the mass of the graphite is 0.8g, the mass of the multi-walled carbon nano tube is 0.2g, and the ratio of the mass of the added raw materials to the mass of the ball milling beads is 1: 30, under the protection of argon atmosphere, the ball milling speed is 500rpm, the ball milling time is 15h, and then the SnTe-CNT-G electrode material is obtained. The structures of the electrode materials prepared in this example are shown in fig. 1 to 2, the components and properties of the electrode materials are shown in fig. 3 to 4, and the properties of the electrode materials are shown in fig. 5a, 5b and 5 c.
Example 2
Weighing a certain mass of raw materials, weighing a certain amount of ball milling beads, wherein the mass of the blocky SnTe is 1.0g, the mass of the graphite is 1.0g, the mass of the multi-walled carbon nano tube is 0g, and the mass ratio of the added raw materials to the ball milling beads is 1: and 20, under the protection of a nitrogen atmosphere, the ball milling rotating speed is 600rpm, the ball milling time is 10h, and then the SnTe-CNT-G electrode material is obtained.
Example 3
Weighing a certain mass of raw materials, weighing a certain amount of ball milling beads, wherein the mass of the blocky SnTe is 1.2g, the mass of the graphite is 0.6g, the mass of the multi-walled carbon nano tube is 0.2g, and the mass ratio of the added raw materials to the ball milling beads is 1: and 40, under the protection of a nitrogen atmosphere, the ball milling rotating speed is 450rpm, the ball milling time is 15h, and then the SnTe-CNT-G electrode material is obtained.
Example 4
Weighing raw materials with certain mass, weighing certain ball milling beads, wherein the mass of the blocky SnTe is 0.8g, the mass of the graphite is 0.8g, the mass of the carbon nano tube is 0.4g, and the mass ratio of the added raw materials to the ball milling beads is 1: and 25, under the protection of argon atmosphere, the ball milling rotating speed is 550rpm, the ball milling time is 20h, and then the SnTe-CNT-G electrode material is obtained.
Example 5
Weighing raw materials with certain mass, weighing certain ball milling beads, wherein the mass of the blocky SnTe is 1.0g, the mass of the graphite is 0.9g, the mass of the carbon nano tube is 0.1g, and the mass ratio of the added raw materials to the ball milling beads is 1: 30, under the protection of nitrogen atmosphere, the ball milling speed is 500rpm, the ball milling time is 15h, and then the SnTe-CNT-G electrode material is obtained.
In summary, the invention provides a tin telluride-based electrode material, a preparation method thereof and a lithium ion battery. The SnTe-CNT-G electrode material is prepared by a simple ball milling method, and the material structure is anchored on a three-dimensional layered carbon framework by superfine few-layer SnTe nanosheets, so that the SnTe-CNT-G electrode material not only has higher conductivity and good electrochemical redox activity, but also has excellent electrochemical stability, and is an excellent lithium ion battery cathode material; the performance advantage of the tin telluride is greatly shown due to the structural advantage, good cycle stability is shown, and meanwhile, the conductivity of the material is greatly improved due to the introduction of the carbon frame, and the reaction kinetics is promoted. The three-dimensional SnTe-CNT-G electrode material assembled by the superfine few-layer tin telluride nanosheets and the layered carbon has the advantages of simple preparation method and low cost, and is beneficial to large-scale production and application of the material.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a tin telluride-based electrode material is characterized by comprising the following steps:
using massive tin telluride, graphite and carbon nanotubes as raw materials, mixing the raw materials in a ball milling tank, and adding ball milling beads;
and then carrying out ball milling under a protective atmosphere to obtain the electrode material.
2. The method for preparing the tin telluride-based electrode material as claimed in claim 1, wherein the mass percentage of the bulk tin telluride in the raw material is 30-60%.
3. The method for preparing the tin telluride-based electrode material as claimed in claim 1, wherein the graphite accounts for 30-50% by mass of the raw material.
4. The method for preparing the tin telluride-based electrode material as claimed in claim 1, wherein the carbon nanotubes are 0-20% by mass of the raw material.
5. The composite thermoelectric material of claim 1, wherein during ball milling, the ratio of the mass of the raw materials to the mass of the ball milled beads is 1: (20-40).
6. The preparation method of the tin telluride-based electrode material as set forth in claim 1, wherein the rotation speed of the ball milling is 400-600 rpm, and the time of the ball milling is 10-20 h.
7. The method for producing a tin telluride-based electrode material as set forth in claim 1, wherein the protective atmosphere is nitrogen or argon.
8. A tin telluride-based electrode material, which is characterized by being prepared by the preparation method of the tin telluride-based electrode material as claimed in any one of claims 1 to 7.
9. A lithium ion battery comprising a negative electrode, wherein the negative electrode material is the tin telluride-based electrode material as set forth in claim 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116646503A (en) * | 2023-07-27 | 2023-08-25 | 河南师范大学 | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery |
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| CN116646503A (en) * | 2023-07-27 | 2023-08-25 | 河南师范大学 | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery |
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Application publication date: 20210115 |