CN109638266B - Carbon-coated selenium indium lithium material and preparation method and application thereof - Google Patents
Carbon-coated selenium indium lithium material and preparation method and application thereof Download PDFInfo
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- ZBMHAKQPBHKTCB-UHFFFAOYSA-N [Li].[In]=[Se] Chemical compound [Li].[In]=[Se] ZBMHAKQPBHKTCB-UHFFFAOYSA-N 0.000 title claims abstract description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 14
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- 239000011669 selenium Substances 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 230000001788 irregular Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 13
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- 238000001816 cooling Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 6
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- 229910052723 transition metal Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
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- 150000004771 selenides Chemical class 0.000 description 4
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- 150000003343 selenium compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a carbon-coated selenium indium lithium material, wherein the molar ratio of Li to In to Se to C In the material is 1:1:2: 0.5-1: 1:2:10 at any ratio, and the particle size of particles of the material is 30-300 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1-8 nanometers, and a small amount of carbon particles with the particle size of 10-20 nanometers are distributed among the carbon-coated selenium indium lithium particles. The novel carbon-coated selenium indium lithium negative electrode material provided by the invention has high electronic conductivity and lithium ion diffusion coefficient, and excellent cycle stability and rate capability. The lithium ion battery has high reversible capacity and excellent cycling stability when rapidly charged and discharged under the current density of 1500mA/g, and is expected to have wide application prospect in the field of lithium ion battery cathode materials.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and relates to a novel carbon-coated selenium indium lithium material, and a preparation method and application thereof.
Background
In recent years, with the wide application of lithium ion batteries in electronic devices and high-power electronic equipment, increasingly higher requirements are made on the aspects of cycle stability, rate capability, long service life and the like of battery cathode materials. The current commercialized negative electrode material is mainly a carbon-based material, wherein graphite is the most typical one, but the lower discharge potential causes the potential of the negative electrode material to have a greater potential safety hazard, and the lithium storage capacity and the rate capability of the negative electrode material are lower, so that the requirements of the current high-power electronic equipment on high energy density and high power density cannot be met. Designing a novel anode material capable of replacing carbon anode materials is one of the main tasks faced by current lithium ion batteries.
Recently, novel transition metal chalcogenides (including metal sulfides, metal selenides, and the like) have attracted much attention due to their excellent electrochemical properties, and are considered as a class of negative electrode materials with great application prospects. Transition metal chalcogenides based on transformation and alloying reactions exhibit higher lithium storage capacities compared to carbon materials. In particular, metal selenides have relatively high electron conductivity and low energy conversion reactions. Thus, metal selenides exhibit longer cycle life than metal sulfides. However, most of the currently studied transition metal selenium compounds are in binary phases, and these binary metal selenium compounds are easily stacked or re-stacked in a bulk material, and may limit the storage space of lithium ions during charging and discharging, thereby resulting in poor electrochemical performance of the electrode material.
Researchers have done a lot of meaningful work in improving the electrochemical performance of transition metal selenium compounds. For example, compounding with graphene and the like, controlling morphology, reducing particle size through nanocrystallization, and the like. Although the graphene composite material can obviously improve the conductivity of the electrode material, the structure of the composite material is not stable enough, the electrode material is still easy to have a pulverization phenomenon in the charging and discharging process, and better cycling stability cannot be obtained. The shape of the material can be controlled to enable the structure of the material to be stable or influence the specific surface area of the material, but the preparation condition of the material is harsh and the repeatability is poor. In addition, the diffusion distance of lithium ions can be shortened during charge and discharge by reducing the particle size through nanocrystallization, but the improvement degree of the electrochemical performance of the material is very limited at present. In contrast, the addition of the third element can lead to a delicate balance among factors such as the structure, chemical bonds and charge transfer of the material, and thus the material exhibits excellent electrochemical performance in the field of energy storage. Based on the above, a novel ternary metal selenide with good cycle stability and rate capability is found, which has very important significance for the research and wide application of transition metal chalcogenide.
The applicant finds that the ternary metal selenide-lithium indium selenide (LiInSe) through long-term research2) The selenium indium lithium material is a lithium ion battery cathode material with good cycling stability, but the selenium indium lithium material still has the indexes of electronic conductivity, lithium ion diffusion coefficient, cycling stability, rate capability and the like, and can not meet the requirement of preparing a high-performance lithium ion battery cathode material. Through retrieval, no report is found on a paper or a patent about preparing a carbon-coated selenium indium lithium material by performing surface carbon coating treatment on the selenium indium lithium material so as to improve the electronic conductivity and the ionic conductivity of the material and further obviously improve the electrochemical performance of the selenium indium lithium.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a novel carbon-coated selenium indium lithium material and a preparation method and application thereof.
The carbon-coated selenium indium lithium material is prepared by LiInSe2The @ C designation, characterized by: the carbon-coated selenium indium lithium material consists of lithium, indium, selenium and carbon elements, wherein the molar ratio of Li to In to Se to C is 1:1:2: 0.5-1: 1:2: 10; the carbon-coated selenium indium lithium material is black powder in appearance, the powder is in the shape of irregular polyhedral particles or approximately spherical polyhedral particles observed under an electron microscope, and the particle size range is 30-300 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1 to 8 nanometers, and a small amount of carbon particles with the particle size range of 10 to 20 nanometers are distributed among the carbon-coated selenium indium lithium particles; the capacity of the carbon-coated selenium indium lithium material is 180mAh/g after the carbon-coated selenium indium lithium material is cycled for 500 times under the current density of 1500 mA/g.
Further, the carbon-coated selenium indium lithium material is composed of lithium, indium, selenium and carbon elements, wherein the molar ratio of the elements Li to In to Se to C is preferably 1:1:2: 0.5-1: 1:2:5.5 In any proportion; the carbon-coated selenium indium lithium material is black powder in appearance, the powder is in the shape of irregular polyhedral particles observed under an electron microscope, and the particle size range of the particles is 30-150 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1-5 nanometers, and a small amount of carbon particles with the particle size range of 10-20 nanometers are distributed among the carbon-coated selenium indium lithium particles.
The preparation method of the carbon-coated selenium indium lithium material comprises the following steps:
(1) selenium indium lithium LiInSe2Polycrystalline raw material synthesis: high-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of Li to In to Se of 1:1:2, and the mixture is vacuumized to 2 x 10 by an autoclave synthesis method-3After Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize LiInSe2Polycrystalline raw materials;
(2) ball milling: using ball mill to make selenium indium lithium LiInSe2The polycrystalline raw material is subjected to ball milling treatment, so that agglomeration of the polycrystalline raw material is reduced, and LiInSe is reduced2Polycrystalline powder particle size; wherein the ball milling speed is 300-600 r/min, and the ball milling time is 3-6 hours;
(3) preparing raw materials of carbon-coated selenium indium lithium: the selenium indium lithium LiInSe after ball milling is added2Respectively weighing the polycrystalline powder and the selected carbon source raw materials according to a set mass ratio;
(4) dispersing materials: weighing the selenium indium lithium LiInSe obtained in the step (3)2Placing the polycrystalline powder and selected carbon source raw materials in absolute ethyl alcohol or ultrapure water, dispersing and stirring to form uniform solid-liquid suspension;
(5) drying: drying the solid-liquid suspension obtained in the step (4) by using drying equipment to obtain a powdery substance;
(6) and (3) calcining: calcining the powder substance obtained in the step (5) in calcining equipment to obtain a product, namely the carbon-coated selenium indium lithium material, and using LiInSe2@ C denotes;
the method is characterized in that:
the carbon source of step (3)Selecting glucose, common coal tar pitch or citric acid as raw materials; the selenium indium lithium LiInSe2The mass ratio of the polycrystalline powder to the selected carbon source raw material is any ratio of 10: 1 to 10: 7.
The volume amount of the absolute ethyl alcohol or the ultrapure water in the step (4) is 5-50 times of that of the material;
the drying equipment in the step (5) is an oven, a drying box or an infrared lamp, and the drying temperature is 60-80 ℃;
and (6) the calcining equipment is a muffle furnace, a resistance furnace or a tubular furnace with a device for accurately controlling the temperature, the calcining atmosphere is argon, the calcining temperature is 500-700 ℃, and the calcining time is 3-8 hours.
The preparation method of the carbon-coated selenium indium lithium material comprises the following steps: the carbon source raw material in the step (3) is preferably common coal pitch; the selenium indium lithium LiInSe2The mass ratio of the polycrystalline powder to the common coal pitch is preferably any ratio of 10: 1 to 10: 5.5.
The preparation method of the carbon-coated selenium indium lithium material comprises the following steps: the volume amount of the absolute ethyl alcohol in the step (4) is preferably 10-30 times of the volume amount of the material.
The preparation method of the carbon-coated selenium indium lithium material comprises the following steps: the calcining equipment in the step (6) is preferably a tubular furnace with a device for accurately controlling the temperature, the calcining atmosphere is argon, the calcining temperature is preferably 550 ℃, and the calcining time is 5 hours.
The carbon-coated selenium indium lithium material is applied to preparation of a lithium ion battery cathode material.
Experiments prove that the selenium indium lithium polycrystalline powder is subjected to nanocrystallization and carbon coating technical treatment, so that the specific capacity, the cycle performance, the rate performance and the like of an electrode of the selenium indium lithium material are greatly improved. The material still has higher reversible capacity and excellent cycling stability when being charged and discharged rapidly under the current density of 1500 mA/g. The novel carbon-coated selenium indium lithium negative electrode material has a wide application prospect in the field of negative electrode materials of lithium ion batteries.
The invention has the beneficial effects that:
1. the preparation process is simple, the operation is easy, the energy is saved, and the production efficiency is high; because the raw material preparation and the reaction equipment are simple, and the reaction process is easy to regulate and control, the method is particularly suitable for industrial batch production.
2. The prepared carbon-coated selenium indium lithium negative electrode material has excellent cycle stability and rate capability.
3. The prepared carbon-coated selenium indium lithium negative electrode material has excellent electronic conductivity and ionic conductivity.
4. The prepared carbon-coated selenium indium lithium negative electrode material is rapidly charged and discharged under high current density, and has high coulombic efficiency and excellent cycle stability.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 1.
Fig. 2a is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 2.
Fig. 2b is a scanning electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 2.
Fig. 2c is a rate capability test of the carbon-coated lithium indium selenide negative electrode material prepared in example 2.
Fig. 3 is a transmission electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 3.
Fig. 4a is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 4.
Fig. 4b is a transmission electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 4.
Fig. 5a is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
Fig. 5b is a transmission electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
FIG. 5c shows the cycling performance of the carbon-coated lithium indium selenide negative electrode material prepared in example 5 at a current density of 100 mA/g.
Fig. 5d is the rate capability of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
FIG. 5e is a graph of the long cycle performance of the carbon-coated lithium indium selenide negative electrode material prepared in example 5 at a current density of 1500 mA/g.
Fig. 5f is an electrochemical impedance diagram of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
Fig. 6a is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
Fig. 6b is a transmission electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 5.
Fig. 7a is an X-ray powder diffraction pattern of the carbon-coated lithium indium selenide negative electrode material prepared in example 9.
Fig. 7b is a transmission electron microscope image of the carbon-coated lithium indium selenide negative electrode material prepared in example 9.
FIG. 7c shows the cycling performance of the carbon-coated lithium indium selenide negative electrode material prepared in example 9 at a current density of 100 mA/g.
Detailed Description
Example 1
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystal powder and 1.0g of the glucose powder were weighed, dispersed in 40mL of ultrapure water and stirred for 30 minutes. Then drying in an oven at 80 ℃. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 1). LiInSe for comparison2The standard XRD pattern is JCPDS.No. 77-2487.
Example 2
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and synthesized by an autoclaveMethod, vacuum pumping to 2 × 10-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystal powder and 1.2g of glucose powder were weighed, dispersed in 40mL of ultrapure water and stirred for 30 minutes. Then drying in an oven at 80 ℃. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 2 a). The scanning electron microscope observation shows that the powder obtained in the embodiment is polyhedral particles, the size range is 100-300 nanometers, and the carbon layer is attached among the particles of pure selenium indium lithium (fig. 2 b). The rate performance test (fig. 2c) of the carbon-coated lithium indium selenide negative electrode material obtained in the embodiment proves that the average capacity can reach 272, 227, 150, 90 and 44mAh/g under the discharge rates of 100, 200, 400, 800 and 1600 mA/g. The rate performance of the carbon-coated selenium indium lithium is proved to be obviously superior to that of pure selenium indium lithium.
Example 3
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystal powder and 1.4g of the glucose powder were weighed, dispersed in 60mL of ultrapure water and stirred for 30 minutes. Then drying by an infrared lamp. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
Transmission electron microscopy showed that the powder obtained in this example was polyhedral in particles with an average size of about 400 nm and that the carbon layer was attached between the particles of pure selenium indium lithium (figure 3).
Example 4
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystalline powder and 0.6g of pitch were weighed, dispersed in 40mL of anhydrous ethanol and stirred for 30 minutes. Then drying by an infrared lamp. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 4 a). The observation of a transmission electron microscope shows that the powder obtained in the embodiment is polyhedral particles, the size range is 40-60 nanometers, and a carbon layer is attached among the particles of pure selenium indium lithium (fig. 4 b).
Example 5
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystalline powder and 1.0g of pitch were weighed, dispersed in 40mL of anhydrous ethanol and stirred for 30 minutes. Then drying by an infrared lamp. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 5 a). The observation of the transmission electron microscope shows that the powder obtained in the present example is polyhedral particles with a size range of 30-50 nm, and the carbon layer is attached between the particles of pure selenium indium lithium (fig. 5 b).
The carbon-coated se-in-li negative electrode material assembled battery obtained in this example was subjected to a cycle performance test (fig. 5 c). The result shows that under the current density of 100mA/g, after 100 cycles, the coulomb efficiency is close to 100 percent, and the capacity reaches 389 mAh/g. The rate performance test (fig. 5d) of the carbon-coated lithium indium selenide negative electrode material obtained in the embodiment proves that the average capacity can reach 358, 312, 256, 216 and 165mAh/g under the discharge rates of 100, 200, 400, 800 and 1600 mA/g. The carbon-coated lithium indium selenide negative electrode material obtained in the example was tested for high-rate long cycle performance (fig. 5 e). The results showed a capacity of 180mAh/g after 500 cycles at a current density of 1500 mA/g. The carbon-coated selenium indium lithium anode material is proved to have excellent cycle performance even under higher current density. The carbon-coated lithium indium selenide negative electrode material obtained in the example was tested for electrochemical ac impedance spectrum after 100 cycles at 100mA/g (fig. 5 f). Compared with the pure selenium indium lithium without modification, the selenium indium lithium negative electrode material after carbon coating has smaller semicircle and larger slope. The electron conductivity and the lithium ion diffusion coefficient of the selenium indium lithium material are obviously improved through carbon coating modification.
Based on the above experimental results, the carbon-coated selenium indium lithium material (LiInSe) of the present invention can be described in summary2@ C) is: the carbon-coated selenium indium lithium material consists of lithium, indium, selenium and carbon elements, wherein the molar ratio of Li to In to Se to C is 1:1:2: 0.5-1: 1:2: 10; the carbon-coated selenium indium lithium material is black powder in appearance, the powder is in the shape of irregular polyhedral particles or approximately spherical polyhedral particles observed under an electron microscope, and the particle size range is 30-300 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1 to 8 nanometers, and a small amount of carbon particles with the particle size range of 10 to 20 nanometers are distributed among the carbon-coated selenium indium lithium particles; the capacity of the carbon-coated selenium indium lithium material is 180mAh/g after the carbon-coated selenium indium lithium material is cycled for 500 times under the current density of 1500 mA/g.
Example 6
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystalline powder and 1.4g of pitch were weighed, dispersed in 70mL of anhydrous ethanol and stirred for 30 minutes. Then drying the mixture by a drying oven at 80 ℃. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. And finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material.
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 6 a). Transmission electron microscopy showed that the powder obtained in this example was polyhedral in particles with an average size of about 50 nm and a carbon layer attached between the particles of pure selenium indium lithium (fig. 6 b).
Example 7
High-purity simple substances Li (3N), In (5N) and Se (5N) are mixed according to the molar ratio of 1:1:2, and are vacuumized to 2 x 10 through an autoclave synthesis method-3And (6) after Pa, putting the mixture into a single-temperature-zone synthesis furnace to synthesize the selenium indium lithium polycrystalline raw material. 30g of selenium indium lithium polycrystal raw materials are put into a ball mill for ball milling, the rotating speed is 500 r/min, and the ball milling time is 5 hours. Obtaining the dark brown selenium indium lithium polycrystalline powder.
2.0g of the selenium indium lithium polycrystalline powder and 1.2g of citric acid were weighed, dispersed with 40mL of ultrapure water and stirred for 30 minutes. Then drying the mixture in an oven at 80 ℃. The powder obtained is kept at 550 ℃ for 5 hours in a tube furnace under argon atmosphere. Finally cooling to room temperature to obtain black powder, namely the novel carbon-coated selenium indium lithium cathode material
The X-ray powder diffraction result shows that the carbon-coated selenium indium lithium nano polycrystalline powder obtained by the experiment has no other impurity phase (figure 7 a). Transmission electron microscope observation shows that the powder obtained in the example is irregular polyhedral particles with the size range of 100-150 nm, and the carbon layer is attached among the particles of pure selenium indium lithium (figure 7 b).
The carbon-coated se-in-li negative electrode material assembled battery obtained in this example was subjected to a cycle performance test (fig. 7 c). The result shows that under the current density of 100mA/g, after 100 cycles, the coulomb efficiency is close to 100 percent, and the capacity reaches 410 mAh/g.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (7)
1. A carbon-coated selenium indium lithium material is represented by LiInSe2@ C, and is characterized in that: the carbon-coated selenium indium lithium material consists of lithium, indium, selenium and carbon elements, wherein the molar ratio of Li to In to Se to C is 1:1:2: 0.5-1: 1:2: 10; the carbon-coated selenium indium lithium material is black powder in appearance, the powder is in the shape of irregular polyhedral particles or approximately spherical polyhedral particles observed under an electron microscope, and the particle size range is 30-300 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1-8 nanometers, and a small amount of carbon particles with the particle size range of 10-20 nanometers are distributed among the carbon-coated selenium indium lithium particles; the capacity of the carbon-coated selenium indium lithium material is 180mAh/g after the carbon-coated selenium indium lithium material is cycled for 500 times under the current density of 1500 mA/g.
2. The carbon-coated selenium indium lithium material of claim 1, wherein: the carbon-coated selenium indium lithium material consists of lithium, indium, selenium and carbon elements, wherein the molar ratio of Li to In to Se to C is 1:1:2: 0.5-1: 1:2: 5.5; the carbon-coated selenium indium lithium material is black powder in appearance, the powder is in the shape of irregular polyhedral particles observed under an electron microscope, and the particle size range of the particles is 30-150 nanometers; the particle structure is characterized in that carbon is coated outside the selenium indium lithium particles, the thickness of the coated carbon layer is 1-5 nanometers, and a small amount of carbon particles with the particle size range of 10-20 nanometers are distributed among the carbon-coated selenium indium lithium particles.
3. The preparation method of the carbon-coated selenium indium lithium material as claimed in claim 1, which comprises the following steps:
(1) synthesis of a selenium indium lithium LiInSe2 polycrystal raw material: mixing high-purity simple substance 3N Li, 5N In and 5N Se according to the molar ratio of Li to In to Se of 1:1:2, vacuumizing to 2 x 10 < -3 > Pa by using an autoclave synthesis method, and putting into a single-temperature-zone synthesis furnace to synthesize a LiInSe2 polycrystalline raw material;
(2) ball milling: carrying out ball milling treatment on the selenium indium lithium LiInSe2 polycrystalline raw material by using a ball mill, so as to reduce agglomeration of the polycrystalline raw material and reduce the particle size of LiInSe2 polycrystalline powder; wherein the ball milling speed is 300-600 r/min, and the ball milling time is 3-6 hours;
(3) preparing raw materials of carbon-coated selenium indium lithium: respectively weighing the ball-milled LiInSe2 polycrystalline powder and the selected carbon source raw materials according to a set mass ratio;
(4) dispersing materials: putting the LiInSe2 polycrystalline powder weighed in the step (3) and a selected carbon source raw material into absolute ethyl alcohol or ultrapure water, and dispersing and stirring to form a uniform solid-liquid suspension;
(5) drying: drying the solid-liquid suspension obtained in the step (4) by using drying equipment to obtain a powdery substance;
(6) and (3) calcining: calcining the powder substance obtained in the step (5) in calcining equipment to obtain a product, namely the carbon-coated selenium indium lithium material, which is expressed by LiInSe2@ C;
the method is characterized in that:
selecting glucose, common coal tar pitch or citric acid as the carbon source raw material in the step (3); the mass ratio of the LiInSe2 polycrystalline powder to the selected carbon source raw material is any ratio of 10: 1 to 10: 7;
the volume amount of the absolute ethyl alcohol or the ultrapure water in the step (4) is 5-50 times of that of the material;
the drying equipment in the step (5) is an oven, a drying box or an infrared lamp, and the drying temperature is 60-80 ℃;
and (6) the calcining equipment is a muffle furnace, a resistance furnace or a tubular furnace with a device for accurately controlling the temperature, the calcining atmosphere is argon, the calcining temperature is 500-700 ℃, and the calcining time is 3-8 hours.
4. The method for preparing the carbon-coated selenium indium lithium material according to claim 3, wherein the method comprises the following steps: selecting common coal pitch as the carbon source raw material in the step (3); the mass ratio of the LiInSe2 polycrystalline powder to the common coal pitch is any ratio of 10: 1 to 10: 5.5.
5. The method for preparing the carbon-coated selenium indium lithium material according to claim 3, wherein the method comprises the following steps: and (4) the volume amount of the absolute ethyl alcohol in the step (4) is 10-30 times of that of the material.
6. The method for preparing the carbon-coated selenium indium lithium material according to claim 3, wherein the method comprises the following steps: and (4) the calcining equipment in the step (6) is a tubular furnace with a device for accurately controlling the temperature, the calcining atmosphere is argon, the calcining temperature is 550 ℃, and the calcining time is 5 hours.
7. The use of the carbon-coated selenium indium lithium material of claim 1 or 2 in the preparation of a negative electrode material for a lithium ion battery.
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