CN111403712A - Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery Download PDFInfo
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Abstract
A lithium-sulfur battery positive electrode material comprising a carbon material, a high-entropy alloy oxide supported on the surface of the carbon material, and sulfur filling pores between the carbon material and the high-entropy alloy oxide or supported on the surface of the carbon material and/or the high-entropy alloy oxide. The application also provides a preparation method of the lithium-sulfur battery positive electrode material and a lithium-sulfur battery. The lithium-sulfur battery positive electrode material comprises a carbon material and a high-entropy alloy oxide, wherein the carbon material is used as a conductive substrate, so that the conductivity of the lithium-sulfur battery positive electrode material is improved; the high-entropy alloy oxide has strong polarity, has strong adsorption performance on polysulfide which is a charging and discharging intermediate product of the lithium-sulfur battery, and prevents the polysulfide from being dissolved in electrolyte; the high-entropy alloy oxide has high stability, so that the cycling stability of the lithium-sulfur battery is improved.
Description
Technical Field
The application relates to the field of electrochemical energy storage, in particular to a lithium-sulfur battery positive electrode material, a preparation method of the lithium-sulfur battery positive electrode material and a lithium-sulfur battery comprising the lithium-sulfur battery positive electrode material.
Background
With the continuous development of human society, people have increasingly vigorous demand for energy, and the energy has become one of the pillars of modern society. The development of energy sources and energy storage devices should supplement each other, and the development of new energy vehicles is a great trend recently, so that it is necessary to develop energy storage devices with high energy density, safety and durability. The lithium-sulfur battery has a high theoretical specific capacity of 1675mAh/g and a high energy density of 2600Wh/kg, however the "shuttling effect" of polysulfides causes a rapid decay of the capacity of the lithium-sulfur battery.
By constructing a suitable sulfur carrier, the active substance can be anchored to the carrier to inhibit the dissolution and shuttling of polysulfides. Among them, carbon-based supports tend to have excellent electron transport ability and large specific surface area and pore volume to be widely used. However, the non-polar nature of the carbon-based support results in poor chemical affinity with the intermediate polysulfide, making it difficult to suppress the dissolution of the polysulfide in the electrolyte. The metal compound can chemically adsorb polysulfide and inhibit the dissolution process of the polysulfide, but most of the metal compounds have poor stability in the charging and discharging processes, so that the cycle stability of the lithium-sulfur battery is reduced.
Disclosure of Invention
In order to solve the deficiencies of the prior art, it is necessary to provide a positive electrode material of a lithium sulfur battery with strong chemical affinity with polysulfide as an intermediate product and good stability, so as to solve the above problems.
In addition, a preparation method of the lithium-sulfur battery positive electrode material is also needed to be provided.
In addition, a lithium-sulfur battery is also needed.
A lithium-sulfur battery positive electrode material comprising a carbon material, a high-entropy alloy oxide supported on the surface of the carbon material, and sulfur filling pores between the carbon material and the high-entropy alloy oxide or supported on the surface of the carbon material and/or the high-entropy alloy oxide.
In some embodiments of the present application, the high entropy alloy oxide accounts for 0.5% -30% of the total mass of the lithium sulfur battery positive electrode material.
In some embodiments of the present application, the metal element in the high entropy alloy oxide is selected from at least five of copper, ferrous iron, cobalt, manganese, nickel, zinc, magnesium, tin, titanium, chromium, vanadium, molybdenum, and zirconium.
In some embodiments of the present application, the high entropy alloy oxide has a particle size of 2nm to 500 nm.
In some embodiments of the present application, the sulfur comprises 30% to 90% of the total mass of the lithium sulfur battery positive electrode material.
A preparation method of a lithium-sulfur battery positive electrode material comprises the following steps:
mixing a solvent, a carbon material, a precipitant and at least five metal salts to obtain a dispersion liquid;
carrying out hydrothermal reaction on the dispersion liquid to obtain precursor powder;
calcining the precursor powder to obtain a high-entropy alloy oxide loaded by a carbon material; and
and mixing the high-entropy alloy oxide loaded by the carbon material with sulfur, and calcining to obtain the lithium-sulfur battery cathode material.
In some embodiments of the present application, the dispersion further comprises a surfactant having a hydrophilic group and a co-surfactant comprising an alcohol compound.
In some embodiments of the present application, the concentration of the metal salt in the dispersion is 0.01mol L-1-5mol·L-1The concentration of the surfactant in the dispersion is 0.5 mol-L-1-10mol·L-1The carbon material is contained in the dispersion at a concentration of 0.01 g-L-1-100g·L-1。
In some embodiments of the present application, the temperature of the hydrothermal treatment is 60 ℃ to 200 ℃ and the time is 2h to 48 h; the temperature of the high-entropy alloy oxide and sulfur loaded on the carbon material after calcination treatment is 100-300 ℃, and the time is 2-48 h.
A lithium sulfur battery comprising the lithium sulfur battery positive electrode material as described above.
The lithium-sulfur battery positive electrode material comprises a carbon material and a high-entropy alloy oxide, wherein the carbon material is used as a conductive substrate, so that the conductivity of the lithium-sulfur battery positive electrode material is improved; the high-entropy alloy oxide has strong polarity, has strong adsorption effect on polysulfide which is a charging and discharging intermediate product of the lithium-sulfur battery, and prevents the polysulfide from being dissolved in electrolyte; the high-entropy alloy oxide has high stability, so that the cycling stability of the lithium-sulfur battery is improved. According to the method, the high-entropy alloy oxide grows on the surface of the carbon material in situ through a hydrothermal method, the binding force of the high-entropy alloy oxide and the carbon material is strong, and the stability of the lithium-sulfur battery cathode material in the charging and discharging process can be further improved.
Drawings
Fig. 1 is a scanning electron microscope test chart of a lithium sulfur battery cathode material according to an embodiment of the present application.
Fig. 2 is a flow chart of a method for preparing a positive electrode material of a lithium-sulfur battery provided by the present application.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
The application provides a lithium-sulfur battery positive electrode material, which comprises a carbon material, a high-entropy alloy oxide and sulfur, wherein the high-entropy alloy oxide is loaded on the surface of the carbon material, and the sulfur is filled in pores between the carbon material and the high-entropy alloy oxide or loaded on the surface of the carbon material and/or the high-entropy alloy oxide.
The high-entropy alloy oxide is a combined crystal lattice formed by five or more than five metal oxides of different metal elements with equal or near equal moles, has a single-phase crystal structure, has very different crystal structures of the metal oxides of the metal elements, does not have any obvious orderliness at positions in the crystal, is also called high entropy, and can prevent the migration of defects in the crystal lattice due to disordered arrangement, so that the high stability of the high-entropy alloy oxide in the charging and discharging process can be maintained.
The carbon material has good conductivity, and is favorable for improving the conductivity of the lithium-sulfur battery anode material as a substrate material. The high-entropy alloy oxide has strong polarity, good affinity with polysulfide of a charging and discharging intermediate product of a lithium-sulfur battery, and strong adsorption effect, so that the dissolution of the polysulfide is inhibited; the shuttle high-entropy alloy oxide has good stability, and can still maintain good stability in the charging and discharging processes.
The metal elements in the high-entropy alloy oxide include, but are not limited to, at least five of copper, ferrous iron, cobalt, manganese, nickel, zinc, magnesium, tin, titanium, chromium, vanadium, molybdenum, and zirconium. The high-entropy alloy oxide accounts for 0.5-30% of the total mass of the lithium-sulfur battery cathode material. The inventor of the application finds that when the high-entropy alloy oxide accounts for less than 0.5% of the total mass of the lithium-sulfur battery cathode material, the adsorption effect of the lithium-sulfur battery cathode material on polysulfide as an intermediate product is weak, so that the energy attenuation of the lithium-sulfur battery is fast; when the high-entropy alloy oxide accounts for more than 30% of the total mass of the lithium-sulfur battery cathode material, the conductivity of the lithium-sulfur battery cathode material is reduced.
Further, the grain size of the high-entropy alloy oxide is 2nm-500 nm. In one embodiment of the present application, referring to fig. 1, the high-entropy alloy oxide includes five metal elements of cobalt, copper, ferrous iron, manganese and nickel, the high-entropy alloy oxide is supported on the surface of the carbon nanotube in a granular form, and the grain size of the high-entropy alloy oxide is about 10 nm.
The mass of the sulfur accounts for 30-90% of the total mass of the lithium-sulfur battery positive electrode material.
Referring to fig. 2, an embodiment of the present application provides a method for preparing a positive electrode material of a lithium-sulfur battery, including the following steps:
step S1: mixing solvent, carbon material, surfactant, cosurfactant, precipitant and at least five metal salts to obtain a dispersion liquid.
Specifically, the solvent and the cosurfactant are mixed according to a certain volume ratio, the surfactant is added, and then the carbon material, the metal salt and the precipitant are added to obtain the dispersion liquid.
The solvent includes an organic solvent as well as an inorganic solvent. Wherein the organic solvent is used for dissolving a surfactant, a cosurfactant and a precipitating agent, and the inorganic solvent is used for dissolving the metal salt. The organic solvent is miscible with the inorganic solvent, so that the metal salt and the carbon material are in full contact, and the high-entropy alloy oxide is favorably grown on the surface of the carbon material.
In one embodiment of the present application, the organic solvent is ethanol, and the inorganic solvent is water.
The co-surfactant typically comprises an alcohol compound, such as ethylene glycol. In one embodiment, the volume ratio of water, ethanol and glycol is (15% -40%): (15% -40%): (20% -70%).
The surfactant has a hydrophilic group, e.g., -OH, -CHO, -COOH, -NH2、-SO3H and the like, and the hydrophilic group is beneficial to fully mixing and contacting the organic matters and the inorganic matters in the dispersion liquid, and is beneficial to the subsequent hydrothermal reaction. In a specific embodiment herein, the surfactant is polyethylene glycol-polypropylene glycol-polyethylene glycol.
The surfactant and the cosurfactant are beneficial to uniform and stable distribution of metal salt and a precipitator in the dispersion liquid, and are beneficial to uniformly loading the subsequently generated high-entropy alloy oxide on the surface of the carbon material, so that the high-entropy alloy oxide with larger grain diameter is prevented from being generated.
Further, the concentration of the surfactant in the dispersion liquid was 0.5mol · L-1-10mol·L-1。
The carbon material comprises at least one of graphene and carbon nano-tubes, and is used as a substrate for in-situ growth of the high-entropy alloy oxide to improve the conductivity of the lithium-sulfur battery positive electrode material, wherein the concentration of the carbon material in the dispersion liquid is 0.01 g-L-1-100g·L-1。
The metal salt includes acetate, chloride, sulfate and nitrate, and the metal element in the metal salt includes but is not limited to at least five of copper, ferrous iron, cobalt, manganese, nickel, zinc, magnesium, tin, titanium, chromium, vanadium, molybdenum and zirconium. For example, in a specific embodiment of the present application, the metal salt may be selected from at least five of copper acetate, ferrous acetate, cobalt acetate, manganese acetate, nickel acetate, zinc acetate, magnesium acetate, tin acetate, titanium acetate, chromium acetate, vanadium acetate, molybdenum acetate, and zirconium acetate; it is to be understood that in another embodiment, the metal salt may be selected from at least five of copper chloride, ferrous chloride, cobalt chloride, manganese chloride, nickel chloride, zinc chloride, magnesium chloride, tin chloride, titanium chloride, chromium chloride, vanadium chloride, molybdenum chloride, and zirconium chloride.
Further, the concentration of the metal salt in the dispersion was 0.01 mol. L-1-5mol·L-1。
The precipitating agent is an organic precipitating agent, the precipitating agent is used for generating precipitates with metal ions in the dispersion liquid, and the precipitates take the carbon material as a substrate and are loaded on the surface of the carbon material.
Step S2: and carrying out hydrothermal reaction on the dispersion liquid to obtain precursor powder.
Specifically, the dispersion liquid is moved to a polytetrafluoroethylene reaction kettle, the reaction kettle is placed in an explosion-proof oven and is kept at the temperature of 60-200 ℃ for 2-48 h, at least five metal salts form a high-entropy metal oxide precursor in a hydrothermal environment, the high-entropy metal oxide precursor is loaded on the surface of the carbon material and precipitates, the precipitate is cleaned by water and ethanol to obtain a clean precipitate, and the precipitate is placed in the oven and dried to obtain precursor powder. Wherein, various metal salts form corresponding metal oxides, and various metal oxides form composite oxides among each other.
Step S3: and calcining the precursor powder to obtain the high-entropy alloy oxide loaded by the carbon material.
And (3) calcining the precursor powder in a muffle furnace, keeping the temperature of 380-450 ℃ for 1-10 h, and crystallizing the composite metal oxide at high temperature to obtain the high-entropy alloy oxide loaded by the carbon material.
Step S4: and mixing the high-entropy alloy oxide loaded by the carbon material with sulfur to calcine to obtain the lithium-sulfur battery cathode material.
Providing elemental sulfur, mixing and grinding the elemental sulfur and the high-entropy alloy oxide loaded on the carbon material according to the mass ratio of 1:1-9:1, then placing the mixture in a tubular furnace, and preserving heat for 2-48 h at the temperature of 100-300 ℃ in protective atmosphere (such as argon and nitrogen) to obtain the lithium-sulfur battery cathode material. In a specific embodiment of the application, the calcination procedure is to heat up to 155 ℃ at a heating rate of 2 ℃/min and keep the temperature for 10 hours; then heating to 220 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 30min, and finally naturally cooling to the room temperature.
The present application also provides a lithium-sulfur battery including the lithium-sulfur battery positive electrode material.
In an embodiment of the present application, the lithium sulfur battery includes a positive plate, an electrolyte, a diaphragm and a lithium plate, the diaphragm is located between the positive plate and the lithium plate, and the electrolyte soaks the positive plate, the diaphragm and the lithium plate. The positive electrode material of the lithium-sulfur battery, a conductive agent, a binder and a solvent are mixed according to a certain proportion and then coated on a positive electrode current collector, and the positive electrode plate is formed after drying. It is understood that a person skilled in the art may select a conductive agent, a binder, a solvent, and a positive electrode current collector, which are conventional in the art, as needed, without limitation.
The present application will be described below with reference to specific examples.
Example 1
Adding 0.4g of polyethylene glycol-polypropylene glycol-polyethylene glycol into a mixed solvent consisting of water, absolute ethyl alcohol and ethylene glycol, wherein the volume of the water is 5m L, the volume of the absolute ethyl alcohol is 10m L, and the volume of the ethylene glycol is 25m L, then adding 0.4g of carbon nano tube, stirring vigorously at room temperature, adding 0.2mmol of copper acetate, 0.2mmol of ferrous acetate, 0.2mmol of cobalt acetate, 0.2mmol of manganese acetate and 0.2mmol of nickel acetate, then adding 0.14g of hexamethylenetetramine, stirring vigorously for 45 minutes to obtain a dispersion liquid.
And transferring the dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal treatment for 15h at 170 ℃, washing precipitates obtained by the hydrothermal treatment for 3 times by using deionized water and absolute ethyl alcohol respectively, and then drying at 60 ℃ to obtain precursor powder.
And (3) putting the precursor powder into a muffle furnace, and calcining at 400 ℃ for 2 hours. Obtaining the high-entropy alloy oxide loaded by the carbon nano tube.
The mass ratio of the carbon nanotube-loaded high-entropy alloy oxide to elemental sulfur is 7: 3, fully grinding for 30min, putting the mixture into a tube furnace, heating to 155 ℃ at the speed of 2 ℃/min in an argon atmosphere, and preserving heat for 10 h; and then heating to 220 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min, and finally naturally cooling to obtain the lithium-sulfur battery cathode material.
Grinding and mixing the lithium-sulfur battery positive electrode material, a conductive agent and a binder in a mortar according to the mass ratio of 8:1:1, transferring the mixture into a weighing bottle, dropwise adding a proper amount of N-methyl pyrrolidone (NMP), stirring for 4 hours to obtain slurry, coating the slurry on a carbon-coated aluminum foil by using a scraper, drying for 12 hours in a vacuum oven at the temperature of 60 ℃, and punching to obtain a positive electrode plate.
The positive plate is assembled into the button cell in a glove box filled with argon according to the following sequence that a positive shell, a gasket, the positive plate, electrolyte, a diaphragm, electrolyte, a lithium plate, the gasket, an elastic sheet and a negative shell are arranged, the electrolyte on two sides of the diaphragm is 20 mu L, wherein the solvent in the electrolyte is a mixed solvent of ethylene glycol dimethyl ether (DME) and 1, 3-dioxolane (DO L) in a volume ratio of 1:1, the lithium salt in the electrolyte is 1M bis (trifluoromethyl) sulfimide lithium (L iTFSI), and the additive is 1% of L iNO3. The subsequent positive casing was compacted at the bottom and negative casing at the top using a button cell sealer for testing. And (3) carrying out cycle performance test on the assembled button cell, wherein the charge-discharge current density of the cycle test is 1.67A/g (1C), and the cycle number is 500 circles.
Example 2
The difference from example 1 is: the metal salt is copper acetate 0.2mmol, ferrous acetate 0.2mmol, cobalt acetate 0.2mmol, zinc acetate 0.2mmol, nickel acetate 0.2 mmol.
The rest is the same as embodiment 1, and is not described herein again.
Example 3
The difference from example 1 is: 0.2mmol of copper acetate, 0.2mmol of ferrous acetate, 0.2mmol of cobalt acetate, 0.2mmol of magnesium acetate and 0.2mmol of nickel acetate.
The rest is the same as embodiment 1, and is not described herein again.
Example 4
The difference from example 1 is: 0.2mmol of copper acetate, 0.2mmol of zinc acetate, 0.2mmol of cobalt acetate, 0.2mmol of magnesium acetate and 0.2mmol of nickel acetate.
The rest is the same as embodiment 1, and is not described herein again.
Example 5
The difference from example 1 is: 0.2mmol of copper acetate, 0.2mmol of zinc acetate, 0.2mmol of cobalt acetate, 0.2mmol of manganese acetate and 0.2mmol of nickel acetate.
The rest is the same as embodiment 1, and is not described herein again.
Example 6
The difference from example 1 is: 0.2mmol of copper acetate, 0.2mmol of zinc acetate, 0.2mmol of ferrous acetate, 0.2mmol of magnesium acetate and 0.2mmol of nickel acetate.
The rest is the same as embodiment 1, and is not described herein again.
Comparative example 1
The difference from example 1 is: 0.25mmol of cobalt acetate, 0.25mmol of ferrous acetate, 0.25mmol of zinc acetate and 0.25mmol of nickel acetate.
The rest is the same as embodiment 1, and is not described herein again.
Comparative example 2
The difference from example 1 is: 0.5mmol of zinc acetate and 0.5mmol of cobalt acetate.
The rest is the same as embodiment 1, and is not described herein again.
Referring to table 1, the main difference conditions for preparing the positive electrode material for a lithium sulfur battery according to examples 1 to 6 and comparative examples 1 to 2 are shown.
TABLE 1
Referring to table 2, the electrochemical performance test results of the assembled lithium sulfur batteries of examples 1 to 6 and comparative examples 1 to 2 are shown, respectively.
TABLE 2
As can be seen from the test results of table 2, the lithium sulfur battery positive electrode materials prepared in examples 1 to 6 assembled batteries have an initial gram capacity superior to that of comparative examples 1 to 2; after 500 cycles of charge and discharge, the capacity retention rate of the lithium-sulfur batteries in examples 1-6 is improved to a certain extent compared with that of comparative examples 1-2, which shows that the lithium-sulfur batteries prepared in examples 1-6 have good cycle stability. Please refer to example 2 and comparative example 1, wherein in example 2, compared to comparative example 1, the cycling stability of example 2 is improved to a certain extent by adding an additional metal element copper; comparing examples 4-5 and comparative example 2, examples 4-5 added three more metal elements, and their cycling stability was also improved, because the high-entropy alloy oxide can adsorb polysulfide and maintain higher stability during charging and discharging, which is beneficial to improving the cycling stability of lithium-sulfur battery.
The lithium-sulfur battery positive electrode material comprises a carbon material and a high-entropy alloy oxide, wherein the carbon material is used as a conductive substrate, so that the conductivity of the lithium-sulfur battery positive electrode material is improved; the high-entropy alloy oxide has strong polarity, has strong adsorption effect on polysulfide which is a charging and discharging intermediate product of the lithium-sulfur battery, and prevents the polysulfide from being dissolved in electrolyte; the high-entropy alloy oxide has high stability, so that the cycling stability of the lithium-sulfur battery is improved. According to the method, the high-entropy alloy oxide grows on the surface of the carbon material in situ through a hydrothermal method, the binding force of the high-entropy alloy oxide and the carbon material is strong, and the stability of the lithium-sulfur battery cathode material in the charging and discharging process can be further improved.
Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.
Claims (10)
1. A lithium-sulfur battery positive electrode material, characterized in that the lithium-sulfur battery positive electrode material comprises a carbon material, a high-entropy alloy oxide and sulfur, wherein the high-entropy alloy oxide is supported on the surface of the carbon material, and the sulfur is filled in pores between the carbon material and the high-entropy alloy oxide or is supported on the surface of the carbon material and/or the high-entropy alloy oxide.
2. The lithium sulfur battery cathode material according to claim 1, wherein the high-entropy alloy oxide accounts for 0.5-30% of the total mass of the lithium sulfur battery cathode material.
3. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the metal element in the high-entropy alloy oxide is at least five selected from the group consisting of copper, ferrous iron, cobalt, manganese, nickel, zinc, magnesium, tin, titanium, chromium, vanadium, molybdenum, and zirconium.
4. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the particle size of the high-entropy alloy oxide is 2nm to 500 nm.
5. The lithium sulfur battery positive electrode material according to claim 1, wherein the sulfur accounts for 30 to 90% of the total mass of the lithium sulfur battery positive electrode material.
6. A method for preparing a positive electrode material for a lithium-sulfur battery according to any one of claims 1 to 5, comprising the steps of:
mixing a solvent, a carbon material, a precipitant and at least five metal salts to obtain a dispersion liquid;
carrying out hydrothermal reaction on the dispersion liquid to obtain precursor powder;
calcining the precursor powder to obtain a high-entropy alloy oxide loaded by a carbon material; and
and mixing the high-entropy alloy oxide loaded by the carbon material with sulfur, and calcining to obtain the lithium-sulfur battery cathode material.
7. The method of claim 6, wherein the dispersion further comprises a surfactant and a co-surfactant, wherein the surfactant has a hydrophilic group, and the co-surfactant comprises an alcohol compound.
8. The method for producing a positive electrode material for a lithium-sulfur battery according to claim 7, wherein the concentration of the metal salt in the dispersion liquid is 0.01mol L-1-5mol·L-1The concentration of the surfactant in the dispersion is 0.5 mol-L-1-10mol·L-1The carbon material is contained in the dispersion at a concentration of 0.01 g-L-1-100g·L-1。
9. The preparation method of the positive electrode material of the lithium-sulfur battery according to claim 6, wherein the hydrothermal reaction is carried out at a temperature of 60 ℃ to 200 ℃ for 2h to 48 h; the temperature of the high-entropy alloy oxide and sulfur loaded on the carbon material after calcination treatment is 100-300 ℃, and the time is 2-48 h.
10. A lithium sulfur battery comprising the lithium sulfur battery positive electrode material according to any one of claims 1 to 5.
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Cited By (5)
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|---|---|---|---|---|
| CN111933926A (en) * | 2020-08-11 | 2020-11-13 | 中钢集团南京新材料研究院有限公司 | Lithium ion battery anode material precursor and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111933926A (en) * | 2020-08-11 | 2020-11-13 | 中钢集团南京新材料研究院有限公司 | Lithium ion battery anode material precursor and preparation method thereof |
| CN112331840A (en) * | 2020-11-02 | 2021-02-05 | 中钢集团南京新材料研究院有限公司 | Nickel-cobalt-rich high-entropy ceramic cathode material for lithium ion battery and preparation method thereof |
| CN113258050A (en) * | 2020-12-23 | 2021-08-13 | 天津工业大学 | Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof |
| KR20230133560A (en) * | 2022-03-11 | 2023-09-19 | 충북대학교 산학협력단 | Manufacturing method of hollow high entropy metal oxide for lithium sulfur battery |
| KR102614900B1 (en) * | 2022-03-11 | 2023-12-19 | 충북대학교 산학협력단 | Manufacturing method of hollow high entropy metal oxide for lithium sulfur battery |
| CN114717588A (en) * | 2022-04-11 | 2022-07-08 | 齐鲁理工学院 | High-entropy metal sulfide NiMnCoCuCrSxPreparation method of (1) |
| CN114717588B (en) * | 2022-04-11 | 2023-10-20 | 齐鲁理工学院 | High-entropy metal sulfide NiMnCoCuCrS x Is prepared by the preparation method of (2) |
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