MATERIAL WITH PINE-BRANCH LIKE SAMARIUM OXIDE/GRAPHENE/SULFUR GEL STRUCTURE, AND PREPARATION METHOD AND USE THEREOF

Abstract

A material with pine-branch like samarium oxide/graphene/sulfur gel structure, and a preparation method and use thereof. The material is reduced graphene oxide carrying pine-branch like samarium oxide on the surface to form a cross-linked gel structure, and sulfur is loaded on the gel structure. The preparation method includes: subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel. The material with pine-branch like samarium oxide/graphene/sulfur gel structure greatly improves the electrochemical performance of lithium-sulfur batteries.

Claims

1. A material with pine-branch like samarium oxide/graphene/sulfur gel structure, wherein reduced graphene oxide carries pine-branch like samarium oxide on the surface to form a cross-linked gel structure, and sulfur is loaded on the gel structure.

2. The material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 1, wherein the load of sulfur is 60-74.8 wt %.

3. The method for preparing a material with pine-branch like samarium oxide/graphene/sulfur gel structure, comprising subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

4. The method for preparing a material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 3, wherein the hydrothermal reduction comprises the steps of: mixing a graphene oxide colloidal solution and the samarium salt solution, adjusting the solution to a basic pH with aqueous ammonia, adding hydrazine hydrate, and heating to at least 160° C. and reacting while sealed.

5. The method for preparing a material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 3, wherein graphene oxide and the samarium salt are added at a ratio of 40:1-2 mg:μmol; or the hydrothermal reduction temperature is 175-185° C.; or the thermolysis temperature is 440-460° C.; or the inert atmosphere is argon atmosphere; or the weight ratio of sulfur to the reduced graphene oxide/pine-branch like samarium oxide gel is 4-5:1; or the sulfur is sublimed sulfur.

6. The method for preparing a material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 3, wherein the melting and diffusing comprises, after the sulfur is mixed with graphene oxide/pine-branch like samarium oxide gel uniformly, heating to 110-120° C. and then heating to 150-160° C.

7. A method comprising producing lithium-sulfur batteries with the material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 1 or the material with pine-branch like samarium oxide/graphene/sulfur gel structure prepared by the method of subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

8. The method comprising producing lithium-sulfur batteries with the material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 7, wherein a cathode material of a lithium-sulfur battery is prepared.

9. A battery cathode material, comprising the material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 1 or the material with pine-branch like samarium oxide/graphene/sulfur gel structure prepared by the method of subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

10. A lithium-sulfur battery, having an anode that is lithium, and a cathode that is the material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 1, the material with pine-branch like samarium oxide/graphene/sulfur gel structure prepared by the method of subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure, or the battery cathode material comprising the material with pine-branch like samarium oxide/graphene/sulfur gel structure according to claim 1 or the material with pine-branch like samarium oxide/graphene/sulfur gel structure prepared by the method of subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings of this specification forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and descriptions thereof are used to explain the present invention but do not constitute an improper limitation on the present invention.

[0020] FIG. 1 shows an XRD pattern of the pine-branch like samarium oxide/graphene gel in Example 1 of the present invention.

[0021] FIG. 2 shows an SEM image of the pine-branch like samarium oxide/graphene/sulfur gel in Example 1 of the present invention.

[0022] FIG. 3 shows a TGA profile of the pine-branch like samarium oxide/graphene/sulfur gel in Example 1 of the present invention.

[0023] FIG. 4 shows a CV curve of the battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel in Example 1 of the present invention.

[0024] FIG. 5 shows a charge and discharge curve of the battery cathode material in Example 1 of the present invention, in which a is 0.5C, and b is 1C.

[0025] FIG. 6 compares the charge and discharge cycles of the battery cathode of pine-branch like samarium oxide/graphene/sulfur gel in Example 1 of the present invention and the battery cathode of the graphene/sulfur gel in Comparative Example 1, in which the test condition is 0.5C.

DETAILED DESCRIPTION

[0026] It should be noted that the following detailed descriptions are all illustrative and are intended to provide further descriptions of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those usually understood by a person of ordinary skill in the art to which the present invention belongs.

[0027] It should be noted that the terms used herein are merely used for describing specific implementations, and are not intended to limit exemplary implementations of the present invention. As used herein, the singular form is also intended to include the plural form unless the present invention clearly dictates otherwise. In addition, it should further be understood that, terms “comprise” and/or “include” used in this specification indicate that there are features, steps, operations, components, assemblies, and/or combinations thereof.

[0028] In view of the technical problems that existing cathode materials of lithium-sulfur batteries have low conductivity, low stability, and poor cycle performance, and that lithium-sulfur batteries have low sulfur load and low cycle life, the present invention provides a material with pine-branch like samarium oxide/graphene/sulfur gel structure, and a preparation method and use thereof.

[0029] In a typical implementation of the present invention, a material with pine-branch like samarium oxide/graphene/sulfur gel structure is provided. in which reduced graphene oxide carries pine-branch like samarium oxide on the surface to form a cross-linked gel structure, and sulfur is loaded on the gel structure.

[0030] The gel in the present invention has a large number of active sites, and can greatly enhance the sulfur load. The net-like cross-linked structure can buffer the volume change of sulfur during the charge and discharge process of the battery. Moreover, the pine-branch like samarium oxide can effectively adsorb the polysulfides, inhibit the dissolution of polysulfides, and promote the reaction of lithium polysulfides, thus greatly improving the electrochemical performance of the lithium-sulfur battery.

[0031] In one or some embodiments of this implementation, the load of sulfur is 60-74.8 wt %.

[0032] In another implementation of the present invention, a method for preparing a material with pine-branch like samarium oxide/graphene/sulfur gel structure is provided. The method comprises subjecting graphene oxide and a samarium salt to hydrothermal reduction to prepare a reduced graphene oxide/samarium precursor; under an inert atmosphere, thermolysing the reduced graphene oxide/samarium precursor to obtain a reduced graphene oxide/pine-branch like samarium oxide gel; and melting and diffusing the sulfur onto the reduced graphene oxide/pine-branch like samarium oxide gel, to obtain the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

[0033] In the present invention, a reduced graphene oxide gel structure with a large number of active sites is obtained by hydrothermal reduction and thermolysis thereby improving the electrochemical performance of the material. When a nanomaterial is prepared by a traditional hydrothermal method, impurities are usually produced. However, no impurities are produced in the hydrothermal reduction process in the present invention, and the operations are simple, environmental friendly and safe.

[0034] The samarium salt in the present invention refers to a compound with a cation that is a samarium ion, for example, samarium nitrate, samarium chloride, samarium sulfate and so on. When samarium nitrate is used, the effect of the prepared material is much better.

[0035] In one or some embodiments of this implementation, the hydrothermal reduction comprises the steps of: mixing a graphene oxide colloidal solution and the samarium salt solution, adjusting the solution to a basic pH with aqueous ammonia, adding hydrazine hydrate, and heating to at least 160° C. and reacting while sealed. Use of the graphene oxide colloidal solution and the samarium salt solution allows graphene oxide and samarium salt to be mixed more evenly, so that the reduced graphene oxide can bind more samarium oxide.

[0036] In this series of embodiments, the graphene oxide colloidal solution is prepared by adding water to graphene oxide and ultrasonically treating.

[0037] In this series of embodiments, the concentration of the samarium salt solution is 0.8-1.6 mmol L.sup.−1. the concentration of the samarium salt solution is, for example, 0.8, 1.2, or 1.6 mmol L.sup.−1.

[0038] In this series of embodiments, the concentration of aqueous ammonia is 20-30 wt %.

[0039] In this series of embodiments, the pH is adjusted to 10-11.

[0040] In order to prevent the production of a large amount of gas and heat caused by too fast addition of hydrazine hydrate to affect the progress of the reaction, in this series of embodiments, hydrazine hydrate is added at a rate of 15˜25 μL/min.

[0041] In this series of embodiments, the weight ratio of graphene oxide to hydrazine hydrate is 1:1.3-1.4.

[0042] In one or some embodiments of this implementation, graphene oxide and the samarium salt are added at a ratio of 40:1-2 mg:μmol.

[0043] In one or some embodiments of this implementation, the hydrothermal reduction temperature is 175-185° C.

[0044] In one or some embodiments of this implementation, the thermolysis temperature is 440-460° C.

[0045] The inert atmosphere described in the present invention is a gas atmosphere provided by, for example, nitrogen, and argon, etc to prevent the oxidation by oxygen. In one or some embodiments of this implementation, the inert atmosphere is argon atmosphere, to provide a better effect.

[0046] In one or some embodiments of this implementation, the weight ratio of sulfur to the reduced graphene oxide/pine-branch like samarium oxide gel is 4-5:1.

[0047] In one or some embodiments of this implementation, the sulfur is sublimed sulfur. The purity of sublimed sulfur is higher to ensure that more sulfur is loaded.

[0048] In one or some embodiments of this implementation, the melting and diffusing comprises, after the sulfur is mixed with graphene oxide/pine-branch like samarium oxide gel uniformly, heating to 110-120° C.; and then heating to 150-160° C.

[0049] In order to mix sulfur with graphene oxide/pine-branch like samarium oxide gel more uniformly, in this series of embodiments, sulfur is ground and mixed with graphene oxide/pine-branch like samarium oxide gel.

[0050] In this series of embodiments, the treatment time at 110-120° C. is 0.5-1.5 hrs.

[0051] In this series of embodiments, the treatment time at 150-160° C. is 10-14 hrs.

[0052] In a third implementation of the present invention, use of the material with pine-branch like samarium oxide/graphene/sulfur gel structure in the preparation of lithium-sulfur batteries is provided. Especially when it is used as a cathode material in a lithium-sulfur battery, the electrochemical performance of the lithium-sulfur battery can be greatly improved.

[0053] In a fourth implementation of the present invention, a battery cathode material is provided, which comprises the material with pine-branch like samarium oxide/graphene/sulfur gel structure.

[0054] In a fifth implementation of the present invention, a lithium-sulfur battery is provided, which has an anode that is lithium, and a cathode that is the material with pine-branch like samarium oxide/graphene/sulfur gel structure or a battery cathode material.

[0055] To enable those skilled in the art to more clearly understand the technical solutions of the present invention, the technical solutions of the present invention will be described in detail below in conjunction with specific examples.

Example 1

[0056] (1) Preparation of reduced graphene oxide/samarium precursor: 80 mg of graphene oxide was weighed and placed in a 100 mL beaker. Then 40 mL of deionized water was added, and ultrasonicated for 2 hrs. 2.5 mL of 1.6 mmol L.sup.−1 samarium nitrate aqueous solution was transferred to a 100 mL beaker, and the graphene oxide colloidal solution was slowly added to the samarium nitrate solution dropwise and mixed well by stirring for 2 hrs to obtain a mixture. 25 wt % aqueous ammonia was added dropwise until the pH was 10. Then, 1.3 mL of 85 mg mL.sup.−1 hydrazine hydrate solution was added dropwise at a rate of 100 microliters every 5 minutes with stirring. The solution was transferred to a reactor and reacted at 180° C. for 6 hrs. The reaction product was cooled naturally, centrifuged, washed, frozen, and freeze drying, to obtain the reduced graphene oxide/samarium precursor gel.

[0057] (2) Preparation of pine-branch like samarium oxide/graphene gel: The reduced graphene oxide/samarium precursor gel was placed in a corundum reaction boat, and high-purity argon was filled in a tubular furnace as a protective gas. The system was heated 450° C., and reacted for 3 hrs. After the reaction system was cooled naturally, a pine-branch like samarium oxide/graphene gel was obtained.

[0058] (3) Battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel: 10 mg of pine-branch like samarium oxide/graphene gel and 40 mg of sublimed sulfur were mixed, fully ground, transferred to a reactor, heated to 115° C. and reacted for 1 hr, and then further heated to 155° C. and reacted for 12 hrs, to obtain a battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel.

[0059] The performance of the prepared battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel was tested. FIG. 1 shows an XRD pattern of the pine-branch like samarium oxide/graphene gel in Example 1. It can be seen from FIG. 1 that after the hydrothermal reaction and the in-situ thermolysis reaction, no other impurity peaks appear. The final sample is samarium oxide/graphene gel.

[0060] FIG. 2 shows an SEM image of the pine-branch like samarium oxide/graphene/sulfur gel material in Example 1. It can be seen from FIG. 2 that pine-branch like samarium oxide is formed on the surface of the reduced graphene oxide and a cross-linked gel structure is formed.

[0061] FIG. 3 shows a TGA profile of the pine-branch like samarium oxide/graphene/sulfur gel material in Example 1. It can be seen from FIG. 3 that this gel structure can load up to 74.8% sulfur.

[0062] FIG. 4 shows a CV curve of the cathode material of pine-branch like samarium oxide/graphene/sulfur gel in Example 1. It can be seen from FIG. 4 that the battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel has good electrochemical performance.

[0063] FIG. 5 shows a charge and discharge curve of the battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel in Example 1. It can be seen from FIG. 5 that the battery cathode material of pine-branch like samarium oxide/graphene/sulfur gel has good charge and discharge performance.

Example 2

[0064] (1) Preparation of reduced graphene oxide/samarium precursor: 80 mg of graphene oxide was weighed and placed in a 100 mL beaker. Then 40 mL of deionized water was added, and ultrasonicated for 2 hrs. 2.5 mL of 1.2 mmol L.sup.−1 samarium nitrate aqueous solution was transferred to a 100 mL beaker, and the graphene oxide colloidal solution was slowly added to the samarium nitrate solution dropwise and mixed well by stirring for 2 hrs to obtain a mixture. 25 wt % aqueous ammonia was added dropwise until the pH was 10. Then, 1.3 mL of 85 mg mL.sup.−1 hydrazine hydrate solution was added dropwise at a rate of 100 microliters every 5 minutes with stirring. The solution was transferred to a reactor and reacted at 180° C. for 6 hrs. The reaction product was cooled naturally, centrifuged, washed, frozen, and freeze drying, to obtain the reduced graphene oxide/samarium precursor gel.

[0065] Steps (2) and (3) are the same as those in Example 1.

Example 3

[0066] (1) Preparation of reduced graphene oxide/samarium precursor: 80 mg of graphene oxide was weighed and placed in a 100 mL beaker. Then 40 mL of deionized water was added, and ultrasonicated for 2 hrs. 2.5 mL of 0.8 mmol L.sup.−1 samarium nitrate aqueous solution was transferred to a 100 mL beaker, and the graphene oxide colloidal solution was slowly added to the samarium nitrate solution dropwise and mixed well by stirring for 2 hrs to obtain a mixture. 25 wt % aqueous ammonia was added dropwise until the pH was 10. Then, 1.3 mL of 85 mg mL.sup.−1 hydrazine hydrate solution was added dropwise at a rate of 100 microliters every 5 minutes with stirring. The solution was transferred to a reactor and reacted at 180° C. for 6 hrs. The reaction product was cooled naturally, centrifuged, washed, frozen, and freeze drying, to obtain the reduced graphene oxide/samarium precursor gel.

[0067] Steps (2) and (3) are the same as those in Example 1.

[0068] The CV curve and charge-discharge performance of the lithium-sulfur battery in Examples 2 to 3 are tested to be similar to those of Example 1. All the batteries have good electrochemical performance.

Comparative Example 1

[0069] (1) Preparation of reduced graphene oxide: 80 mg of graphene oxide was weighed and placed in a 100 mL beaker. Then 40 mL of deionized water was added, and ultrasonicated for 2 hrs. 25 wt % aqueous ammonia was added dropwise until the pH was 10. Then, 1.3 mL of 85 mg mL.sup.−1 hydrazine hydrate solution was added dropwise at a rate of 100 microliters every 5 minutes with stirring. The solution was transferred to a reactor and reacted at 180° C. for 6 hrs. The reaction product was cooled naturally, centrifuged, washed, frozen, and freeze drying, to obtain the reduced graphene oxide gel.

[0070] (2) Battery cathode material of graphene/sulfur gel: 10 mg of graphene gel and 40 mg of sublimed sulfur were mixed, fully ground, transferred to a reactor, heated to 115° C. and reacted for 1 hr, and then further heated to 155° C. and reacted for 12 hrs, to obtain a battery cathode material of graphene/sulfur gel.

[0071] FIG. 6 compares the charge and discharge cycle life of the battery cathode of pine-branch like samarium oxide/graphene/sulfur gel in Example 1 of the present invention and the battery cathode of the graphene/sulfur gel in the comparative example. As shown in FIG. 6, the presence of pine-branch like samarium oxide in the cathode material, can significantly increase the reversible charge and discharge capacity of the lithium-sulfur battery, resulting in a lithium-sulfur battery with better performance.

[0072] The foregoing descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. A person skilled in the art may make various alterations and variations to the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.