CN113707884A - 3D Mo2C-Mo3N2In-situ preparation method and application of/rGO heterostructure material - Google Patents

3D Mo2C-Mo3N2In-situ preparation method and application of/rGO heterostructure material Download PDF

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CN113707884A
CN113707884A CN202110695278.5A CN202110695278A CN113707884A CN 113707884 A CN113707884 A CN 113707884A CN 202110695278 A CN202110695278 A CN 202110695278A CN 113707884 A CN113707884 A CN 113707884A
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rgo
heterostructure material
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situ preparation
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罗永松
韩嘉慧
张德扬
王阳博
柏祖雪
郭英
张梦杰
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Xinyang Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses 3D Mo2C‑Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps: s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring; s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed; s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S1, and performing spray drying treatment by using the solution as a precursor solution of spray drying; s4: carbonizing the product obtained in the step S3 in a tube furnace; s5: the melamine and the product obtained from S4 are respectively placed in the upstream and middle parts of a tube furnace and nitridedReacting to obtain 3D Mo2C‑Mo3N2a/rGO heterostructure material. The prepared 3D Mo2C‑Mo3N2the/rGO sample has good controllability and high crystallinity. The positive electrode material applied to the lithium-sulfur battery shows excellent rate performance and cycle performance.

Description

3D Mo2C-Mo3N2In-situ preparation method and application of/rGO heterostructure material
Technical Field
The invention relates to the field of synthesis of nano materials and electrochemical energy storage, in particular to 3D Mo2C-Mo3N2An in-situ preparation method and application of/rGO heterostructure material.
Background
In recent years, with the rapid development of portable mobile devices and electric automobiles, development of secondary battery systems with higher energy density has become urgent. At present, although the specific energy of the lithium ion battery reaches 250Wh/kg, the specific energy is limited by the low theoretical specific capacity of the anode material, and the specific energy is difficult to be greatly improved, so that a new battery system is imperative to be developed. In a new battery system, a lithium-sulfur battery system constructed by taking lithium metal as a negative electrode and taking sulfur elementary substance as a positive electrode has the advantages that the theoretical specific capacity is up to 1675mAh/g, the theoretical specific energy is up to 2600Wh/kg, and the theoretical specific energy is more than 5 times that of a common commercial lithium ion battery. In addition, sulfur is a non-polluting, environmentally friendly element, which is abundant, light in weight and inexpensive. Lithium-sulfur batteries are therefore considered to be one of the most currently studied secondary battery systems.
The charging and discharging principle of the lithium-sulfur battery is as follows: during discharging, the negative electrode reacts to enable lithium to lose electrons and become lithium ions, the positive electrode reacts to enable sulfur, the lithium ions and the electrons to react to generate sulfide, and the potential difference between the positive electrode and the negative electrode is the discharging voltage provided by the lithium sulfur battery. Under the action of an applied voltage, the reaction of the positive electrode and the negative electrode of the lithium-sulfur battery is carried out reversely, namely, the charging process is carried out. According to the capacity which can be provided by completely changing the elemental sulfur of unit mass into S, the theoretical specific discharge mass capacity of the sulfur is 1675mAh/g, and similarly, the theoretical specific discharge mass capacity of the elemental lithium is 3860mAh/g. The theoretical discharge voltage of a lithium-sulfur battery is 2.287V, and lithium sulfide (Li) is generated when sulfur and lithium are completely reacted2S), the corresponding theoretical specific energy of discharge mass is 2600 Wh/kg.
However, the lithium-sulfur battery is still under research, and there are some problems in large-scale use, that is, (1) shuttle effect of polysulfide, which is caused by concentration difference between positive and negative electrodes of the battery when lithium polysulfide is dissolved in organic electrolyte, resulting in shuttle effect between the positive and negative electrodes. Low lithium sulfide (Li) with electronic insulation due to shuttle effect2S/Li2S2) The lithium is generated on the surface of the negative electrode, so that the ion conduction capability is reduced, and a large amount of active substances are lost, thereby reducing the capacity of the battery and shortening the service life of the battery; (2) elemental sulfur is an electronic and ionic insulator, and the utilization rate of active substances as an electrode material is low, so that the actual specific capacity of the sulfur electrode is reduced: (3) during the charging and discharging process, the conversion of elemental sulfur and sulfide can change the volume of the positive electrode, so that the capacity of the battery is attenuated, and even the structure of the battery is damaged. The "shuttling effect" of polysulfides among others severely limits the commercial application of lithium sulfur batteries. Commercialization of lithium sulfur cells can therefore only be achieved by suppressing the "shuttling effect" of polysulfides while promoting the conversion of polysulfides to enhance the electrochemical and kinetic performance of lithium sulfur cells.
Some researchers use carbon materials to adsorb discharge products LiPSs of sulfur, inhibit the dissolution of the discharge products LiPSs in electrolyte, and achieve the purpose of weakening shuttle effect, so that the electrochemical performance of the lithium-sulfur battery is improved. Research shows that Mo2C has a strong adsorption capacity for polysulfides, but has a poor ability to catalyze the conversion of polysulfides. Mo3N2The catalyst is a widely-used catalyst, can effectively improve the catalytic capability of polysulfide, but has poor adsorption capability of polysulfide. If Mo can be converted into Mo2C and Mo3N2The above advantages are effectively combined, so that the shuttling effect of polysulfide can be inhibited, and the conversion of polysulfide can be promoted to improve the electrochemical and dynamic performances of the lithium-sulfur battery.
Based on the above considerations, we willMo2Partial nitration of C to Mo3N2And using rGO as a carbon matrix, thereby preparing Mo2C-Mo3N2the/rGO heterostructure material regulates and controls the adsorption and catalytic conversion performance of polysulfide, so that the redox kinetics of lithium polysulfide is accelerated, and the electrochemical performance of the lithium-sulfur battery is effectively improved.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the 3D Mo is provided2C-Mo3N2In-situ preparation method of/rGO heterostructure material and Mo prepared by same2C-Mo3N2/rGO heterostructure with Mo2Strong adsorption of C to polysulfide and Mo3N2Strong catalytic activity on polysulfide, thereby balancing the adsorption and catalytic conversion efficiency of polysulfide, and further improving the reaction kinetics of lithium-sulfur batteries. Simultaneously, rGO not only improves the conductivity of the sulfur anode, but also can be used as a protective layer to prevent the structure from being damaged in the circulating process. The 3D porous structure constructed by taking the PS spheres as the sacrificial template can realize high sulfur load, and the high sulfur load target of the lithium-sulfur battery is realized. Due to Mo2C-Mo3N2The existence of a heterogeneous interface and the balance of the adsorption and conversion behaviors of polysulfide so as to accelerate the overall redox kinetics of the battery and finally realize a lithium-sulfur battery system with high rate and long cycle life. This Mo2C-Mo3N2the/rGO heterostructure material also lays a foundation for the application of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the 3D Mo of the invention2C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the method comprises the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a precursor solution of spray drying;
s4: transferring the product obtained in the step S3 into a tube furnace, carrying out carbonization treatment under the protection of argon, and then naturally cooling to room temperature;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of the tube furnace, and carrying out in-situ nitridation under the protection of inert gas to finally obtain 3D Mo2C-Mo3N2a/rGO heterostructure material.
Preferably, in the step S1, the volume ratio of the mixed solution of deionized water and absolute ethyl alcohol is 3: 1;
preferably, the inlet temperature of the spray drying in the step S3 is 140 ℃, and the feeding speed is 600ml h < -1 >;
preferably, in the step S4, the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
preferably, in the step S5, the nitriding temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1;
has the advantages that: compared with the prior art, the invention has the following beneficial effects:
(1) 3D Mo of the invention2C-Mo3N2The in-situ preparation method of the/rGO heterostructure material has low requirements on preparation conditions, and the used nitrogen source (melamine) is cheap and easy to obtain;
(2) prepared 3D Mo2C-Mo3N2the/rGO heterostructure material has Mo2Strong adsorption of C to polysulfide and Mo3N2The catalyst has strong catalytic performance on polysulfide, so that the adsorption and catalytic conversion efficiency of the polysulfide are balanced, and the reaction kinetics of the lithium-sulfur battery are improved;
(3) prepared 3D Mo2C-Mo3N2the/rGO heterostructure material has Mo2C-Mo3N2Hetero-interface due to Mo2C and Mo3N2The difference in conductivity between the two electrodes is small, so that the interfaces have rapid electron shuttling, thereby being beneficial to improving the electrochemical performance of the lithium-sulfur battery.
(3) Prepared 3D Mo2C-Mo3N2the/rGO heterostructure material shows good rate capability and cycle capability as a sulfur positive electrode host material of a lithium-sulfur battery. At high rates of 1C and 2C, it was able to achieve specific capacities of 1230 and 940 mAh/g. Mo2C-Mo3N2Mo after 300 cycles of the/rGO electrode under the multiplying power of 0.5C2C-Mo3N2The capacity retention of/rGO @ S is 1365mAh/g, and the capacity loss rate is 0.084%.
Drawings
FIG. 1 shows Mo synthesized in example 2 of the present invention2C-Mo3N2XRD pattern of/rGO material;
FIG. 2 shows Mo synthesized in example 2 of the present invention2C-Mo3N2High resolution transmission electron microscopy of/rGO material;
FIG. 3 shows Mo synthesized in example 2 of the present invention2C-Mo3N2CV plot of/rGO material at 0.5mV s-1 scan rate;
FIG. 4 shows Mo synthesized in example 2 of the present invention2C-Mo3N2A multiplying power performance graph of the/rGO material under different current densities;
FIG. 5 shows Mo synthesized in example 2 of the present invention2C-Mo3N2Cycle plot of/rGO material at current density of 0.5C.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the embodiments and the drawings, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 3: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
Example 2:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
The 3D Mo prepared in this example2C-Mo3N2The XRD pattern of/rGO heterostructure material is shown in FIG. 1. The results show that: mo2C (JCPDS No.35-0787) and Mo3N2(JCPDS No.89-3712) the characteristic peak appears in Mo at the same time2C-Mo3N2XRD patterns of/rGO, thus proving that Mo is successfully prepared by the in-situ method2C-Mo3N2a/rGO heterostructure material. In addition, a peak exists near 26 degrees and corresponds to a carbon peak, and the existence of rGO is just proved.
FIG. 2 shows the 3D Mo prepared in this example2C-Mo3N2High resolution transmission electron microscopy of/rGO heterostructure materialsAnd (3) slicing. Two lattice fringes with a spacing of 0.26nm and 0.24nm appear in FIG. 2, which correspond to Mo, respectively2C (100) plane and Mo3N2The (111) plane of (1). FIG. 2 also shows Mo2C (100) plane and Mo3N2(111) A clear heterogeneous interface between the faces, which facilitates charge transport and accelerates the conversion rate of the LiPSs.
Mo at a scan rate of 0.1mV/s2C-Mo3N2The CV curve for/rGO @ S is shown in FIG. 3, which is a typical positive sulfur CV curve. The CV curve of the first cycle exhibited C-II and C-I reduction peaks at 2.286V and 2.110V, respectively, due to the reduction of sulfur to Li2Sx (x is more than or equal to 4 and less than or equal to 8) and further reduced into Li2S caused by. The oxidation peak (A-I) at 2.350V is represented by Li2Reversible oxidation of S to LiPSs or S8. In the subsequent cycles, the redox peaks overlapped with those of the first cycle, and no significant change was observed in the intensity of the peaks and the corresponding voltage positions, indicating that Mo2C-Mo3N2the/rGO @ S positive electrode has high electrochemical stability.
Mo2C-Mo3N2The rate performance of the/rGO @ S electrode is shown in fig. 4, and the test method is that the rate is increased from 0.1C to 2C in sequence and then restored to 0.1C for 10 cycles per cycle. Mo at cycle rates of 0.1, 0.2, 0.5, 1 and 2C2C-Mo3N2The specific discharge capacity of the/rGO @ S electrode is 1452, 1369, 1284, 1133 and 940mAh/g respectively. When the cycle rate was restored to 0.1C, the capacity was restored to 1392mAh/g, and these results indicate that Mo2C-Mo3N2the/rGO @ S positive electrode has excellent stability. Mo2C-Mo3N2The cycling profile of/rGO @ S at a current density of 0.5C is shown in fig. 5, with an initial capacity of 1365mAh/g, a capacity of 1250mAh/g after 300 cycles, and a capacity fade of 0.084% (calculated from cycle 2).
Example 3:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 1: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
Example 4:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 160 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
Example 5:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carrying out carbonization treatment under the protection of argon, and then naturally cooling to room temperature, wherein the carbonization temperature is 700 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 2 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
Example 6:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 700 ℃, the constant temperature time is 2 hours, the melamine and the step SThe mass ratio of the product obtained from S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.
Example 7:
the embodiment discloses a 3D Mo2C-Mo3N2The in-situ preparation method and the application of the/rGO heterostructure material comprise the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution, wherein the volume ratio of the mixed solution of the deionized water to the absolute ethyl alcohol is 3: 1;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a spray-dried precursor solution, wherein the inlet temperature of the spray drying is 140 ℃, and the feeding speed is 600ml h < -1 >;
s4: transferring the product obtained in the step S3 into a tube furnace, carbonizing under the protection of argon, and naturally cooling to room temperature, wherein the carbonization temperature is 800 ℃, and the constant temperature time is 5 hours;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of a tube furnace, and carrying out in-situ nitridation under the protection of inert gas, wherein the nitridation temperature is 800 ℃, the constant temperature time is 3 hours, and the mass ratio of the melamine to the product obtained in the step S4 is 1: 1, finally obtaining the 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material for lithium sulfur batteries.

Claims (9)

1. 3D Mo2C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the method comprises the following steps:
s1: uniformly dispersing polystyrene spheres into a mixed solution of deionized water and absolute ethyl alcohol, then respectively adding ammonium molybdate tetrahydrate and sucrose, and fully stirring to obtain a uniformly mixed solution;
s2: adding graphene oxide and hexadecyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment until the graphene oxide and the hexadecyl trimethyl ammonium bromide are uniformly dispersed;
s3: slowly adding the solution obtained in the step S2 into the solution obtained in the step S2, and then performing spray drying treatment by using the obtained mixed solution as a precursor solution of spray drying;
s4: transferring the product obtained in the step S3 into a tube furnace, carrying out carbonization treatment under the protection of argon, and then naturally cooling to room temperature;
s5: respectively placing melamine and the product obtained in the step S4 into the upstream part and the middle part of the tube furnace, and carrying out in-situ nitridation under the protection of inert gas to finally obtain 3D Mo2C-Mo3N2a/rGO heterostructure material.
S6: loading elemental sulfur on Mo by vacuum melting diffusion method2C-Mo3N2on/rGO and used as a positive electrode material to lithium sulfur batteries.
2. The 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the polystyrene spheres in the step S1 are prepared in an argon atmosphere by water bath at 80 ℃ and continuously stirring for 10 hours.
3. The 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: in the step S2, the graphene oxide is prepared by an improved Hummer method.
4. According to claim 1The 3D Mo2C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the volume ratio of the deionized water to the absolute ethyl alcohol mixed solution in the step S1 is 3: 1-1: 1.
5. the 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: in the step S2, the mass ratio of the graphene oxide to the cetyltrimethylammonium bromide is 1: 1.
6. the 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the inlet temperature of the spray drying in the step S3 is 120-160 ℃, and the feeding speed is 600-800 ml h < -1 >.
7. The 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the carbonization temperature in the step S4 is 800-900 ℃, and the constant temperature time is 3-5 h.
8. The 3D Mo of claim 12C-Mo3N2The in-situ preparation method of the/rGO heterostructure material is characterized by comprising the following steps: the nitriding temperature in the step S5 is 800-900 ℃, the constant temperature time is 1-3 h, and the mass ratio of melamine to the product obtained in the step S4 is 1: 1-1: 3.
9. 3D Mo prepared in situ for claim l2C-Mo3N2The application of the/rGO heterostructure material as a sulfur positive host material of the lithium-sulfur battery.
CN202110695278.5A 2021-06-23 2021-06-23 3D Mo2C-Mo3N2In-situ preparation method and application of/rGO heterostructure material Pending CN113707884A (en)

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