阅读说明：本技术 一种超级电容器用钼酸锰纳米线/石墨烯复合材料的设计合成方法 (Design and synthesis method of manganese molybdate nanowire/graphene composite material for supercapacitor ) 是由 孙嬿 李春生 毛子旺 朱珠 殷公社 杨晨 王笛笛 曾康钰 陈嘉巧 于 2021-02-19 设计创作，主要内容包括：本发明专利的目标产物主要应用于储能材料领域,具体涉及一种超级电容器用钼酸锰纳米线/石墨烯复合材料的设计合成方法。该技术以石墨烯、分析纯钼酸铵白色粉末及硝酸锰为反应原料,蒸馏水为溶剂和分散剂；借助微波辐射法可控合成结构规整、物相单一的钼酸锰纳米线/石墨烯三维纳米复合材料。产物的XRD、SEM及TEM分析结果测试表明其为纯相钼酸锰纳米线/石墨烯复合材料,是一种具有优良储能性能的电池材料。(The invention discloses a target product mainly applied to the field of energy storage materials, and particularly relates to a design and synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor. Graphene, analytically pure ammonium molybdate white powder and manganese nitrate are used as reaction raw materials, and distilled water is used as a solvent and a dispersing agent; the manganese molybdate nanowire/graphene three-dimensional nano composite material with a regular structure and a single phase can be controllably synthesized by a microwave radiation method. The XRD, SEM and TEM analysis results of the product show that the product is a pure-phase manganese molybdate nanowire/graphene composite material, and is a battery material with excellent energy storage performance.)

1. The invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which comprises the steps of respectively taking graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials, and taking distilled water as a solvent and a dispersing agent; the manganese molybdate nanowire/graphene three-dimensional nano composite material with a regular structure and a single phase can be controllably synthesized by a microwave radiation method, and the specific synthesis steps are as follows:

firstly, accurately weighing 12011201-model graphene powder material sold by 0.0010-10.0000 g of aladdin company under room temperature environment, wherein the graphene powder material has a thickness of 750m²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 25-250 mL quartz round-bottom flask, adding 10-100 mL distilled water, and stirring for 3-5 min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; the quartz round bottom flask was then placed in an atmospheric pressure micro-flask with reflux cooling deviceIn the microwave reactor, the microwave reactor is an improved microwave oven, the power of the microwave reactor is 200-1400W, the model is PJ21C-AU, the frequency is 2450MHz, the reaction raw materials are heated to 70-100 ℃, the reaction is continued for 1-10 h, the black graphene uniform slurry is obtained, and the black graphene uniform slurry is naturally cooled to the room temperature for later use;

secondly, 5.0000-15.0000 g of analytically pure ammonium molybdate white powder is weighed, added to the black graphene uniform slurry obtained in the pretreatment in the first step, and stirred for 0.5-3.0 hours to obtain uniform suspension;

thirdly, measuring 5-30 mL of 50 wt% manganese nitrate aqueous solution, wherein the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 10-150 mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5-1.5 h to obtain a uniform solution;

fourthly, adding the uniform solution obtained in the third step into a quartz round-bottom flask containing the suspension obtained in the second step, then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device in the first step, setting the power of the equipment to be 200-1400W, heating the solution to 70-100 ℃, and continuously reacting for 1-10 hours;

fifthly, naturally cooling the product obtained in the fourth step to room temperature, placing the product in a high-speed centrifuge with the speed of 5000-10000 rpm, setting the centrifugation time to be 1-10 min, washing the obtained precipitate with distilled water for 3-5 times, and placing the washed product in a forced air drying oven with the temperature of 50-80 ℃ for drying for 5-20 h to obtain the target manganese molybdate nanowire/graphene powder; the XRD, SEM and TEM analysis results of the sample prove that the material is a pure-phase manganese molybdate nanowire/graphene composite material.

[ summary of the invention ]: the invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which is characterized in that graphene, analytically pure ammonium molybdate white powder and manganese nitrate are respectively used as reaction raw materials, distilled water is used as a solvent and a dispersing agent, and a microwave radiation method is adopted to synthesize the manganese molybdate nanowire/graphene composite material.

[ technical solution of the present invention ]: the invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which comprises the steps of respectively taking graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials, and taking distilled water as a solvent and a dispersing agent; the manganese molybdate nanowire/graphene three-dimensional nano composite material with a regular structure and a single phase can be controllably synthesized by a microwave radiation method, and the specific synthesis steps are as follows:

firstly, accurately weighing 12011201-model graphene powder material sold by 0.0010-10.0000 g of aladdin company under room temperature environment, wherein the graphene powder material has a thickness of 750m²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 25-250 mL quartz round-bottom flask, adding 10-100 mL distilled water, and stirring for 3-5 min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved microwave oven, the power of the microwave reactor is 200-1400W, the model is PJ21C-AU, the frequency is 2450MHz, heating the reaction raw materials to 70-100 ℃, continuously reacting for 1-10 h to obtain black graphene uniform slurry,naturally cooling to room temperature for later use;

secondly, 5.0000-15.0000 g of analytically pure ammonium molybdate white powder is weighed, added to the black graphene uniform slurry obtained in the pretreatment in the first step, and stirred for 0.5-3.0 hours to obtain uniform suspension;

thirdly, measuring 5-30 mL of 50 wt% manganese nitrate aqueous solution, wherein the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 10-150 mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5-1.5 h to obtain a uniform solution;

fourthly, adding the uniform solution obtained in the third step into a quartz round-bottom flask containing the suspension obtained in the second step, then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device in the first step, setting the power of the equipment to be 200-1400W, heating the solution to 70-100 ℃, and continuously reacting for 1-10 hours;

fifthly, naturally cooling the product obtained in the fourth step to room temperature, placing the product in a high-speed centrifuge with the speed of 5000-10000 rpm, setting the centrifugation time to be 1-10 min, washing the obtained precipitate with distilled water for 3-5 times, and placing the washed product in a forced air drying oven with the temperature of 50-80 ℃ for drying for 5-20 h to obtain the target manganese molybdate nanowire/graphene powder; the XRD, SEM and TEM analysis results of the sample prove that the material is a pure-phase manganese molybdate nanowire/graphene composite material.

[ advantages and effects of the invention ]: the invention relates to a method for designing and synthesizing a manganese molybdate nanowire/graphene composite material for a supercapacitor, which has the following advantages and effects: (1) the reserves of molybdenum ore in China are abundant, the cost of molybdate is low, and the deep development of high-quality nanoscale manganese molybdate materials is deeply developed, so that the promotion of product upgrading and the vigorous development of supercapacitors is facilitated; (2) the manganese molybdate nanowire/graphene composite material is synthesized by a microwave radiation method, so that the crystal form and the dimensionality of the target manganese molybdate can be effectively controlled; (3) the synthesis method disclosed by the invention can be used for obtaining the pure-phase manganese molybdate nanowire/graphene, and is characterized by regular morphology and single phase, and the electrochemical performance of the supercapacitor can be improved.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) spectrum of a homogeneous slurry of black graphene in sample 1

FIG. 2 is an SEM image of the composite material of sample 1 at a magnification of 1.3 ten thousand

FIG. 3 is an SEM image of the composite material of sample 1 at 2.5 ten thousand times magnification

FIG. 4 is an SEM image of the composite material of sample 1 at a magnification of 5 ten thousand

FIG. 5 is an SEM image of the composite material of sample 1 at a magnification of 10 ten thousand

FIG. 6 is a projection electron microscope (TEM) spectrum of the composite material in sample 1

Detailed Description

Example 1: preparation of manganese molybdate nanowire/graphene composite sample 1

A graphene powder material model 12011201 sold by the company aladdin, 0.0100g, was accurately weighed in a room temperature environment, and had a particle size of 750m²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 250mL quartz round-bottom flask, adding 50mL distilled water, and stirring at a high speed for 4min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is a modified microwave oven, the power of the microwave reactor is 1000W, the model is PJ21C-AU, the frequency is 2450MHz, heating the reaction raw materials to 80 ℃, continuously reacting for 8 hours to obtain black graphene uniform slurry, and naturally cooling to room temperature for later use; as shown in fig. 1, the monodisperse graphene is a net structure, and obtains a uniform sheet-like regular morphology with a thickness of 25nm, which provides a basis for performance optimization of the supercapacitor composite material of the invention patent; secondly, weighing 10.5000g of analytically pure ammonium molybdate white powder, adding the powder to the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; then 14.0mL of 50 wt% manganese nitrate aqueous solution is measured, the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 25mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5h to obtain a uniform solution; adding the homogeneous solution to the suspensionPutting the turbid liquid in a quartz round-bottom flask, heating the turbid liquid in a normal-pressure microwave reactor with a reflux cooling device in the first step to 80 ℃, and continuously reacting for 8 hours; finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifuge with 9000rpm, setting the centrifugation time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a forced air drying oven with the temperature of 80 ℃ for drying for 12h to obtain a target manganese molybdate nanowire/graphene powder sample 1; XRD testing of the sample showed: the product corresponds to JCPDS 39-84; the SEM images of the sample are shown in figures 2-5, the sample is uniform in morphology and size, and lamellar graphene is uniformly distributed on the surface of a manganese molybdate material, so that the improvement of electron conductivity is facilitated; as shown in fig. 6, which is a TEM spectrum of the sample, it was confirmed that the crystallinity of the material was excellent and the lattice fringes were clear. Therefore, the pure-phase manganese molybdate nanowire/graphene composite material can be obtained by the method

Example 2: preparation of manganese molybdate nanowire/graphene composite sample 2

A graphene powder material sold by the company aladdin of model 12011201 of 0.02000g is accurately weighed in a room temperature environment, and the powder material has a thickness of 750m²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 250mL quartz round-bottom flask, adding 50mL distilled water, and stirring at a high speed for 4min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is a modified microwave oven, the power of the microwave reactor is 1000W, the model is PJ21C-AU, the frequency is 2450MHz, heating the reaction raw materials to 80 ℃, continuously reacting for 8 hours to obtain black graphene uniform slurry, and naturally cooling to room temperature for later use; weighing 10.0000g of analytically pure ammonium molybdate white powder, adding the powder to the black graphene uniform slurry, and stirring for 1.0h to obtain a turbid liquid; then 10mL of 50 wt% manganese nitrate aqueous solution is measured, wherein the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 25mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5h to obtain a uniform solution; adding the obtained homogeneous solution into the suspensionPlacing the quartz round-bottom flask in a normal-pressure microwave reactor with a reflux cooling device in the first step, heating the quartz round-bottom flask to 80 ℃, and continuously reacting for 8 hours; and finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifuge with 9000rpm, setting the centrifugation time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a forced air drying oven with the temperature of 80 ℃ for drying for 12h to obtain the target manganese molybdate nanowire/graphene powder sample 2.

Example 3: preparation of manganese molybdate nanowire/graphene composite sample 3

0.1500g of a graphene powder material model 12011201 sold by the company aladdin, having a thickness of 750m, was precisely weighed in a room temperature environment²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 250mL quartz round-bottom flask, adding 50mL distilled water, and stirring at a high speed for 4min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is a modified microwave oven, the power of the microwave reactor is 1000W, the model is PJ21C-AU, the frequency is 2450MHz, heating the reaction raw materials to 80 ℃, continuously reacting for 8 hours to obtain black graphene uniform slurry, and naturally cooling to room temperature for later use; secondly, 15.0000g of analytically pure ammonium molybdate white powder is weighed, added to the black graphene uniform slurry, and stirred for 0.5h to obtain a suspension; then 10mL of 50 wt% manganese nitrate aqueous solution is measured, wherein the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 25mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5h to obtain a uniform solution; adding the obtained uniform solution into the quartz round-bottom flask filled with the suspension, placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device in the first step, heating the quartz round-bottom flask to 80 ℃, and continuously reacting for 8 hours; finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifuge with 9000rpm, setting the centrifugation time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in an air-blast drying oven at 80 ℃ for dryingAnd drying for 12h to obtain a target manganese molybdate nanowire/graphene powder sample 3.

Comparative example 1: publication No. CN 107459063 a (publication No. 2017.12.12) provides a preparation method: (1): dissolving manganese acetate tetrahydrate in ethanol or ethylene glycol under stirring to obtain a mixed solution A; (2) dissolving sodium molybdate dihydrate in ethanol or ethylene glycol under stirring to obtain a mixed solution B; (3) mixing and stirring the mixed solution A and the mixed solution B according to the volume ratio of 1: 1-2 for 15 minutes, transferring the mixed solution A and the mixed solution B into a reaction kettle, and sealing the reaction kettle; fully reacting at 120-180 ℃, and then performing suction filtration, washing and drying on the obtained product; (4) calcining the product obtained in the step (3) at the temperature of 400-700 ℃, and cooling to room temperature to obtain manganese molybdate micro-nano materials with different morphologies.

The invention discloses a design and synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor; for example, example 1: preparation of manganese molybdate nanowire/graphene composite sample 1. accurately weighing 0.0100g of graphene powder material model 12011201 sold by aladdin company under room temperature environment, wherein the powder material has a particle size of 750m²The specific surface area per gram provides material guarantee for improving the comprehensive performance of the material; then placing the weighed graphene powder into a 250mL quartz round-bottom flask, adding 50mL distilled water, and stirring at a high speed for 4min until the materials are uniform, thereby forming a black mixed suspension with uniformly dispersed solid content; then placing the quartz round-bottom flask into a normal-pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is a modified microwave oven, the power of the microwave reactor is 1000W, the model is PJ21C-AU, the frequency is 2450MHz, heating the reaction raw materials to 80 ℃, continuously reacting for 8 hours to obtain black graphene uniform slurry, and naturally cooling to room temperature for later use; secondly, weighing 5.0000g of analytically pure ammonium molybdate white powder, adding the powder to the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; then 10mL of 50 wt% manganese nitrate aqueous solution is measured, the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126 g/mL; adding 25mL of distilled water under the strong stirring condition of 120rpm, and continuously stirring for 0.5h to obtain a uniform solution; adding the uniform solution into a quartz round-bottom flask filled with the suspension,placing the mixture into a normal-pressure microwave reactor with a reflux cooling device in the first step, heating the mixture to 80 ℃, and continuously reacting for 8 hours; and finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifuge with 9000rpm, setting the centrifugation time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a forced air drying oven with the temperature of 80 ℃ for drying for 12h to obtain the target manganese molybdate nanowire/graphene powder sample 1.

The preparation method related to the publication No. CN 107459063A adopts solvothermal-calcination to synthesize the manganese molybdate micro-nano material, the reaction temperature range span is large, and the obtained target product has the advantages of difficult control of microscopic morphology, large size and poor uniformity. According to the method, the manganese molybdate nanowire/graphene composite material is synthesized by using a microwave radiation method, the electrochemical performance of manganese molybdate is effectively improved by compounding graphene and manganese molybdate, the morphology and the size of the target manganese molybdate nanowire/graphene composite material can be effectively controlled, the product is regular in morphology and single in phase, and the requirement for preparing the manganese molybdate nanowire/graphene composite material for the supercapacitor is met.