CN112875757B - Design synthesis method of manganese molybdate nanowire/graphene composite material for supercapacitor - Google Patents

Design synthesis method of manganese molybdate nanowire/graphene composite material for supercapacitor Download PDF

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CN112875757B
CN112875757B CN202110188592.4A CN202110188592A CN112875757B CN 112875757 B CN112875757 B CN 112875757B CN 202110188592 A CN202110188592 A CN 202110188592A CN 112875757 B CN112875757 B CN 112875757B
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李春生
刘鹏超
孙嬿
毛子旺
朱珠
殷公社
杨晨
王笛笛
曾康钰
陈嘉巧
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Suzhou University of Science and Technology
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Abstract

The invention discloses a target product of a patent, which is mainly applied to the field of energy storage materials, in particular to a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor. The technology takes graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials, distilled water as a solvent and a dispersing agent; and a manganese molybdate nanowire/graphene three-dimensional nanocomposite with regular structure and single phase is controllably synthesized by a microwave radiation method. XRD, SEM and TEM analysis results show that the product is a pure-phase manganese molybdate nanowire/graphene composite material, and is a battery material with excellent energy storage performance.

Description

Design synthesis method of manganese molybdate nanowire/graphene composite material for supercapacitor
[ PREPARATION METHOD ]: the invention belongs to the field of energy storage materials, and particularly relates to a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor.
[ PREPARATION METHOD ]: in order to cope with the problems of the world such as the accelerated energy consumption, the large emission of greenhouse gases, the environmental deterioration, etc., the sustainable development of new energy materials is one of the important directions. The electrochemical energy storage device has the outstanding advantages of stable input and output of chemical energy, and can well overcome the defects of indirection and instability of clean energy sources such as wind energy, solar energy, tidal energy and the like; in addition, energy storage devices for power and energy storage are in a trend of high-speed development. With the intensive research of energy storage devices, it is expected that the energy storage devices can meet the requirements of green life, and meanwhile, the requirements on the doubling performance and the safety of the energy storage devices are gradually improved. Among the various energy storage devices, research into supercapacitors has become a hotspot. Compared with the traditional energy storage device, the super capacitor has the advantages of high power density, excellent stability and high capacity retention rate. For example, in the field of new energy automobiles, supercapacitors can reach application scenarios of fast charging and heavy current charging to solve the problem of short plates of conventional new energy automobile batteries, which exhibit a bright market prospect (Zhihui Xu, shimuai Sun, yue Han, et al, high energy density asymmetric supercapacitor based on durable and stable manganese molybdate nanostructures electrode for energy storage system [ J ]. ACS Applied Energy materials.2020,3 (6): 5393-5404.).
The practical application of the super capacitor has the defect that the energy density is lower than that of a traditional secondary battery; it is an important factor that hinders the popularization of super capacitors, so development of high-performance, high-energy-density electrode materials is urgently needed. The manganese molybdate material has the advantages of high specific capacity, low discharge potential, good cycle performance and the like, has excellent electrochemical activity, and is widely studied in the energy storage field (Thangappan R, kumar R D and Jayavel R. Synthesis, structural and electrochemical properties of Mn-MoO) 4 /graphene nanocomposite electrode material with improved performance for supercapacitor application[J].The Journal of Enegy storage 2020, 27: 101069.). Graphene is used as an important novel carbon-based material, and can improve the conductivity and mechanical strength of the material after being compounded with other electrode materials, so that the application effects of accelerating the charging speed and prolonging the cycle life are achieved. Meanwhile, compared with the conventionally synthesized manganese molybdate, the electrode material is nanocrystallized, the electrochemical stability of the composite material is optimized by virtue of the nanoscale structure and the morphological advantages of the electrode material (Li Minmin, cao Fan, gu Shuangfeng, and the like; the manganese molybdate nanomaterial [ J ] is prepared by electron beam irradiation]Electron microscopy report 2017, 36 (4): 328-335.). The common composite technique of manganese molybdate material is chemical precipitation method, vapor deposition method, hydrothermal method, electrodeposition method, etc. (Namvar F, beshkar F, salavati-Niasari M. Novel microwave-assisted synthesis of leaf-like MnMoO) 4 nanostructures and investigation of their photocatalytic performance[J]Journal of Materials Science: materials in electronics.2017, 28 (11): 7962-7968.). However, the synthetic material prepared by the method still has a great improvement in the aspect of micro morphology control and uniform size.
Aiming at the scientific problem, the invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor; the composite material is synthesized by adopting a microwave radiation method. The traditional heating relies on the heat conduction of the solvent to slowly heat, and the microwave radiation technology can act on the internal molecular structure of the reactant, so that the internal and external heating of the reaction raw materials is uniform and consistent, the heat energy utilization rate is high, and the construction of the three-dimensional nano composite material with a regular structure is facilitated. The XRD, SEM, TEM analysis result of the target product designed by the patent shows that the target product is a pure-phase manganese molybdate nanowire/graphene composite material, and has great development potential and wide development prospect in super capacitors.
[ invention ] the following: the invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which takes graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials, distilled water as a solvent and a dispersing agent, and adopts a microwave radiation method to synthesize the manganese molybdate nanowire/graphene composite material.
[ solution ] according to the present invention: the invention provides a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which takes graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials and distilled water as a solvent and a dispersing agent respectively; the manganese molybdate nanowire/graphene three-dimensional nanocomposite with regular structure and single phase is controllably synthesized by means of a microwave radiation method, and the specific synthesis steps are as follows:
first, under room temperature environment, accurately weighing 0.0010-10.0000 g of model 12011201 sold by Aladin company, the graphene powder having 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniform solid content dispersion; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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, and naturally cooling to room temperature for standby;
weighing 5.0000-15.0000 g of analytically pure ammonium molybdate white powder, adding the powder into the black graphene uniform slurry obtained by the pretreatment in the first step, and stirring for 0.5-3.0 h to obtain uniform suspension;
thirdly, weighing 5-30 mL of 50wt% manganese nitrate aqueous solution, wherein the molecular weight of the manganese nitrate is 178.95, and the density of the manganese nitrate is 1.5126g/mL; adding 10-150 mL 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, and then placing the quartz round bottom flask into a normal pressure microwave reactor with a reflux cooling device in the first step, wherein the equipment power is set to be 200-1400W, the heating temperature is 70-100 ℃, and the continuous reaction is carried out for 1-10 h;
fifthly, naturally cooling the product obtained in the fourth step to room temperature, placing the product in a high-speed centrifuge at 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 blast drying box at 50-80 ℃ for drying for 5-20 h to obtain target manganese molybdate nanowire/graphene powder; the XRD, SEM, TEM analysis results of the samples all confirm that the pure-phase manganese molybdate nanowire/graphene composite material.
[ advantages and effects of the present invention ]: the invention relates to a design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor, which has the following advantages and effects: (1) The reserves of molybdenum ores in China are rich, the molybdate cost is low, the deep development of the high-quality nanoscale manganese molybdate material is deeply developed, and the promotion of product upgrading and the vigorous development of super capacitors is facilitated; (2) The manganese molybdate nanowire/graphene composite material synthesized by a microwave radiation method can effectively control the crystal form and the dimension of target manganese molybdate; (3) The pure-phase manganese molybdate nanowire/graphene obtained by the synthesis method disclosed by the invention is characterized by regular morphology and single phase, and can be used for improving the electrochemical performance of the supercapacitor.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) spectrum of a uniform slurry of black graphene in sample 1
FIG. 2 is an SEM spectrum of a composite material of sample 1 at 1.3 ten thousand magnification
FIG. 3 is an SEM spectrum of a composite material of sample 1 at 2.5 ten thousand times magnification
FIG. 4 is an SEM spectrum of a composite material of sample 1 at 5 ten thousand magnification
FIG. 5 is an SEM spectrum of a 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 of sample 1
Detailed Description
Example 1: preparation of manganese molybdate nanowire/graphene composite sample 1
Under the room temperature environment, 0.0100g of a graphene powder material sold by Aladin company and having a model number of 12011201 is accurately weighed, and the powder material has a size of 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniformly dispersed solid content; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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 standby; as shown in fig. 1, the monodisperse graphene is in a network structure, and a uniform flaky regular morphology with the thickness of 25nm is obtained, which provides a basis for the 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 into the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; 14.0mL of 50wt% manganese nitrate aqueous solution with molecular weight of 178.95 and density of 1.5126g/mL is measured again; 25mL of distilled water is added under the strong stirring condition of 120rpm, and stirring is continued for 0.5h, so as to obtain a uniform solution; adding the uniform solution into a quartz round bottom flask containing the suspension, and then placing the quartz round bottom flask into a normal pressure microwave reactor with a reflux cooling device in the first step, heating to 80 ℃, and continuously reacting for 8 hours; finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifugal machine at 9000rpm, setting the centrifugal time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a blast drying oven at 80 ℃ for drying for 12h to obtain a target manganese molybdate nanowire/graphene powder sample 1; XRD testing of the samples showed that: which corresponds to JCPDS39-84; as shown in SEM figures 2-5 of the sample, the morphology and the dimension are uniform, and the lamellar graphene is uniformly distributed on the surface of the manganese molybdate material, so that the electron conductivity can be improved; as shown in FIG. 6, which is a TEM spectrum of a sample, it was confirmed that the crystallinity of the material was excellent, and the lattice fringesClear. 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
Accurately weighing 0.02000g of a graphene powder material sold by Aladin company under the model 12011201 under the room temperature environment, wherein the powder material has 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniformly dispersed solid content; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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 standby; weighing 10.0000g of analytically pure ammonium molybdate white powder, adding the analytically pure ammonium molybdate white powder into the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; then 10mL of 50wt% manganese nitrate aqueous solution is measured, the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126g/mL; 25mL of distilled water is added under the strong stirring condition of 120rpm, and stirring is continued for 0.5h, so as to obtain a uniform solution; adding the obtained uniform solution into the quartz round bottom flask containing the suspension, and then placing the quartz round bottom flask into a normal pressure microwave reactor with a reflux cooling device in the first step, heating 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 centrifugal machine with the speed of 9000rpm, setting the centrifugal time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a blast 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
Under the room temperature environment, 0.1500g of a graphene powder material sold by Aladin company and having the model number of 12011201 is accurately weighed, and the powder material has the size of 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniformly dispersed solid content; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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 standby; secondly, weighing 15.0000g of analytically pure ammonium molybdate white powder, adding the powder into the black graphene uniform slurry, and stirring for 0.5h to obtain a suspension; then 10mL of 50wt% manganese nitrate aqueous solution is measured, the molecular weight of the manganese nitrate is 178.95, and the density is 1.5126g/mL; 25mL of distilled water is added under the strong stirring condition of 120rpm, and stirring is continued for 0.5h, so as to obtain a uniform solution; adding the obtained uniform solution into the quartz round bottom flask containing the suspension, and then placing the quartz round bottom flask into a normal pressure microwave reactor with a reflux cooling device in the first step, heating 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 centrifugal machine with the speed of 9000rpm, setting the centrifugal time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a blast drying oven with the temperature of 80 ℃ for drying for 12h to obtain the target manganese molybdate nanowire/graphene powder sample 3.
Comparative example 1: publication number CN 107459063A (publication date 2017.12.12) provides a method of preparation: (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; fully reacting at 120-180 ℃, and then carrying out suction filtration, washing and drying on the mixture; (4) Calcining the product of the step (3) at the temperature of 400-700 ℃, and cooling to room temperature to obtain the manganese molybdate micro-nano material with different morphologies.
The invention discloses a design 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 under ambient temperature, 0.0100g of a graphene powder material sold by Aladin Co., ltd. And having a size of 12011201 was accurately weighed, the powder material having a size of 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniformly dispersed solid content; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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 standby; secondly, weighing 5.0000g of analytically pure ammonium molybdate white powder, adding the powder into the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; weighing 10mL of 50wt% manganese nitrate aqueous solution, wherein the molecular weight of the manganese nitrate is 178.95, and the density of the manganese nitrate is 1.5126g/mL; 25mL of distilled water is added under the strong stirring condition of 120rpm, and stirring is continued for 0.5h, so as to obtain a uniform solution; adding the uniform solution into a quartz round bottom flask containing the suspension, and then placing the quartz round bottom flask into a normal pressure microwave reactor with a reflux cooling device in the first step, heating 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 centrifugal machine at 9000rpm, setting the centrifugal time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a blast drying oven at 80 ℃ for drying for 12h to obtain the target manganese molybdate nanowire/graphene powder sample 1.
The preparation method related to the publication number 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 the microcosmic appearance, larger size and poor uniformity. According to the method, the manganese molybdate nanowire/graphene composite material is synthesized by utilizing a microwave radiation method, the electrochemical performance of manganese molybdate is effectively improved through the compounding of 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 of preparing the manganese molybdate nanowire/graphene composite material for the super capacitor is met.

Claims (1)

1. A design synthesis method of a manganese molybdate nanowire/graphene composite material for a supercapacitor respectively takes graphene, analytically pure ammonium molybdate white powder and manganese nitrate as reaction raw materials, and distilled water as a solvent and a dispersing agent; the manganese molybdate nanowire/graphene three-dimensional nanocomposite with regular structure and single phase is controllably synthesized by means of a microwave radiation method, and the specific synthesis steps are as follows:
first, under room temperature environment, 0.0100g of a graphene powder material sold by aladin company under model 12011201 was weighed, and the powder material had a particle size of 750m 2 The specific surface area of the material is/g, so that material guarantee is provided 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, so as to form black mixed suspension with uniformly dispersed solid content; then placing the quartz round bottom flask in a normal pressure microwave reactor with a reflux cooling device, wherein the microwave reactor is an improved American 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 standby; secondly, weighing 10.5000g of analytically pure ammonium molybdate white powder, adding the powder into the black graphene uniform slurry, and stirring for 1.0h to obtain a suspension; 14.0mL of 50wt% manganese nitrate aqueous solution with molecular weight of 178.95 and density of 1.5126g/mL is measured again; 25mL of distilled water is added under the strong stirring condition of 120rpm, and stirring is continued for 0.5h, so as to obtain a uniform solution; adding the uniform solution into quartz round bottom flask containing the suspension, placing into a first step of normal pressure microwave reactor with reflux cooling device, heating to a temperatureThe reaction is continued for 8 hours at 80 ℃; finally, naturally cooling the obtained product to room temperature, placing the product in a high-speed centrifugal machine with the speed of 9000rpm, setting the centrifugal time to be 2min, washing the obtained precipitate with distilled water for 4 times, and placing the washed product in a blast drying oven with the temperature of 80 ℃ for drying for 12h to obtain a target manganese molybdate nanowire/graphene powder sample; XRD testing of the samples showed that: which corresponds to JCPDS39-84; the sample has uniform morphology and dimension, and the lamellar graphene is uniformly distributed on the surface of the manganese molybdate material, so that the electron conduction capability is improved; TEM spectrum of the sample proves that the crystallinity of the material is excellent, and the lattice fringes are clear.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502847A (en) * 2011-11-07 2012-06-20 河北联合大学 Preparation method for manganese molybdate nanospheres regular in shape
CN104752067A (en) * 2015-03-27 2015-07-01 新疆大学 Microwave-assisted method of nickel molybdate graphene composite material used for capacitor
CN110895999A (en) * 2019-12-03 2020-03-20 西安交通大学 Porous graphene-enhanced supercapacitor and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502847A (en) * 2011-11-07 2012-06-20 河北联合大学 Preparation method for manganese molybdate nanospheres regular in shape
CN104752067A (en) * 2015-03-27 2015-07-01 新疆大学 Microwave-assisted method of nickel molybdate graphene composite material used for capacitor
CN110895999A (en) * 2019-12-03 2020-03-20 西安交通大学 Porous graphene-enhanced supercapacitor and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
αMnMoO4 /graphene hybrid composite: high energy density supercapacitor electrode material;Debasis Ghosh等;《Dalton Transactions》;20140101;第43卷(第28期);第11067–11076页 *

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