CN114920301A - Electrode material based on multi-metal molybdate cluster and preparation method and application thereof - Google Patents

Electrode material based on multi-metal molybdate cluster and preparation method and application thereof Download PDF

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CN114920301A
CN114920301A CN202210669492.8A CN202210669492A CN114920301A CN 114920301 A CN114920301 A CN 114920301A CN 202210669492 A CN202210669492 A CN 202210669492A CN 114920301 A CN114920301 A CN 114920301A
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魏巍
巫云萍
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Xian Jiaotong University
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Abstract

The invention discloses an electrode material based on multi-metal molybdate clusters and a preparation method and application thereof. The invention has the characteristics of simple preparation process, strong repeatability, high specific capacity of the sodium-ion battery, good cycling stability, excellent rate performance and the like, and has good economic benefit and environmental benefit.

Description

Electrode material based on multi-metal molybdate cluster and preparation method and application thereof
Technical Field
The invention belongs to the field of material science and sodium ion battery cathode materials, and particularly relates to an electrode material based on a multi-metal molybdate cluster, and a preparation method and application thereof.
Background
Self-assembly synthesis is an effective means for developing novel functional materials, and the mechanical, optical or electrochemical properties of the materials can be obviously improved through a multi-level ordered structure constructed by self-assembly. However, traditional assembly units (such as organic molecules, macromolecules, biological macromolecules, nanoparticles, etc.) are difficult to assemble into highly ordered spatial structures under weak interactions due to their single structure and lack of multiple adjustable chemical driving forces.
Polymetallic molybdate cluster (P) of multinuclear structureOMs, such as: mo 7 O 24 6- ,PMo 12 O 40 3- Etc.) has the characteristics of large geometric dimension, more carried charges, etc., and the POMs can be arranged into an ordered complex structure according to a certain mode by taking the POMs as an assembly element through the interaction of static electricity, hydrogen bonds, etc. between organic molecules containing nitrogen/oxygen, etc., and can be further assembled into a multi-scale nano functional material. The POMs cluster-based assembly not only has the characteristics and functionality of inorganic and organic materials, but also can obtain a material with a novel structure and practical characteristics by adjusting the action between internal molecules and the assembly driving force. However, because the traditional organic connector is exposed to the problems of incompatibility with the POMs cluster size, limited chemical action and the like, the early-stage assembly structure is still in low dimensionality or simple ordered arrangement, and breakthroughs are difficult to obtain in the aspects of multi-dimensionality ordered assembly of the POMs cluster and micro-nano structure/interface regulation.
Disclosure of Invention
The electrode material of the thermally vulcanized POMs has a multi-pore channel structure, high dispersion and high activity electrochemical reaction sites, and durable and strong interface stable configuration and action, so that the electrode material has excellent reversible capacity, high rate performance and ultra-long cycle life in the application of sodium ion battery cathodes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
s1, dispersing melamine in deionized water, completely dissolving at a preset temperature to obtain a uniform solution, namely a solution A, and then adding a transition metal Co (II) ion solution for reaction to obtain a solution B;
s2, dispersing the POMs into deionized water to obtain a solution C; adding the solution C into the solution B, continuously stirring for reaction to obtain a solution D, transferring the solution D into a reaction kettle, and carrying out assembly reaction at a preset temperature and time; obtaining a precipitate after the assembly reaction is finished, and washing and drying the precipitate to obtain the POMs cluster composite material with the multidimensional ordered structure;
and S3, mixing the POMs cluster composite material with sulfur powder, and then roasting in an inert atmosphere to obtain the thermally vulcanized POMs cluster electrode material.
Further, in step S1, the melamine is dispersed in the deionized water, the concentration of the obtained solution is 0.08-0.15 mol/L, the preset temperature is 60-90 ℃, the molar ratio of the melamine to the transition metal Co (II) ions is (6-8): 1, and the time for adding the transition metal Co (II) ion solution for reaction is 10-60 min.
Further, in step S2, the molar ratio of the transition metal Co (ii) ions to the POMs cluster is 1:1, and the POMs cluster is one of ammonium tetramolybdate, ammonium heptamolybdate, ammonium octamolybdate and phosphomolybdic acid.
Further, in the step S2, the concentration of the solution C is 0.01-0.05 mol/L, the solution C is added dropwise, and the reaction time of the solution D is 15-45 min.
Further, in step S2, the temperature of the assembly reaction is 150-200 ℃ and the time is 8-16 h.
Further, in step S2, the internal microstructure of the obtained POMs cluster composite material is that the POMs clusters are linearly and orderly arranged on the two-dimensional layered Co-Mela substrate, and are further assembled into a regular nano-pillar structure in a three-dimensional space under the common driving of coordination and conjugation.
Furthermore, in step S3, the mass ratio of the POMs cluster composite material to the sulfur powder is 1 (2-4).
Further, in step S3, the roasting temperature is carried out in a tube furnace in a temperature programming mode, firstly, the temperature is raised to 200 ℃ at a temperature raising rate of 0.5-1 ℃/min, the temperature is kept for 2h, then, the temperature is raised to 450-550 ℃ at a temperature raising rate of 1-2.5 ℃/min, and the temperature is kept for 2 h.
An electrode material based on multi-metal molybdate clusters is prepared by adopting the preparation method.
An application of an electrode material based on a multi-metal molybdate cluster in a negative electrode material of a sodium-ion battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the method not only selects the POMs as a novel construction unit of the sodium-ion battery cathode material, but also develops a two-dimensional layered structure connecting ligand and a limited domain environment which are suitable for adjusting the surface chemical action and the spatial arrangement configuration of the POMs, drives the POMs to be distributed between substrate layers in a linear arrangement mode, and assembles into a regular nano-columnar structure in a three-dimensional space. The invention further proves that the method has universality and popularization and application values for the assembly of the POMs cluster multi-dimensional structures of different types and sizes.
2. The invention can realize the self-assembly of the POMs cluster multidimensional ordered structure by a one-step hydrothermal method, has simple and efficient synthesis process, can synthesize powder in kilogram by one pot by increasing the feeding amount of the reaction, and is beneficial to industrial scale generation and application. In addition, the source of the raw materials for synthesizing the multi-metal molybdate cluster composite material is wide, the cost is low, the safety is high, the synthesis process is green and sustainable, and the economic benefit is high.
3. The POMs cluster composite material obtained by the invention has regular and strong chemical action force in the molecule, can promote the POMs cluster to be converted into high-activity sulfide in situ through simple hot vulcanization, limits the size of active particles, prevents the active particles from being aggregated at high temperature, and simultaneously reacts with C 3 N 4 The porous network forms a close interface fit through rich Co-N bonds. The obtained derivative material has a moderate specific surface area, the in-situ converted sulfide nanocrystalline particles have the characteristics of high dispersion and high activity, a large number of electrochemical active sites are provided for sodium ion storage, the infiltration of electrolyte and ion/electron transmission are facilitated, the structural change in the electrochemical reaction process is effectively relieved, the excellent cycle stability and high rate performance of the electrode material are ensured, and the derivative material has a wide application prospect in the field of sodium ion battery energy storage.
Drawings
The following drawings illustrate only certain embodiments of the invention and are therefore not to be considered limiting of its scope.
Fig. 1 is an XRD pattern of the POMs cluster composite obtained in example 1.
FIG. 2 is a transmission electron micrograph of POMs cluster composites obtained in example 1: a is a low power electron microscope image, and b is a high power electron microscope image.
Fig. 3 is an XRD pattern of the electrode material of the thermally vulcanized POMs clusters obtained in example 1.
FIG. 4 is a transmission electron micrograph of the electrode material of the thermally vulcanized POMs cluster obtained in example 1: a is a low power electron microscope image, and b is a high power electron microscope image.
Fig. 5 is a graph of rate capability and cycle performance of the electrode material of the thermally vulcanized POMs cluster obtained in example 1 as a negative electrode material for a sodium ion battery.
Fig. 6 is a transmission electron micrograph of the POMs cluster composite obtained in example 2: a is a low power electron microscope image, and b is a high power electron microscope image.
Fig. 7 is characterization data for the electrode material of the thermally vulcanized POMs cluster obtained in example 2: a is a transmission electron microscope image, and b is an XRD image.
Fig. 8 is a graph of rate capability and cycle performance of the electrode material of the thermally vulcanized POMs cluster obtained in example 2 as a negative electrode material for a sodium ion battery.
FIG. 9 is a transmission electron micrograph of POMs cluster composites obtained in example 3: a is a low power electron microscope image, and b is a high power electron microscope image.
Fig. 10 is characterization data for the electrode material of the thermally vulcanized POMs cluster obtained in example 3: a is a transmission electron microscope image, and b is an XRD image.
Fig. 11 is a graph of rate capability and cycle performance of the electrodes of the thermally vulcanized POMs cluster obtained in example 3 as negative electrode material for sodium ion batteries.
Fig. 12 is a transmission electron micrograph of the POMs cluster composite obtained in example 4: a is a low power electron microscope image, and b is a high power electron microscope image.
Fig. 13 is characterization data for the electrode material of the thermally vulcanized POMs cluster obtained in example 4: a is a transmission electron micrograph, and b is an XRD micrograph.
Fig. 14 is a graph of rate capability and cycle performance of the electrodes of the thermally vulcanized POMs clusters obtained in example 4 as negative electrode material for sodium ion batteries.
Detailed Description
The invention is described in further detail below:
a preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
s1, dispersing a certain amount of melamine in deionized water, completely dissolving the melamine at a proper temperature to obtain a uniform solution, namely solution A, adding a transition metal Co (II) ion solution at the temperature, and reacting for a period of time to obtain solution B; wherein the concentration of melamine in the aqueous solution is 0.08-0.15 mol/L, the reaction temperature is 60-90 ℃, the molar ratio of melamine to transition metal Co (II) ions is (6-8): 1, and the reaction time for obtaining the solution B is 10-60 min;
s2, dispersing the POMs into deionized water to obtain a solution C; adding the solution C into the solution B, continuously stirring and reacting for a period of time to obtain a solution D, transferring the solution D into a reaction kettle, and assembling at a proper temperature and for a proper time; obtaining a precipitate after the reaction is finished, and washing and drying the precipitate to obtain the POMs cluster composite material with the multidimensional ordered structure; wherein the molar ratio of the transition metal Co (II) ions to the POMs is 1:1, and the POMs comprise one of ammonium tetramolybdate, ammonium heptamolybdate, ammonium octamolybdate and phosphomolybdic acid; the concentration of the solution C is 0.01-0.05 mol/L, the solution C is added dropwise, and the reaction time for obtaining the solution D is 15-45 min; the assembly temperature is 150-200 ℃, and the assembly time is 8-16 h; the internal microstructure of the obtained POMs cluster composite material is that the POMs clusters are linearly and orderly arranged on a two-dimensional layered Co-Mela substrate, and are further assembled into a regular nano columnar structure in a three-dimensional space under the common drive of coordination action and conjugation action;
s3, mixing the obtained POMs cluster composite material with sulfur powder, then roasting in an inert atmosphere, and obtaining the thermally vulcanized POMs cluster electrode material at a proper temperature and time, wherein the mass ratio of the POMs cluster composite material to the sulfur powder is 1 (2-4); the roasting temperature is carried out in a tubular furnace in a programmed heating mode, the temperature is firstly increased to 200 ℃ at the heating rate of 0.5-1 ℃/min, the temperature is kept for 2 hours at the temperature, and then the temperature is maintained at 1-2.5 ℃/mThe temperature rise rate of the in is up to 450-550 ℃, the temperature is kept for 2h at the temperature, the appearance of the electrode material of the POMs cluster is changed into a porous structure column from an original smooth column after heat vulcanization, and the POMs cluster is converted into high-dispersity small-grain CoMoS in situ 3.13 And is anchored C 3 N 4 In the frame, is CoMoS 3.13 @C 3 N 4 . Resulting CoMoS 3.13 @C 3 N 4 The material has a porous structure and a large specific surface area, and is favorable for the infiltration of electrolyte and ion transmission; CoMoS 3.13 And C 3 N 4 Rich Co-N bonds exist between the two groups, so that the transmission rate of electrons is accelerated, and the problem that the metal sulfide structure is easy to collapse in the charging and discharging process can be effectively solved.
An electrode material based on multi-metal molybdate clusters (POMs) is characterized in that the internal microstructure of the electrode material is that POMs are linearly and orderly arranged on a two-dimensional layered Co (II) coordinated melamine/cyanuric acid (Co-Mela) substrate and assembled into a regular nano columnar structure in a three-dimensional space; further carrying out hot vulcanization on the obtained POMs cluster composite material, wherein the electrode material of the hot vulcanized POMs cluster can keep the basic structure of a columnar body, and meanwhile, the POMs cluster is converted into high-dispersion CoMoS rich in grain boundary in situ 3.13 Is anchored to C by rich Co-N bonds 3 N 4 In the layered frame, an electrode material of a multi-metal molybdate cluster with large specific surface area, high electrochemical active site and stable interface structure is formed.
The electrode material based on the multi-metal molybdate cluster prepared by the invention can be used as a cathode material of a sodium-ion battery.
According to the preparation method provided by the invention, POMs clusters with various geometric configurations and rich surface effects are selected as electrode material construction units, melamine/cyanuric acid layered organic ligands containing Co (II) ion coordination points are used as a connecting agent and a regulating agent, the regulation of the spatial coordination connection and the interface electronic effect of the POMs clusters is realized through a hydrothermal assembly process, the POMs clusters are driven to be linearly arranged in a two-dimensional limited-area environment, and a highly ordered column-shaped composite material of the POMs clusters is formed in a three-dimensional space. By selecting different classesAnd a series of POMs cluster composite materials with high consistency and multidimensional ordered structures can be obtained by the type and size of POMs cluster (such as phosphomolybdic acid, ammonium octamolybdate, ammonium heptamolybdate and ammonium tetramolybdate). Because of the strong ordered chemical action between the POMs cluster unit and the substrate, the electrode material of the POMs cluster is still in a columnar structure after hot vulcanization, and small metal sulfide grains derived from the POMs cluster are evenly anchored on the C in situ 3 N 4 Within the layered framework of (a). The obtained electrode material of the thermally vulcanized POMs has a porous structure, high dispersion and high activity electrochemical reaction sites, and a durable and strong interface stable configuration and action, so that the electrode material of the thermally vulcanized POMs shows excellent reversible capacity, high rate performance and ultra-long cycle life in the application of a sodium ion battery cathode.
The following detailed description of the present invention will be provided in conjunction with examples and drawings to facilitate a more complete understanding of the present invention by those skilled in the art, but it is not intended to limit the present invention to all embodiments. All other embodiments obtained without making any inventive step are within the scope of protection of the present invention.
Example 1
A preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
(1) weighing 0.5g of melamine and dispersing in 30mL of deionized water to obtain a solution A; then 0.15g of Co (NO) 3 ) 2 Dispersing in 2mL of aqueous solution to obtain solution B; dispersing 0.62g of ammonium heptamolybdate into 10mL of aqueous solution to obtain solution C; stirring the solution A to dissolve at the temperature of 80 ℃, then adding the solution B, continuously stirring and reacting for 15min, then dropwise adding the solution C, and stirring and reacting for 30min to obtain a reaction solution D; transferring the solution D into a reaction kettle, and reacting for 10 hours in an oven at 180 ℃ to obtain purple precipitate.
(2) Filtering and washing the purple precipitate with ethanol and water for three times, and drying in a vacuum oven at 60 ℃ for 12h to obtain a purple heptamolybdate composite material with a multi-dimensional ordered structure; then carrying out thermal vulcanization treatment, mixing 0.2g of ammonium heptamolybdate composite material with 0.4g of sulfur powder, placing the mixture in an argon atmosphere, firstly heating to 200 ℃ at 1 ℃/min, vulcanizing for 2h, and thenHeating to 500 ℃ at the speed of 2 ℃/min, and calcining for 2h to obtain the CoMoS 3.13 @C 3 N 4 。
(3) The prepared CoMoS 3.13 @C 3 N 4 Uniformly mixing the conductive carbon black and polyvinylidene fluoride according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone serving as a solvent, coating the solvent on a pure copper foil, drying the pure copper foil in vacuum at 80 ℃ for 12 hours, using a pure sodium sheet as a counter electrode, using glass fiber as a diaphragm, and using 1mol/L sodium trifluoromethanesulfonate (dispersed in diglyme) as electrolyte. Electrochemical testing was then performed using a button half cell.
FIG. 1 is the XRD pattern of the ammonium heptamolybdate composite material of this example, demonstrating that the ammonium heptamolybdate composite material consists essentially of melamine/cyanuric acid and ammonium heptamolybdate.
FIG. 2 is a TEM image of the heptamolybdate composite material of this example, wherein the heptamolybdate composite material is a uniform column as seen in FIG. a; the cylinders are further enlarged and, as seen in panel b, consist of ammonium heptamolybdate arranged linearly in layers of melamine/cyanuric acid.
FIG. 3 is an XRD pattern of electrode material of heptamolybdate of the example, confirming that the electrode material of heat-vulcanized heptamolybdate is CoMoS 3.13 @C 3 N 4 (ii) a And due to CoMoS 3.13 At C 3 N 4 The surface is uniformly distributed, and no corresponding C appears 3 N 4 The diffraction peak of (4).
FIG. 4 shows the CoMoS of this example 3.13 @C 3 N 4 From FIG. a, it can be seen that the thermally vulcanized heptamolybdate electrode material is still a column, small particle nanocrystalline CoMoS 3.13 Is tightly chelated at C 3 N 4 The frame is internally provided with a porous structure; the columns are further enlarged, CoMoS is seen from panel b 3.13 @C 3 N 4 There are many grain boundaries.
FIG. 5 a shows the CoMoS of the present embodiment 3.13 @C 3 N 4 The rate performance graph of the sodium ion battery of (1). As can be seen from the graph, the capacity of 616.2mAh/g can be achieved when the battery density is 0.1A/g, the capacity of 567.9mAh/g can be achieved when the current density is increased to 1A/g,the capacity of 401.6mAh/g can be achieved when the current density is continuously increased to 20A/g; after the current density is switched back to 0.1mA/g at the 50 th circulation, the capacity of 687.0mAh/g can be still maintained, and the excellent rate capability of the electrode material is shown; b is the CoMoS of the invention 3.13 @C 3 N 4 The battery can still maintain 521.1mAh/g after being cycled for 2500 circles under the high current density of 2A/g, which shows that the novel electrode has excellent structural stability.
Example 2
A preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
(1) weighing 0.66g of melamine and dispersing in 35mL of deionized water to obtain a solution A; then 0.19g of Co (NO) is added 3 ) 2 Dispersing in 2mL of aqueous solution to obtain solution B; dispersing 1.19g of phosphomolybdic acid into 15mL of aqueous solution to obtain solution C; stirring the solution A to dissolve at 60 ℃, then adding the solution B, continuing stirring and reacting for 60min, then dropwise adding the solution C, and stirring and reacting for 15min to obtain a reaction solution D; transferring the solution D into a reaction kettle, and reacting for 16h in an oven at 150 ℃ to obtain purple precipitate.
(2) Filtering and washing the purple precipitate with ethanol and water for three times, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain a purple phosphomolybdic acid composite material with a multi-dimensional ordered structure; then carrying out heat vulcanization treatment, mixing 0.2g of phosphomolybdic acid composite material with 0.6g of sulfur powder, placing the mixture in an argon atmosphere, heating to 200 ℃ at a speed of 0.5 ℃/min, vulcanizing for 2h, then heating to 550 ℃ at a speed of 2.5 ℃/min, and calcining for 2h to obtain the CoMoS 3.13 @C 3 N 4 。
(3) The prepared CoMoS 3.13 @C 3 N 4 Uniformly mixing the conductive carbon black and polyvinylidene fluoride according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone serving as a solvent, coating the solvent on a pure copper foil, drying the pure copper foil in vacuum at 80 ℃ for 12 hours, using a pure sodium sheet as a counter electrode, using glass fiber as a diaphragm, and using 1mol/L sodium trifluoromethanesulfonate (dispersed in diglyme) as electrolyte. Then electrochemical by using button type half cellAnd (5) performing a chemical test.
Fig. 6 is a TEM image of the phosphomolybdic acid composite material according to the present example, and it can be seen from fig. a that the phosphomolybdic acid composite material is a columnar body; the columns are further enlarged and, as seen in panel b, consist of phosphomolybdic acid arranged linearly in layered melamine/cyanuric acid.
Fig. 7 a is a transmission electron micrograph of the electrode material of the thermally vulcanized phosphomolybdic acid of the present example, which shows that the electrode material of the thermally vulcanized phosphomolybdic acid is still a column, and the small-particle nanocrystalline CoMoS 3.13 Is tightly chelated at C 3 N 4 The frame is internally provided with a porous structure; b is an XRD pattern of the electrode material of the phosphomolybdic acid after the thermal vulcanization, and the electrode material of the phosphomolybdic acid after the thermal vulcanization is confirmed to be CoMoS 3.13 @C 3 N 4 。
In FIG. 8, a represents the CoMoS of the present example 3.13 @C 3 N 4 The rate performance graph of the sodium ion battery shows that the capacity of 616.6mAh/g can be reached when the battery density is 0.1A/g, the capacity of 606.1mAh/g can be reached when the current density is increased to 1A/g, and the capacity of 398.6mAh/g can be reached when the current density is continuously increased to 20A/g; after the current density is switched back to 0.1mA/g at the 50 th circulation, the capacity of 682.0mAh/g can be still maintained, and the excellent rate capability of the electrode material is shown; b is the CoMoS of the invention 3.13 @C 3 N 4 The battery can still maintain 459.1mAh/g after circulating 1000 circles under the high current density of 2A/g, which shows that the novel electrode has excellent structural stability.
Example 3
A preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
(1) weighing 0.20g of melamine and dispersing in 20mL of deionized water to obtain a solution A; then 0.077g of Co (NO) was added 3 ) 2 Dispersing in 2mL of aqueous solution to obtain solution B; dispersing 0.18g of ammonium tetramolybdate into 27mL of aqueous solution to obtain solution C; stirring the solution A to dissolve at 90 deg.C, adding the solution B, stirring for 10min, adding the solution C dropwise, and stirringReacting for 45min to obtain a reaction solution D; transferring the solution D into a reaction kettle, and reacting in an oven at 200 ℃ for 8h to obtain purple precipitate.
(2) Then, filtering and washing the purple precipitate with ethanol and water for three times, and drying the filtrate in a vacuum drying oven at 60 ℃ for 12 hours to obtain a purple tetramolybdate composite material with a multi-dimensional ordered structure; then carrying out thermal vulcanization treatment, mixing 0.2g of tetramolybdate composite material with 0.8g of sulfur powder, placing the mixture in an argon atmosphere, heating to 200 ℃ at the speed of 0.8 ℃/min, vulcanizing for 2h, then heating to 450 ℃ at the speed of 1 ℃/min, and calcining for 2h to obtain the CoMoS 3.13 @C 3 N 4 。
(3) The prepared CoMoS 3.13 @C 3 N 4 Uniformly mixing the conductive carbon black and polyvinylidene fluoride according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone serving as a solvent, coating the solvent on a pure copper foil, drying the pure copper foil in vacuum at 80 ℃ for 12 hours, using a pure sodium sheet as a counter electrode, using a glass fiber film as a diaphragm, and using 1mol/L sodium trifluoromethanesulfonate (dispersed in diglyme) as electrolyte. Electrochemical testing was then performed using a button half cell.
FIG. 9 is a TEM image of the ammonium tetramolybdate composite material of this example, which is a cylindrical body as seen from FIG. a; the columns are further enlarged and, as can be seen in the diagram b, consist of ammonium tetramolybdate arranged linearly in layers of melamine/cyanuric acid.
FIG. 10 a is a transmission electron micrograph of the electrode material of the thermally vulcanized ammonium tetramolybdate of this example, which shows that the electrode material of the thermally vulcanized ammonium tetramolybdate is still columnar, and the nanocrystalline CoMoS particles are small 3.13 Is tightly chelated at C 3 N 4 The frame is internally provided with a porous structure; b is the XRD pattern of the electrode material of the ammonium tetramolybdate after the thermal vulcanization, and the electrode material of the thermally vulcanized ammonium tetramolybdate is confirmed to be CoMoS 3.13 @C 3 N 4 。
FIG. 11 a shows the CoMoS of this example 3.13 @C 3 N 4 As can be seen from the rate performance graph of the sodium ion battery, the capacity of 583.3mAh/g can be achieved when the battery density is 0.1A/g, and the capacity of 583.3mAh/g can be achieved when the current density is increased to 1A/gTo 473.1mAh/g, a capacity of 422.6mAh/g can be achieved when continuing to increase the current density to 20A/g; after the current density is switched back to 0.1mA/g in the 50 th cycle, 598.0mAh/g of capacity can be still maintained, and the excellent rate capability of the electrode material of the polyoxometallate cluster is shown; b is the CoMoS of the invention 3.13 @C 3 N 4 The battery can still maintain the capacity of 337.8mAh/g after the battery is cycled for 1000 circles under the high current density of 2A/g, which shows that the novel electrode has excellent long cycle performance.
Example 4
A preparation method of an electrode material based on multi-metal molybdate clusters comprises the following steps:
(1) weighing 0.45g of melamine and dispersing in 30mL of deionized water to obtain a solution A; then 0.15g of Co (NO) is added 3 ) 2 Dispersing in 2mL of aqueous solution to obtain solution B; dispersing 0.65g of ammonium octamolybdate into 26mL of aqueous solution to obtain solution C; stirring the solution A to dissolve at 70 ℃, then adding the solution B, continuing stirring and reacting for 30min, then dropwise adding the solution C, and stirring and reacting for 25min to obtain a reaction solution D; transferring the solution D into a reaction kettle, and reacting for 9 hours in an oven at 170 ℃ to obtain purple precipitate.
(2) Filtering and washing the purple precipitate with ethanol and water for three times, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain a purple octamolybdate composite material with a multi-dimensional ordered structure; then carrying out thermal vulcanization treatment, mixing 0.2g of octamolybdate composite material with 0.5g of sulfur powder, placing the mixture in an argon atmosphere, heating to 200 ℃ at the speed of 0.7 ℃/min, vulcanizing for 2h, then heating to 520 ℃ at the speed of 1.5 ℃/min, and calcining for 2h to obtain the CoMoS 3.13 @C 3 N 4 。
(3) The prepared CoMoS 3.13 @C 3 N 4 Mixing with conductive carbon black and polyvinylidene fluoride uniformly according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone as a solvent, coating the mixture on a pure copper foil, drying the pure copper foil in vacuum at 80 ℃ for 12h, using a pure sodium sheet as a counter electrode, using a glass fiber film as a diaphragm, and using 1mol/L sodium trifluoromethanesulfonate (dispersed in diglyme) as a separatorAnd (3) an electrolyte. Electrochemical testing was then performed using a button half cell.
FIG. 12 is a TEM image of the ammonium octamolybdate composite material of the present example, which is also a cylinder as seen from FIG. a; the cylinders are further enlarged and, as can be seen in the diagram b, consist of ammonium octamolybdate arranged linearly in layers of melamine/cyanuric acid.
FIG. 13 a is a transmission electron micrograph of the thermally vulcanized ammonium octamolybdate electrode material of this example, which shows that the thermally vulcanized ammonium octamolybdate electrode material is also columnar and has small-particle nanocrystalline CoMoS 3.13 Is closely embedded in C 3 N 4 The frame is internally provided with a porous structure; b is the XRD pattern of the electrode material of the ammonium octamolybdate after the hot vulcanization, which confirms that the electrode material of the hot vulcanized ammonium octamolybdate is CoMoS 3.13 @C 3 N 4 。
FIG. 14A shows the CoMoS of this example 3.13 @C 3 N 4 The rate performance graph of the sodium ion battery shows that the capacity of 537.9mAh/g can be reached when the battery density is 0.1A/g, the capacity of 501.8mAh/g can be reached when the current density is increased to 1A/g, and the capacity of 401.0mAh/g can be reached when the current density is continuously increased to 20A/g; after the current density is switched back to 0.1mA/g in the 50 th cycle, the capacity of 539.9mAh/g can be still maintained, and the excellent rate capability of the electrode material of the polyoxometallate cluster is shown; b is the CoMoS of the invention 3.13 @C 3 N 4 The battery can still maintain 365.8mAh/g after circulating for 1000 circles under the high current density of 2A/g, which shows that the novel electrode has excellent structural stability.
In conclusion, the preparation method is suitable for assembling ordered structures of POMs (polyoxymethylene) clusters of different types and sizes, including ammonium tetramolybdate, ammonium heptamolybdate, ammonium octamolybdate and phosphomolybdic acid. The electrode material of the vulcanized POMs cluster assembly not only maintains a regular columnar structure, but also can guide the POMs cluster to be converted into high-dispersion high-activity CoMoS containing rich crystal boundaries in situ 3.13 Small crystal grains; small grains anchored in situ to porous C 3 N 4 In the layered framework, the layer-shaped frame,and with C 3 N 4 Forming abundant Co-N covalent bonds. The excellent micro-nano configuration constructed based on the POMs cluster not only improves the ion and electron transmission characteristics of the electrode material of the POMs cluster after thermal vulcanization as the cathode of the sodium ion battery, but also can effectively inhibit the problems of interface inactivation, structure collapse and the like in the charging and discharging processes of metal sulfides. Compared with the prior art, the method has the characteristics of simple preparation process, strong repeatability, high specific capacity of the sodium-ion battery, good cycling stability, excellent rate performance and the like, and has good economic benefit and environmental benefit.

Claims (10)

1. A preparation method of an electrode material based on multi-metal molybdate clusters is characterized by comprising the following steps:
s1, dispersing melamine in deionized water, completely dissolving at a preset temperature to obtain a uniform solution, namely a solution A, and then adding a transition metal Co (II) ion solution for reaction to obtain a solution B;
s2, dispersing the POMs into deionized water to obtain a solution C; adding the solution C into the solution B, continuously stirring for reaction to obtain a solution D, transferring the solution D into a reaction kettle, and carrying out assembly reaction at a preset temperature and time; obtaining a precipitate after the assembly reaction is finished, and washing and drying the precipitate to obtain the POMs cluster composite material with the multidimensional ordered structure;
and S3, mixing the POMs cluster composite material with sulfur powder, and then roasting in an inert atmosphere to obtain the thermally vulcanized POMs cluster electrode material.
2. The method for preparing an electrode material based on a multi-metal molybdate cluster according to claim 1, wherein in step S1, melamine is dispersed in deionized water, the concentration of the obtained solution is 0.08-0.15 mol/L, the preset temperature is 60-90 ℃, the molar ratio of melamine to transition metal Co (II) ions is (6-8): 1, and the time for adding the transition metal Co (II) ion solution to react is 10-60 min.
3. The method according to claim 1, wherein in step S2, the molar ratio of the transition metal Co (II) ions to the POMs is 1:1, and the POMs are selected from ammonium tetramolybdate, ammonium heptamolybdate, ammonium octamolybdate and phosphomolybdic acid.
4. The method according to claim 1, wherein in step S2, the concentration of solution C is 0.01-0.05 mol/L, the solution C is added dropwise, and the reaction time of solution D is 15-45 min.
5. The method for preparing an electrode material based on a multi-metal molybdate cluster according to claim 1, wherein the temperature of the assembly reaction is 150 to 200 ℃ and the time is 8 to 16 hours in step S2.
6. The method for preparing an electrode material based on multi-metal molybdate clusters as claimed in claim 1, wherein in step S2, the internal microstructure of the obtained POMs cluster composite material is that POMs clusters are linearly and orderly arranged on a two-dimensional layered Co-Mela substrate, and are further assembled into a regular nano-pillar structure in a three-dimensional space under the joint drive of coordination and conjugation.
7. The method for preparing the electrode material based on the multi-metal molybdate cluster as claimed in claim 1, wherein in the step S3, the mass ratio of the POMs cluster composite material to the sulfur powder is 1 (2-4).
8. The method for preparing the electrode material based on the multi-metal molybdate cluster according to the claim 1, wherein in the step S3, the roasting temperature is carried out in a tube furnace by adopting a temperature programming mode, firstly, the temperature is raised to 200 ℃ at a temperature raising rate of 0.5-1 ℃/min, the temperature is kept for 2h, and then, the temperature is raised to 450-550 ℃ at a temperature raising rate of 1-2.5 ℃/min, and the temperature is kept for 2 h.
9. An electrode material based on multi-metal molybdate clusters, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. Use of the electrode material based on multi-metal molybdate clusters as claimed in claim 9 as negative electrode material for sodium ion batteries.
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