CN113130865B - Bimetallic selenide carbon microsphere composite material and preparation method and application thereof - Google Patents

Bimetallic selenide carbon microsphere composite material and preparation method and application thereof Download PDF

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CN113130865B
CN113130865B CN202110349409.4A CN202110349409A CN113130865B CN 113130865 B CN113130865 B CN 113130865B CN 202110349409 A CN202110349409 A CN 202110349409A CN 113130865 B CN113130865 B CN 113130865B
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selenide
metal
carbon microsphere
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microsphere composite
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CN113130865A (en
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丁治英
谢旭
童汇
喻帅
刘洋
涂瑞萱
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Central South 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • C01B19/00—Selenium; Tellurium; Compounds thereof
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H—ELECTRICITY
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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a bimetallic selenide carbon microsphere composite material and a preparation method and application thereof. In the double-metal selenide carbon microsphere composite material, two metal selenides are mutually crosslinked through a carbon substrate and uniformly combined into a microsphere, one of the two metal selenides has a relatively high metal valence state, the other metal valence state is lower, and the introduction of high-valence metal can improve the electron and ion transmission effect of low-valence metal to generate the double-metal synergistic effect, so that the activity and the sodium storage performance of the material are improved. The carbon matrix not only provides a conductive network, but also limits the volume expansion of the material.

Description

Bimetallic selenide carbon microsphere composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion battery cathode materials, and particularly relates to a bimetallic selenide carbon microsphere composite material as well as a preparation method and application thereof.
Background
In order to reduce energy consumption and meet market demands, the utilization of new energy and the development of novel energy storage technology are the current trends in the development of the world energy industry. New energy sources such as solar energy, wind energy and tidal energy are processed and recycled through energy storage and conversion devices due to the discontinuity and uncontrollable property of time and space. Among numerous energy storage and conversion devices, a chemical power supply has the advantages of high conversion efficiency, strong applicability, convenience in use and the like, and is a hotspot of the current energy technology research. Lithium ion batteries are widely used in the fields of portable electronic devices, electric vehicles, aerospace, and the like due to their high energy density and power density. However, the lithium resource reserves are scarce and unevenly distributed, which hinders further development of lithium ion batteries.
In recent years, sodium ion batteries are receiving more and more extensive attention from researchers due to the abundant sodium resource reserves, low price and the similar energy storage mechanism of lithium ion batteries, and are expected to become the mainstream energy storage system of the next generation. The main components of the sodium ion battery are the same as those of the lithium ion battery, and the sodium ion battery comprises anode and cathode materials, a diaphragm, electrolyte and other accessory materials, wherein the characteristics of the anode and cathode materials are main determining factors of the energy density of the battery. However, the large ionic radius and molar mass of sodium ions results in slow ion diffusion kinetics and limited cycle life. Therefore, the development of positive and negative electrode materials with high capacity, long cycle stability, suitable voltage plateau and high safety is the core of commercialization of sodium ion batteries.
For the negative electrode material of the sodium ion battery, a carbon material, an intercalation-type, an alloy-type, and a conversion-type (such as transition metal oxide, sulfide, selenide, etc.) negative electrode material is generally included. The conversion type negative electrode material has become one of hot spots of research on the negative electrode of the sodium ion battery due to large theoretical capacity and simple synthesis method, but most of the materials show poor conductivity and Na is removed/inserted + The process is accompanied by large volume change and metal agglomeration, thereby influencing the cycle stability of the sodium-ion battery. The metal oxide has large polarization and low conductivity. The metal sulfide has the problem of polysulfide ion dissolution in the electrochemical cycle process, which results in poor cycle and rate performance. Although metal selenide (M) x Se y ) The polarization is relatively small, the conductivity is relatively high, the metal selenide can effectively avoid the problem of polysulfide ion dissolution in the metal sulfide in the circulation process, meanwhile, the selenium atom has the characteristics of larger diameter and stronger metallicity than the sulfur atom, and the metal selenide has the characteristics of larger diameter and stronger metallicity than the metal sulfideLarger interlayer spacing and higher electrical conductivity. However, the metal selenide has an agglomeration phenomenon in the process of sodium intercalation and deintercalation, the electron and ion transmission rates of the metal selenide are poor, and the structure is collapsed due to volume expansion.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a bimetallic selenide carbon microsphere composite material, which solves the problems of agglomeration phenomenon, large volume expansion and poor conductivity of selenide in charging and discharging overcharge.
The invention also provides a preparation method of the bimetallic selenide carbon microsphere composite material.
The invention also provides application of the bimetallic selenide carbon microsphere composite material.
The invention also provides a sodium ion battery containing the bimetallic selenide carbon microsphere composite material.
The invention provides a bimetallic selenide carbon microsphere composite material, which takes carbon microspheres as a matrix, and bimetallic selenide nano-particles are distributed in the matrix and on the surface of the matrix.
The bimetallic selenide carbon microsphere composite material disclosed by the invention at least has the following beneficial effects:
in the double-metal selenide carbon microsphere composite material, two metal selenides are mutually crosslinked through a carbon matrix and uniformly combined into microspheres, and in the two metal selenides, double-transition metal ions exert a metal synergistic effect, so that the surface potential energy of the material is dispersed, and the deep implementation of an oxidation-reduction reaction is facilitated. The bimetal synergistic effect can improve the whole electron and ion transmission function of the material, thereby improving the activity and sodium storage performance of the material. The carbon matrix not only provides a conductive network, but also limits the volume expansion of the material.
The bimetallic selenide carbon microsphere composite material has cheap and easily obtained raw materials. Has excellent ion and electron transmission rate. The advantages of a zinc selenide low-voltage working platform and high capacity of cobalt selenide are considered, and the bimetal synergistic effect enables the material to obtain good rate capability and cycle performance. The material has good stability and high sodium storage capacity, and is suitable for commercial application.
In the double metal selenide carbon microsphere composite material, one higher price and one lower price of two metals are not necessary. Firstly, the bimetallic selenide has stronger metallicity, lower forbidden bandwidth and higher conductivity. Thus, the bimetal selenide exhibits stronger chemical activity as well as higher electrochemical activity. In the bimetallic ion dispersion material, the synergistic effect can induce and improve the surface energy dispersion of the material, and is beneficial to the oxidation-reduction reaction of the material.
According to some embodiments of the invention, the particle size of the composite material is between 2 μm and 10 μm.
According to some embodiments of the invention, the bimetallic selenide comprises two of cobalt selenide, zinc selenide, iron selenide, nickel selenide, and copper selenide.
According to some embodiments of the invention, the molar percentage of cobalt in the bimetallic selenide is between 3% and 7%.
The metal cobalt is expensive and is in short supply, thus becoming a developed resource short board.
According to some embodiments of the present invention, the bimetallic selenide may be cobalt selenide and zinc selenide.
ZnSe, CoSe when the bimetallic selenide is cobalt selenide or zinc selenide 2 High-priced Co uniformly combined into microspheres 4+ The introduction of (2) improves the divalent Zn 2+ The electron and ion transmission rate of the material plays a role in synergism of bimetal, the activity and sodium storage performance of the material are improved, the agglomeration problem and volume expansion of selenide in the charging and discharging processes are solved, and the conductivity is improved. It should be noted that the bimetallic selenide does not necessarily need to have two valence states, and is a transition metal ion, so that the synergistic effect of the bimetallic selenide can be exerted.
A second aspect of the present invention provides a method for preparing a bimetallic selenide carbon microsphere composite material, comprising the steps of:
s1: uniformly dispersing a metal source and a selenium source in a solvent to obtain a solution A;
s2: adding a carbon source and alkali into the solution A, and uniformly stirring to obtain a solution B;
s3: and placing the solution B in a high-pressure reaction kettle for hydrothermal reaction.
The preparation method of the bimetallic selenide carbon microsphere composite material does not need a precursor, has simple and clear process steps and does not have harsh reaction conditions.
According to some embodiments of the invention, the metal source comprises two of zinc acetate dihydrate, cobalt nitrate hexahydrate, ferric chloride, cupric chloride, nickel chloride, ferric nitrate hexahydrate, nickel nitrate hexahydrate, and cupric nitrate.
According to some embodiments of the invention, the metal source may be zinc acetate dihydrate and cobalt nitrate hexahydrate.
According to some embodiments of the invention, the solvent comprises water, methanol or ethanol.
According to some embodiments of the invention, the source of selenium is selenium powder.
According to some embodiments of the invention, the carbon source comprises at least one of glucose, soluble starch and citric acid monohydrate.
According to some embodiments of the invention, after step S3, the method further comprises drying the product.
According to some embodiments of the invention, the hydrothermal reaction is carried out at a temperature of 120 ℃ to 180 ℃ for 12h to 30 h.
The third aspect of the invention provides an application of the bimetallic selenide carbon microsphere composite material in the preparation of a sodium-ion battery.
The fourth aspect of the invention provides a sodium-ion battery, which contains the bimetallic selenide carbon microsphere composite material.
Drawings
FIG. 1 is a scanning electron microscope image of the bimetallic selenide carbon microsphere composite material of the invention.
FIG. 2 is an X-ray diffraction pattern of the bimetallic selenide carbon microsphere composite material of the invention.
Fig. 3 is a result of a rate capability test of a sodium ion battery made of the bimetallic selenide carbon microsphere composite material of the invention.
Fig. 4 is a graph showing the cycle performance of a sodium ion battery made of the bimetallic selenide carbon microsphere composite material of the invention.
Fig. 5 is a result of a charge-discharge long cycle test of the monometallic zinc selenide carbon microsphere composite of comparative example 1.
Fig. 6 is a microscopic topography of the monometallic zinc selenide carbon microsphere composite of comparative example 1.
Fig. 7 is a microscopic morphology view of the monometallic cobalt selenide composite carbon material of comparative example 2.
Fig. 8 is a microscopic topography of the bimetallic selenide carbon microsphere composite of comparative example 3.
Fig. 9 is a microscopic topography of the dual metal selenide carbon microsphere composite of comparative example 4.
Fig. 10 is a microscopic topography of the dual metal selenide carbon microsphere composite of comparative example 5.
Fig. 11 is a microscopic topography of the dual metal selenide carbon microsphere composite of comparative example 6.
Fig. 12 is a microscopic topography of the bimetallic selenide carbon microsphere composite of comparative example 7.
Fig. 13 is a microscopic topography of the dual metal selenide carbon microsphere composite of comparative example 8.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment prepares the bimetallic selenide carbon microsphere composite material, and specifically comprises the following steps:
(1) weighing 9.5mmol of zinc acetate dihydrate, 0.5mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 18 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
Wherein the step (1) is used for dissolving and dispersing the bimetal source and the selenium source in the solvent.
The step (2) has the function of leading the selenium powder and the sodium hydroxide to have disproportionation reaction:
3Se+6NaOH＝Na 2 SeO 3 +2Na 2 Se+3H 2 O，
glucose provides a carbon source for the material.
In the hydrothermal reaction process in the step (3), the following reactions occur:
Zn(CH 3 COO) 2 +2NaOH＝Zn(OH) 2 (precipitation) +2CH 3 COONa，
Zn(CH 3 COO) 2 +Na 2 Se＝ZnSe+2CH 3 COONa，
Co 4+ +2Na 2 Se＝CoSe 2 +4Na + ，
Excess sodium hydroxide, effect of excess sodium hydroxide: 2NaOH + Zn (OH) 2 ＝Na 2 Zn(OH) 4 ，
Na 2 Zn(OH) 4 Dissolved in water and washed away in a subsequent centrifugal washing step.
The micro-morphology of the bimetallic selenide carbon microsphere composite material prepared by the embodiment is observed, as shown in fig. 1. As can be seen from the figure, the ZnSe and CoSe of the zinc selenide and the CoSe of the cobalt selenide are uniformly distributed on the surface of the material 2 The nanospheres, the nanospheres and the carbon network are combined into micron-sized microspheres, and the surface of the material has abundant defects and provides a shuttle channel for sodium ions.
ZnSe and CoSe 2 Through mutual cross-linking of carbon matricesSelf-assembling into micro-spheres. Due to the large van der Waals force of the Co-Se bond, partial agglomeration can be generated, so that the composite material is polymerized into the microspheres. And are uniformly distributed in the interior and on the surface of the microspheres.
Tetravalent cobalt ions enter, the synergistic action and the catalytic effect of bimetal are exerted, so that carbon matrixes with ordered long ranges are promoted to grow on the surfaces of the cobalt selenide and the zinc selenide nano particles, the conductivity of the material is improved, and the transmission rate of ions and electrons is improved.
The introduction of the metal cobalt reduces the forbidden bandwidth of the composite material, has stronger metallicity, improves the conductivity and reduces the energy required by the conversion reaction. Meanwhile, due to the double-metal synergistic effect and the catalytic effect, the material has rich active sites and a larger specific surface area, so that the infiltration of electrolyte is facilitated, and the ion transmission rate is increased.
Because the element cobalt has smaller element radius than the element zinc, the lattice spacing of the material is reduced, the ionic and electronic conductivity is improved, the sodium ion de-intercalation reaction is accelerated by the catalytic effect of the bimetal synergistic effect, and the agglomeration effect of the material is reduced. Meanwhile, zinc selenide and cobalt selenide are crosslinked through a carbon matrix, so that the volume expansion is limited.
The X-ray diffraction pattern of the bimetallic selenide carbon microsphere composite material prepared in this example was tested, as shown in fig. 2. From FIG. 2, it can be seen that ZnSe and CoSe are present in the composite material 2 The crystallization of (3) is preferred.
Example 2
In this embodiment, the battery pole piece is prepared from the bimetallic selenide carbon microsphere composite material prepared in embodiment 1. The method specifically comprises the following steps:
taking 70mg of the bimetallic selenide carbon microsphere composite material, a conductive agent and a binder, mixing the mixture in a ratio of 7: 1.5: 1.5, mixing, grinding and smearing.
And after the pole piece is dried in vacuum, stamping the pole piece into a battery pole piece.
Example 3
In this example, the battery electrode plate prepared in example 2 was assembled into a sodium ion battery for electrochemical performance test.
The rate capability is shown in FIG. 3, and it can be seen from FIG. 3 that when the current density is 5A g -1 The specific charge capacity of the material is 367.5mAh g -1 When the current density is returned to 0.1A · g -1 And the charging specific capacity is recovered to 508.7 mAh.g -1 (initial Current Density 0.1A. g -1 The specific charging capacity is 503.7mAh g -1 ) Therefore, the composite cathode material of the sodium-ion battery has excellent rate performance. The material can still obtain excellent rate performance even under the large current of 5A/g, and the electron and ion transmission rate of the material is excellent.
The long cycle performance is shown in FIG. 4. it can be seen from FIG. 4 that when the material is subjected to a charge-discharge long cycle test, the current density is 0.1 A.g -1 The charging specific capacity after 50 cycles of circulation is 482.5mAh g -1 (initial Current Density 0.1A. g -1 The specific charging capacity is 485mAh g -1 ) Therefore, the composite cathode material of the sodium-ion battery prepared by the invention has higher cycling stability.
Comparative example 1
This comparative example differs from example 1 in that this example is the preparation of monometallic zinc selenide.
The preparation method of the single-metal zinc selenide carbon microsphere composite material comprises the following steps:
(1) weighing 10mmol of zinc acetate dihydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 18 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying in vacuum for 12h, and after drying, grinding the material to obtain the monometal zinc selenide carbon microsphere composite material.
As shown in FIG. 6, the scanning electron microscope of the monometal zinc selenide carbon microsphere shows that the material is microspherical, the particle size of the surface nanoparticles is not uniform, and the material has a polyhedral, nanosphere and larger blocky structure, which is not beneficial to the whole oxidation-reduction reaction of the material.
The materials were assembled into a sodium ion battery, and the materials were subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles of circulation is 412.6mAh g -1
Comparative example 2
This comparative example differs from example 1 in that the present example is the preparation of monometallic cobalt selenide.
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain a purple brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 18 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (5) putting the solid material collected in the step (4) into a 60 ℃ oven, drying for 12 hours in vacuum, and after drying is finished, grinding the material to obtain the single-metal cobalt selenide carbon microsphere composite material.
The scanning electron microscope image of the monometallic cobalt selenide composite carbon material is shown in fig. 7, the material is not spherical, the distribution is uneven, and the cobalt selenide nano-agglomeration is serious.
The material was assembled into a sodium ion battery, and the material was subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles is 248mAh g -1 And the capacity decays faster in the first 10 cycles, with 53% capacity decaying in the first 10 cycles.
Comparative example 3
This comparative example differs from example 1 in the hydrothermal reaction time.
(1) Weighing 9.5mmol of zinc acetate dihydrate, 0.5mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material hydrothermal at 180 ℃ for 30 hours is shown in fig. 8, and as can be seen from fig. 8, the composite material still has a microsphere structure, the microsphere is uniformly formed by nanoparticles of cobalt selenide and zinc selenide, and the particle size of the material is larger.
The material is assembled into a sodium ion battery, and the material is subjected to charge-discharge long-cycle test, and as can be seen from figure 5, when the current density is 0.1A g -1 The charging specific capacity after 50 cycles is only 421mAh g -1 。
Comparative example 4
The comparative example is different from example 1 in the proportion of metal ions, and metal Co accounts for 10%.
(1) Weighing 9mmol of zinc acetate dihydrate, 1mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material with the cobalt accounting for 10 percent of the molar ratio is shown in fig. 9, and as can be seen from fig. 9, the composite material still basically has a microsphere structure, microsphere nanoparticles are unevenly distributed, and the composite material is formed by a large rod-shaped structure besides fine nanoparticles, so that the particle size of the material is large.
The material was assembled into a sodium ion battery, and the material was subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles of circulation is 363.51mAh g -1 。
Comparative example 5
The comparative example is different from example 1 in the proportion of metal ions, and the metal Co accounts for 15%.
(1) Weighing 8.5mmol of zinc acetate dihydrate, 1.5mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material with 15 percent of cobalt in molar ratio is shown in figure 10.
The material was assembled into a sodium ion battery, and the material was subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 Circularly filling for 50 circlesThe specific capacity is 363.96mAh g -1 。
Comparative example 6
The comparative example is different from example 1 in the proportion of metal ions, and the metal Co accounts for 20%.
(1) Weighing 8mmol of zinc acetate dihydrate, 2mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material with 20% cobalt in mole ratio is shown in fig. 11.
The materials were assembled into a sodium ion battery, and the materials were subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles is 413.01mAh g -1 。
Comparative example 7
The comparative example is different from example 1 in the proportion of metal ions, and the metal Co accounts for 25%.
(1) Weighing 7.5mmol of zinc acetate dihydrate, 2.5mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material with 25% cobalt in mole ratio is shown in fig. 12.
The material was assembled into a sodium ion battery, and the material was subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles is 367.92mAh g -1 。
Comparative example 8
The difference between the comparative example and the example 1 is that the proportion of metal ions is different, and the metal Co accounts for 50 percent.
(1) Weighing 5mmol of zinc acetate dihydrate, 5mmol of cobalt nitrate hexahydrate and 10mmol of selenium powder, adding 50mL of distilled water, and stirring for 30min to fully dissolve, wherein the solution is black;
(2) adding 1mmol of glucose and 0.1mol of sodium hydroxide into the black solution in the step (1), and magnetically stirring for 2 hours to obtain brown solution;
(3) putting the solution in the step (2) into a high-pressure reaction kettle, heating the solution in an oven to perform hydrothermal reaction at the reaction temperature of 180 ℃ for 30 hours;
(4) naturally cooling to room temperature after the reaction is finished, and centrifugally collecting;
(5) and (4) placing the solid material collected in the step (4) in a 60 ℃ oven, drying for 12h in vacuum, and after drying is finished, grinding the material to obtain the bimetallic selenide carbon microsphere composite material.
An electron scanning microscope of the bimetallic selenide carbon microsphere composite material with the cobalt accounting for 50 percent of the molar ratio is shown in figure 13.
The material was assembled into a sodium ion battery, and the material was subjected to a charge-discharge long cycle test, as can be seen from FIG. 5, when the current density was 0.1A · g -1 The charging specific capacity after 50 cycles is 290.79mAh g -1 And capacity decays rapidly in the first 15 revolutions。
In example 1, when the molar percentage of Co in the bimetallic selenide is 5%, the current density is 0.1 A.g -1 The charging specific capacity after 50 cycles is 482.5mAh g -1 The capacity attenuation rate is 0.31 percent compared with the second circle;
comparative example 1 is a monometallic zinc selenide with a current density of 0.1A g -1 The charging specific capacity after 50 cycles is 412.6mAh g -1 The capacity attenuation rate is 19.07 percent compared with the second circle;
comparative example 2 is a monometallic cobalt selenide with a current density of 0.1A g -1 The charging specific capacity after 50 cycles is 248mAh g -1 And the capacity attenuation is faster in the first 10 circles, and the capacity attenuation in the first 10 circles is 53%;
comparative example 3 is a hydrothermal reaction time of 30 hours, when the current density is 0.1A g -1 The charging specific capacity after 50 cycles is only 421mAh g -1 The capacity attenuation rate is 12.68 percent compared with the second circle;
in comparative example 4, the current density was 0.1 A.g when the molar percentage of Co in the bimetallic selenide was 10% -1 The charging specific capacity after 50 cycles is 363.51mAh g -1 The capacity attenuation rate is 1.18 percent compared with the second circle;
comparative example 5, the current density was 0.1 A.g when the molar percentage of Co in the bimetallic selenide was 15% -1 The charging specific capacity after 50 cycles of circulation is 363.96mAh g -1 The attenuation rate is 13.42 percent compared with the second circle capacity;
comparative example 6, the current density was 0.1 A.g when the molar percentage of Co in the bimetallic selenide was 20% -1 The charging specific capacity after 50 cycles is 413.01mAh g -1 The capacity attenuation rate is 34.90% compared with the second circle;
comparative example 7, current density was 0.1A g with Co in the bimetallic selenide of 25 mol% -1 The charging specific capacity after 50 cycles is 367.92mAh g -1 The attenuation rate is 39.30% compared with the second circle capacity;
comparative example 8, the current density was 0.1 A.g when the molar percentage of Co in the bimetallic selenide was 50% -1 The charging specific capacity after 50 cycles is 290.79mAhg -1 And capacity decays rapidly by 40.12% in the first 15 revolutions.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.

Claims (7)

1. The bimetallic selenide carbon microsphere composite material is characterized by comprising a carbon microsphere matrix, wherein bimetallic selenide nano-particles are distributed in the carbon microsphere matrix and on the surface of the carbon microsphere matrix;
the preparation method of the bimetallic selenide carbon microsphere composite material comprises the following steps:
s1: uniformly dispersing a metal source and a selenium source in a solvent to obtain a solution A;
s2: adding a carbon source and alkali into the solution A, and uniformly stirring to obtain a solution B;
s3: placing the solution B in a reaction kettle for hydrothermal reaction;
the bimetallic selenide comprises two of cobalt selenide, zinc selenide, iron selenide, nickel selenide and copper selenide;
the carbon source comprises at least one of glucose, soluble starch and citric acid monohydrate.
2. The bi-metal selenide carbon microsphere composite material of claim 1, wherein the molar percentage of cobalt in the bi-metal selenide is 3-7%.
3. The dual metal selenide carbon microsphere composite of claim 1, wherein the metal source includes two of zinc acetate dihydrate, cobalt nitrate hexahydrate, ferric chloride, cupric chloride, nickel chloride, ferric nitrate hexahydrate, nickel nitrate hexahydrate, and copper nitrate.
4. The dual metal selenide carbon microsphere composite of claim 1, wherein the selenium source is selenium powder.
5. The dual metal selenide carbon microsphere composite according to claim 1, further comprising drying the product after the step S3.
6. The bi-metal selenide carbon microsphere composite material of claim 1, wherein the temperature of the hydrothermal reaction is 120 ℃ to 180 ℃ and the time is 12h to 30 h.
7. The use of the bimetallic selenide carbon microsphere composite of claim 1 in the preparation of sodium ion batteries.
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CN113823790B (en) * 2021-08-23 2022-11-29 中南大学 Cobalt iron selenide/graphene nanoribbon composite negative electrode material and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220232A (en) * 2001-01-23 2002-08-09 Japan Storage Battery Co Ltd Method for manufacturing lithium-containing metal compound
CN105618781A (en) * 2016-01-02 2016-06-01 华东理工大学 Preparation method of Au@Cu2-xSe cage-like core-shell nanostructures
CN105789584A (en) * 2016-03-27 2016-07-20 华南理工大学 Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material
CN111790406A (en) * 2020-07-20 2020-10-20 济南大学 Preparation method of gold-copper selenide-cobalt-nickel layered double hydroxide composite paper

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101920942B (en) * 2010-09-20 2012-02-15 东华大学 Method for controlling synthesis of zinc selenide multi-morphological nano material
CN104016313B (en) * 2014-06-10 2015-09-23 郑州轻工业学院 A kind of preparation method of six side's copper selenide nanometer sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220232A (en) * 2001-01-23 2002-08-09 Japan Storage Battery Co Ltd Method for manufacturing lithium-containing metal compound
CN105618781A (en) * 2016-01-02 2016-06-01 华东理工大学 Preparation method of Au@Cu2-xSe cage-like core-shell nanostructures
CN105789584A (en) * 2016-03-27 2016-07-20 华南理工大学 Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material
CN111790406A (en) * 2020-07-20 2020-10-20 济南大学 Preparation method of gold-copper selenide-cobalt-nickel layered double hydroxide composite paper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Xuejiao Hu.Core–shell MOF-derived N-doped yolk–shell carbon nanocages homogenously filled with ZnSe and CoSe2 nanodots as excellent anode materials for lithium- and sodium-ion batteries.《Journal of Materials Chemistry A》.2019, *

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