CN114671414B - Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method - Google Patents
Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method Download PDFInfo
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Abstract
The invention discloses an iron-copper-tin ternary selenide nano material for a sodium ion battery, which uses FeSe 2 Is a matrix with FeSe 2 A phase structure; the Cu and Sn transition metal elements are uniformly dispersed in FeSe 2 In (a) and (b); microcosmic nanometer polyhedron stacked appearance, and fine nanometer particles are attached to part of the surface of the nanometer polyhedron. The invention also discloses a preparation method of the nano material, wherein a transition metal source adopts dichloride, water is used as a solvent, and citric acid is added, and the precursor solution is homogenized by continuous stirring; adding selenium source sodium selenite and selenium powder, dripping hydrazine hydrate, and performing hydrothermal reaction to obtain the nano material. The invention realizes the multielement recombination of the selenides and forms the multielement metal selenides with uniform distribution of each transition metal element. The sodium ion battery is assembled by taking the iron-copper-tin ternary selenide nano material as an electrode material, and has the advantages of ultra-long cycle life, ultra-fast charging property and ultra-wide temperature range working property.
Description
Technical Field
The invention belongs to the field of nano materials and energy sources, and particularly relates to a multi-selenide nano material and a preparation method thereof, which can be used as an electrode material of a high-performance sodium ion battery.
Background
With the increase of economy, the energy crisis and environmental pollution problems of the 21 st century are becoming more serious, and in order to meet the energy demands of our future, clean energy should be developed to replace traditional fossil fuels, such as solar energy, wind energy, nuclear energy, biological energy, tidal energy and other novel environment-friendly energy. However, these green energy sources are unstable and cannot be used directly by people, and an energy storage device is required to store energy which is converted and output stably and can be used directly by people. Rechargeable secondary ion batteries have been widely studied and used because of their high energy density, long cycle life and environmental friendliness. At present, the development of lithium ion batteries is limited by the shortage of lithium metal resources, while sodium metal resources are abundant and low in price, so that the sodium ion batteries are attracting attention. Because the radius of sodium ions is larger than that of lithium ions, the conventional graphite applied to the anode material of the lithium ion battery cannot meet the requirement of the sodium ion battery, so that a proper anode material of the sodium ion battery needs to be searched.
In recent years, transition metal oxides, sulfides and selenides have been widely studied as sodium ion battery anode materials with high theoretical specific capacities, good cycle stability and excellent rate capability. The transition metal selenide has the best conductivity, is expected to become a sodium ion battery anode material with high rate performance, and can meet the development requirements of quick charge of mobile phones and quick charge of new generation electric automobiles.
Currently, transition metal selenides have received extensive attention in the fields of superconductors, optoelectronic devices, catalysis, fuel-sensitized solar cells, supercapacitors and the like, and research in the field of sodium ion batteries is also increasing. The invention designs an electrode material for a high-efficiency sodium ion battery, which can be applied to future sodium ion batteries, in particular to sodium ion batteries working in harsh environments.
Disclosure of Invention
The invention aims to provide an electrode material for a high-performance sodium ion battery and a preparation method thereof.
The invention provides an iron-copper-tin ternary selenide nano material for a sodium ion battery, which is a transition metal selenide and comprises three transition metal elements of Fe, cu and Sn, wherein the molar ratio of Fe to Cu to Sn is about (7.7-8.3) 1:1; the iron-copper-tin ternary selenide nano material matrix is FeSe 2 With FeSe 2 A phase structure; the Cu and Sn transition metal elements are uniformly dispersed in FeSe 2 Is a kind of medium. The iron-copper-tin ternary selenide nano material is microscopically presented as a stacked shape of a plurality of nano polyhedrons, and the lengths of all sides of the nano polyhedrons are basically equal and are 500-900 nm; fine nano particles are attached to the surface of a part of the nano polyhedron.
For nanomaterials, multiple recombination or multiple doping is difficult, especially to form a uniform elemental distribution. For selenide nanomaterials, it is particularly a difficulty how to form uniform multi-element metal selenides because selenium combines with metal elements weakly relative to oxides. The iron-copper-tin ternary selenide nano material provided by the invention can be seen from the analysis of the microscopic morphology, the phase structure and the analysis of the energy spectrum on the element distribution, realizes the real multi-element recombination or multi-element doping of the selenide, forms the uniform distribution of each composite transition metal element, promotes the combination of selenium and metal elements, and obtains uniform multi-element metal selenide.
Further, the invention also provides a preparation method of the iron-copper-tin ternary selenide nano material, which comprises the following steps: weighing 1.58-1.62 mmol of ferric chloride, 0.19-0.21 mmol of copper chloride and 0.19-0.21 mmol of tin dichloride, wherein the adding molar ratio of three transition metal elements of Fe, cu and Sn is about (7.7-8.3) 1:1; dissolving in 19-21 mL of deionized water, adding citric acid after complete dissolution, and continuously stirring; adding 1.8-2.1 g of citric acid; then adding 2.8-3.2 mmol of sodium selenite and 0.9-1.1 mmol of selenium powder, and then adding 28-32 mL of deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 9-11 mL of hydrazine hydrate in the vigorous stirring to form a suspension; transferring the suspension into a 100 mL reaction kettle, and reacting for 12-18 hours at 140-180 ℃; and after the reaction is finished, obtaining a reaction product through a centrifugal way, repeatedly cleaning the reaction product with deionized water and ethanol for 3-5 times, and drying the reaction product at 70 ℃ for 12 hours to obtain the required product, namely the iron-copper-tin ternary selenide nanomaterial. The technological parameters can be amplified or reduced in the same proportion, and the same effect is achieved.
According to the preparation method, the transition metal sources are all metal dichlorides, so that the precursors can be uniformly mixed. The chemical properties of the three precursors are similar, the iron, copper and tin are all +2, and the three elements show synergistic effect; and ferric dichloride is used as a main precursor, copper dichloride and tin dichloride are used as auxiliary doping precursors, and the system stability can be improved. In the preparation method, citric acid is added, and stirring is continued, so that the precursor solution is more homogenized. Particularly, sodium selenite and selenium powder are added as selenium sources, so that the combination of metal elements and selenium elements is promoted, and the uniform combination of the metal elements and the selenium elements can be promoted; if sodium selenite and selenium powder are not added at the same time, the effect cannot be achieved. These characteristics enable the three elements of iron, copper and tin to be effectively combined with selenium element to form uniform multi-element metal selenide.
The iron-copper-tin ternary selenide nano material is used as an electrode material to assemble a sodium ion battery, and has the following performance indexes: the internal resistance of the battery is about 5 omega; the initial specific capacity is 470mAh/g under the current density of 1C, and the initial specific capacity is kept at 506mAh/g after 10000 circles of circulation; the coulomb efficiency in the electrochemical circulation process is more than 98 percent; the specific capacity is 290mAh/g under the ultra-high current density of 150 ℃; the specific capacity is 310mAh/g at the ultralow temperature of minus 50 ℃ and 340mAh/g at the ultrahigh temperature of plus 90 ℃; meanwhile, the composite material has excellent comprehensive electrochemical performances of low internal resistance, high capacity, long service life, ultra-fast charge, ultra-wide temperature range, high coulombic efficiency and the like. The electrochemical performance of ternary transition metal selenides is significantly improved over conventional mono-and binary transition metal selenides, such as: after 10000 circles, the water is kept at 506mAh/g, and the water has an ultra-long cycle life; the specific capacity is 290mAh/g under the ultra-high current density of 150 ℃, the ultra-high charge characteristic is realized, and the energy density is maintained at a high level under the ultra-high charge rate; can work at the ultra-low temperature of-50 ℃ and the ultra-high temperature of +90 ℃, and has the ultra-wide temperature range working characteristic; these characteristics are not achievable with other electrode materials.
The beneficial results of the invention are as follows:
(1) The invention realizes ternary transition metal selenide uniformly compounded by transition metal elements, and the provided iron-copper-tin ternary selenide nano material has good chemical stability, has the characteristic of high conductivity of transition metal selenide, is favorable for charge transfer in a battery, has a nano polyhedral structure, has high specific surface area, and can become an ideal electrode material of a sodium ion battery.
(2) The sodium ion battery manufactured by taking the material as the electrode has the advantages of high specific capacity, excellent multiplying power performance, ultra-fast charge, long cycle life and the like, can work in extreme environments of ultra-low temperature and ultra-high temperature, and has huge application potential.
(3) The preparation method provided by the invention overcomes the technical difficulties that the nano material, especially selenide, is difficult to multiplex or dope in multiple ways and difficult to form uniform element distribution by controlling the selection and process of the source material, and obtains uniform ternary metal selenide. The preparation method adopts a one-step hydrothermal synthesis method, does not need templates and surfactants, is simple and easy, has short flow, does not need complex equipment, has low cost and is beneficial to industrialization.
(4) The iron-copper-tin ternary selenide nano material provided by the invention mainly uses iron metal elements, has rich source materials, is low in cost and easy to obtain, has the effect of doping modification on copper and tin, has lower raw material cost, and is suitable for industrial production and sustainable development.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the iron-copper-tin ternary selenide nanomaterial prepared in example 1.
Fig. 2 is an x-ray diffraction (XRD) pattern of the iron-copper-tin ternary selenide nanomaterials prepared in example 1, example 2 and example 3.
Fig. 3 is a cycle performance chart of a sodium ion battery with an electrode assembled from the iron-copper-tin ternary selenide nanomaterial prepared in example 1.
Fig. 4 is a graph showing the rate characteristics of a sodium-ion battery with an electrode assembled from the iron-copper-tin ternary selenide nanomaterial prepared in example 1.
Fig. 5 is a graph showing the rate characteristics of a sodium-ion battery with an electrode assembled from the iron-copper-tin ternary selenide nanomaterial prepared in example 1.
Fig. 6 is a graph showing the high and low temperature performance of a sodium ion battery with an electrode assembled from the iron-copper-tin ternary selenide nanomaterial prepared in example 1.
Detailed Description
The present invention is further described below in conjunction with specific embodiments to provide a better understanding of the present invention to those skilled in the art. The present invention is not limited to the following examples.
Example 1
Weighing 1.60 mmol of ferric chloride, 0.20 mmol of copper chloride and 0.20 mmol of tin dichloride, dissolving in 20 mL deionized water, adding 1.8g of citric acid after complete dissolution, and continuously stirring; then adding 3 mmol of sodium selenite and 1mmol of selenium powder, and adding 30 mL deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 10 mL hydrazine hydrate in vigorous stirring to form suspension; transferring the suspension into a 100 mL reaction kettle, and reacting for 15 hours at 160 ℃; and after the reaction is finished, obtaining a reaction product by a centrifugal way, repeatedly cleaning the reaction product with deionized water and ethanol for 3-5 times, and drying the reaction product at 70 ℃ for 12 hours to obtain the required product, wherein the product is the iron-copper-tin ternary selenide nanomaterial.
Example 2
1.58 mmol of ferric chloride, 0.19 mmol of copper chloride and 0.19 mmol of tin dichloride are weighed and dissolved in 19 mL deionized water, after complete dissolution, 2.0g of citric acid is added and stirring is continued; then, adding 2.8 mmol of sodium selenite and 1.1mmol of selenium powder, and then adding 28 mL deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 9 mL hydrazine hydrate in vigorous stirring to form a suspension; transferring the suspension into a 100 mL reaction kettle, and reacting for 12 hours at 140 ℃; and after the reaction is finished, obtaining a reaction product by a centrifugal way, repeatedly cleaning the reaction product with deionized water and ethanol for 3-5 times, and drying the reaction product at 70 ℃ for 12 hours to obtain the required product, wherein the product is the iron-copper-tin ternary selenide nanomaterial.
Example 3
1.62mmol of ferric chloride, 0.21mmol of copper chloride and 0.21mmol of tin dichloride are weighed and dissolved in 21 mL deionized water, after complete dissolution, 2.1g of citric acid is added and stirring is continued; then, adding 3.2mmol of sodium selenite and 0.9mmol of selenium powder, and then adding 32mL deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 11mL hydrazine hydrate in vigorous stirring to form suspension; transferring the suspension into a 100 mL reaction kettle, and reacting for 18 hours at 180 ℃; and after the reaction is finished, obtaining a reaction product by a centrifugal way, repeatedly cleaning the reaction product with deionized water and ethanol for 3-5 times, and drying the reaction product at 70 ℃ for 12 hours to obtain the required product, wherein the product is the iron-copper-tin ternary selenide nanomaterial.
Performance test:
1) SEM test: and observing the samples prepared and finally obtained by the examples under a scanning electron microscope to obtain similar morphology. FIG. 1 is a sample microstructure obtained in example 1, from which it can be seen that: the nanomaterial presents a polyhedral shape, comprising different polyhedral surface numbers from pentahedron to octahedron and the like; the side length of each polyhedron is basically equal and is 500-900 nm; fine nano particles are attached to the surface of a part of the nano polyhedron. And (3) testing by adopting an SEM attached energy spectrometer to obtain: the obtained product contains three transition metal elements of Fe, cu and Sn, and is uniformly distributed; the molar ratio of Fe to Cu to Sn in the sample prepared in the example is about 8:1:1, and is basically consistent with the adding ratio of the source material, so that the sample prepared in the example is proved to realize multi-element compounding or multi-element doping of the selenide, and uniform transition metal element distribution is formed, and the example forms uniform multi-element metal selenide.
2) XRD test: the samples prepared in the examples above were subjected to XRD tests and also showed a completely similar XRD pattern. FIG. 2 shows XRD patterns of samples obtained in example 1, example 2 and example 3, diffraction peaks of the samples and FeSe 2 The characteristic peaks of the PDF card (79-1892) are in one-to-one correspondence, which indicates that the obtained product has FeSe 2 The phase structure shows that the matrix of the sample is FeSe 2 The addition of the other two elements Cu and Sn does not change the phase structure of the matrix material; it was also confirmed that the two transition metal elements Cu and Sn were uniformly dispersed in FeSe 2 In the material, no accumulation is formed to change the matrix material FeSe 2 Is a phase structure of (a).
3) Electrochemical performance test: and (3) taking the iron-copper-tin ternary selenide nano material prepared in the embodiment as an electrode to assemble the sodium ion battery. The general process of assembling the battery is as follows: directly taking an iron-copper-tin ternary selenide nano material as an electrode material, dissolving the electrode material in an N-methyl pyrrolidone solvent to form slurry, coating the slurry on a copper foil without adding a conductive additive and a binder to form an anode; sodium metal is used as a counter electrode; glass fiber (GF/F) is used as a diaphragm; naCF 3 SO 3 The electrolyte was dissolved in an N-methylpyrrolidone ((DIGLYME) solvent to form a solution, and the solution was assembled into a 2032-type coin cell in a glove box.
Through electrochemical performance tests, the electrochemical performance of the sodium ion battery assembled by the electrode material prepared by the embodiment is basically consistent, and the yield and the repeatability of the product are good. The performance index is given in detail below by taking example 1 as an example.
Fig. 3 shows the ac impedance spectrum of a sodium ion battery, and it can be seen that the internal resistance of the battery is small, about 5 Ω.
FIG. 4 is a graph of the cycling performance at a current density of 1C, with an initial specific capacity of 470mAh/g, which can reach 512mAh/g after 1000 cycles due to activation of the electrode material, and remain stable thereafter, and still reach 506mAh/g after 10000 cycles, showing that the electrode material has a very high specific capacity and an ultra-long cycle life; in all electrochemical cycling processes, the coulombic efficiency is above 98%, which indicates that the battery has excellent reversible charge and discharge characteristics.
Fig. 5 is a graph of the rate capability of the sodium ion battery, which can still stably work under the ultra-high current density of 150C, and the specific capacity can still reach 290mAh/g, showing that the sodium ion battery has ultra-high rate capability and ultra-fast charging rate.
FIG. 6 is a high-low temperature performance diagram of the sodium ion battery, which can work at an ultra-wide temperature range of-50 ℃ to 90 ℃, the specific capacity can still be kept at 310mAh/g at the ultra-low temperature of-50 ℃, and the specific capacity can still reach 340mAh/g at the ultra-high temperature of 90 ℃, so that the sodium ion battery has extremely excellent high-low temperature performance, and can be suitable for extreme working environments such as high cold, high heat and the like.
Claims (4)
1. An iron-copper-tin ternary selenide nanomaterial for a sodium ion battery is characterized in that: the iron-copper-tin ternary selenide nano material matrix is FeSe 2 With FeSe 2 A phase structure; the Cu and Sn transition metal elements are uniformly dispersed in the FeSe 2 In (a) and (b); the Fe-Cu-Sn ternary selenide nano material is microscopically presented as a plurality of nano polyhedron stacked shapesThe appearance of the nano polyhedron has each side length of 500-900 nm; fine nano particles are attached to the surface of part of the nano polyhedron;
in the iron-copper-tin ternary selenide nano material, the molar ratio of Fe to Cu to Sn is (7.7-8.3) 1:1.
2. A method for preparing the iron-copper-tin ternary selenide nano material for a sodium ion battery according to claim 1, which is characterized by comprising at least the following steps:
1) Dissolving ferric chloride, cupric chloride and tin dichloride in deionized water, adding citric acid after complete dissolution, and continuously stirring; forming a metal solution;
2) Adding sodium selenite and selenium powder into the metal solution, adding deionized water to form a mixed solution, stirring for a certain time by ultrasonic, keeping stirring, and adding hydrazine hydrate dropwise to form a suspension;
3) Transferring the suspension into a reaction kettle for parallel hydrothermal reaction; after the reaction is finished, obtaining a reaction product by a centrifugal mode;
4) Repeatedly cleaning and drying the reaction product by using deionized water and ethanol to obtain the iron-copper-tin ternary selenide nano material;
in the step 1), the added amounts of ferric dichloride, cupric dichloride and stannic dichloride are respectively 1.58-1.62 mmol, 0.19-0.21 mmol and 0.19-0.21 mmol; and the mol ratio of the addition of the three transition metal elements of Fe, cu and Sn is (7.7-8.3) 1:1;
adding 1.8-2.1 g of citric acid;
in the step 2), adding 2.8-3.2 mmol of sodium selenite and 0.9-1.1 mmol of selenium powder, and 28-32 mL of deionized water respectively;
stirring for 2-3 hours by ultrasonic, and adding 9-11 mL of hydrazine hydrate;
in the step 3), the hydrothermal reaction is carried out for 12-18 hours at 140-180 ℃.
3. The method for preparing the ternary selenide nanometer material of iron, copper and tin for sodium ion battery according to claim 2, which is characterized in that: in step 4), drying is carried out at 70℃for 12 hours.
4. The use of an iron-copper-tin ternary selenide nanocomposite for a sodium ion battery according to claim 1, wherein: the iron-copper-tin ternary selenide nano material is used as an electrode material to assemble a sodium ion battery, and the internal resistance of the battery is as low as 5 omega; under the current density of 1C, the initial specific capacity reaches 470mAh/g, and the initial specific capacity still remains 506mAh/g after 10000 circles of circulation; the coulomb efficiency in the electrochemical circulation process is more than 98 percent; the specific capacity is up to 290mAh/g under the ultra-high current density of 150 ℃; the specific capacity reaches 310mAh/g at the ultralow temperature of minus 50 ℃ and 340mAh/g at the ultrahigh temperature of plus 90 ℃.
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