CN114671414A - Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof - Google Patents
Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an iron-copper-tin ternary selenide nano material for a sodium ion battery, which is prepared from FeSe2As a matrix, with FeSe2A phase structure; cu and Sn two transition metal elements are uniformly dispersed in FeSe2Performing the following steps; microcosmically, the nano polyhedron is in a stacked shape, and fine nano particles are attached to the surfaces of part of the nano polyhedron. The invention also discloses a preparation method of the nano material, wherein a dichloride is adopted as a transition metal source, water is used as a solvent, citric acid is added, and the mixture is continuously stirred to homogenize a precursor solution; adding selenium source sodium selenite and selenium powder, dripping hydrazine hydrate, and performing hydrothermal reaction to obtain the nanometer material. The invention realizes the selenizationThe compound is compounded in a plurality of ways, and a plurality of metal selenides with evenly distributed transition metal elements are formed. The iron-copper-tin ternary selenide nano-material is used as an electrode material to assemble a sodium ion battery, and the sodium ion battery has the characteristics of ultra-long cycle life, ultra-fast charging and ultra-wide temperature range working characteristics.
Description
Technical Field
The invention belongs to the field of nano materials and energy, and particularly relates to a multi-element 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 in the 21 st century become more severe, and in order to meet the energy demand in the future, clean energy should be developed to replace the conventional 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 directly used by people, and an energy storage device is required to store, convert and output the energy into stable energy sources which can be directly used by people. Rechargeable secondary ion batteries have been widely studied and used due to 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, and sodium metal resources are abundant and low in price, so that sodium ion batteries attract attention of people. Because the radius of the sodium ions is larger than that of the lithium ions, the graphite which is traditionally applied to the anode material of the lithium ion battery can not meet the requirement of the sodium ion battery, and therefore, a proper anode material of the sodium ion battery needs to be found.
In recent years, transition metal oxides, sulfides and selenides have been extensively studied as sodium ion battery anode materials by virtue of high theoretical specific capacity, good cycling stability and excellent rate performance. 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 charging of mobile phones and quick charging of new-generation electric automobiles.
At present, transition metal selenides have attracted much attention in the fields of superconduction, photoelectric devices, catalysis, fuel-sensitized solar cells, super capacitors and the like, and research in the field of sodium ion batteries is 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 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) to 1: 1; the iron-copper-tin ternary selenide nano-material matrix is FeSe2Having FeSe2A phase structure; cu and Sn two transition metal elements are uniformly dispersed in FeSe2In (1). The iron-copper-tin ternary selenide nano-material is microscopically in the stacking shape of a plurality of nano polyhedrons, and the side lengths of the nano polyhedrons are basically equal and are 500-900 nm; fine nano-particles are attached to the surface of part of the nano polyhedron.
For nanomaterials, multiple compounding or multiple doping is difficult, especially to form a uniform distribution of elements. For selenide nano-materials, it is a particular difficulty how to form uniform multi-metal selenides because selenium is weakly bonded to metal elements 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 and the phase structure of the material and the analysis of the energy spectrum on the element distribution, the invention realizes the real multi-element compounding or multi-element doping of the selenide, forms the uniform distribution of each composite transition metal element, promotes the combination of selenium and the metal element, and obtains the 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 iron dichloride, 0.19-0.21 mmol of copper dichloride and 0.19-0.21 mmol of tin dichloride, wherein the molar ratio of the added three transition metal elements of Fe, Cu and Sn is (7.7-8.3): 1: 1; dissolving in 19-21 mL of deionized water, adding citric acid after complete dissolution, and continuously stirring; wherein 1.8-2.1 g of citric acid is added; 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 vigorous stirring to form a suspension; transferring the suspension into a 100 mL reaction kettle, and reacting at 140-180 ℃ for 12-18 hours; and after the reaction is finished, obtaining a reaction product in a centrifugal mode, repeatedly cleaning the reaction product for 3-5 times by using deionized water and ethanol, and drying the reaction product for 12 hours at 70 ℃ to obtain a required product, namely the iron-copper-tin ternary selenide nano material. The above process parameters can be enlarged or reduced in the same proportion to achieve the same effect.
According to the preparation method, the transition metal source adopts metal dichloride, so that the precursors can be uniformly mixed. The three precursors have similar chemical properties, the iron, the copper and the tin are all in a valence of +2, and the three elements show synergistic action; and the iron dichloride is used as a main precursor, and the copper dichloride and the tin dichloride are used as auxiliary doped precursors, so that the stability of the system can be improved. In the preparation method, citric acid is added and continuously stirred, so that the precursor solution is more homogenized. Particularly, the sodium selenite and the selenium powder are added as selenium sources at the same time, 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 the sodium selenite and the selenium powder are not added simultaneously, the effect can not be achieved. These characteristics enable the three elements of iron, copper and tin to be effectively combined with the selenium element to form uniform multi-metal selenide.
The sodium ion battery is assembled by taking the iron-copper-tin ternary selenide nano material as an electrode material, and has the following performance indexes: the internal resistance of the battery is about 5 omega; under the current density of 1C, the initial specific capacity is 470 mAh/g, and the specific capacity is maintained to be 506mAh/g after circulation for 10000 cycles; the coulombic efficiency in the electrochemical circulation process is more than 98 percent; the specific capacity is 290mAh/g under the condition of 150 ℃ ultrahigh current density; the specific capacity is 310mAh/g at the ultra-low temperature of-50 ℃, and is 340mAh/g at the ultra-high temperature of +90 ℃; meanwhile, the electrochemical material has excellent comprehensive electrochemical properties such as low internal resistance, high capacity, ultra-long service life, ultra-fast charge, ultra-wide temperature range, high coulombic efficiency and the like. Compared with the conventional unitary and binary transition metal selenides, the electrochemical performance of the ternary transition metal selenide is remarkably improved, such as: the circulation time is 10000 cycles, the circulation time is 506mAh/g, and the ultra-long circulation life is realized; under the condition of 150 ℃ ultrahigh current density, the specific capacity is 290mAh/g, the ultra-fast charging characteristic is realized, and the energy density is also maintained at a high level under the ultra-fast charging rate; the temperature control device can work at-50 ℃ ultralow temperature and +90 ℃ ultrahigh temperature, and has the working characteristic of ultra-wide temperature range; these characteristics are not achievable with other electrode materials.
The beneficial results of the invention are as follows:
(1) the invention realizes the ternary transition metal selenide formed by uniformly compounding various transition metal elements, and the provided iron-copper-tin ternary selenide nano material has good chemical stability, has the high conductivity characteristic of the transition metal selenide, is beneficial to the transfer of charges in a battery, has high specific surface area due to the nano polyhedral structure, and can be an ideal electrode material of a sodium ion battery.
(2) The iron-copper-tin ternary selenide nano material provided by the invention has the advantages of high specific capacity, excellent rate capability, super quick charge, long cycle life and the like, can work in extreme environments of ultralow temperature and ultrahigh temperature, and is a sodium ion battery with huge application potential.
(3) The preparation method provided by the invention overcomes the technical difficulties that the multi-element compounding or multi-element doping of nano materials, especially selenides, is difficult to form uniform element distribution by controlling the selection and the process of source materials, and obtains uniform ternary metal selenides. The preparation method adopts a one-step hydrothermal synthesis method, does not need a template and a surfactant, 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 nanometer material provided by the invention mainly uses iron metal elements, has rich source materials, is cheap and easy to obtain, has the doping modification effect on copper and tin, has low 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 nanomaterial prepared in example 1, example 2, and example 3.
Fig. 3 is a cycle performance diagram of a sodium ion battery assembled by using the iron-copper-tin ternary selenide nano-material prepared in example 1 as an electrode.
Fig. 4 is a rate characteristic diagram of the sodium ion battery assembled by using the iron-copper-tin ternary selenide nano-material prepared in example 1 as an electrode.
Fig. 5 is a rate characteristic diagram of the sodium-ion battery assembled by using the iron-copper-tin ternary selenide nano-material prepared in example 1 as an electrode.
Fig. 6 is a high-low temperature performance diagram of the sodium ion battery assembled by taking the iron-copper-tin ternary selenide nano-material prepared in example 1 as an electrode.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention. The present invention is not limited to the following examples.
Example 1
Weighing 1.60 mmol of iron dichloride, 0.20 mmol of copper dichloride and 0.20 mmol of tin dichloride, dissolving in 20 mL of 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 then adding 30 mL of deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 10 mL of hydrazine hydrate in vigorous stirring to form a 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 in a centrifugal mode, repeatedly cleaning the reaction product for 3-5 times by using deionized water and ethanol, and drying the reaction product for 12 hours at 70 ℃ to obtain a required product, namely the iron-copper-tin ternary selenide nano material.
Example 2
Weighing 1.58 mmol of iron dichloride, 0.19 mmol of copper dichloride and 0.19 mmol of tin dichloride, dissolving in 19 mL of deionized water, adding 2.0g of citric acid after complete dissolution, and continuously stirring; then, adding 2.8 mmol of sodium selenite and 1.1mmol of selenium powder, and then adding 28 mL of deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 9 mL of 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 in a centrifugal mode, repeatedly cleaning the reaction product by using deionized water and ethanol for 3-5 times, and drying the reaction product for 12 hours at 70 ℃ to obtain a required product, namely the iron-copper-tin ternary selenide nano material.
Example 3
Weighing 1.62 mmol of iron dichloride, 0.21 mmol of copper dichloride and 0.21 mmol of tin dichloride, dissolving in 21 mL of deionized water, adding 2.1g of citric acid after complete dissolution, and continuously stirring; then, adding 3.2 mmol of sodium selenite and 0.9mmol of selenium powder, and then adding 32 mL of deionized water to form a mixed solution; after ultrasonic stirring for 2-3 hours, dropwise adding 11 mL of hydrazine hydrate in vigorous stirring to form a 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 in a centrifugal mode, repeatedly cleaning the reaction product for 3-5 times by using deionized water and ethanol, and drying the reaction product for 12 hours at 70 ℃ to obtain a required product, namely the iron-copper-tin ternary selenide nano material.
And (3) performance testing:
1) and (4) SEM test: the samples finally obtained by the preparation of the above examples are observed under a scanning electron microscope, and similar appearances are obtained. FIG. 1 is a microscopic image of the sample prepared in example 1, from which it can be seen that: the nano material is in a polyhedral shape and comprises different polyhedral surfaces from pentahedron to octahedron and the like; the side lengths of all the polyhedrons are basically equal and are 500-900 nm; fine nano-particles are attached to the surface of part of the nano polyhedron. And (3) performing an energy spectrometer test attached to the SEM 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 the molar ratio is basically consistent with the adding ratio of the source material, so that the sample prepared in the example realizes the multi-element compounding or multi-element doping of the selenide, the uniform distribution of the transition metal elements is formed, and the uniform multi-element metal selenide is formed in the example.
2) XRD test: the sample prepared in the above example was subjected to XRD testing and also showed a completely similar XRD pattern. FIG. 2 is the XRD patterns of the samples prepared in example 1, example 2 and example 3, the diffraction peaks and FeSe of the samples2The characteristic peaks of the PDF card (79-1892) are in one-to-one correspondence, which shows that the obtained product has FeSe2Phase structure, indicating that the matrix of the sample is FeSe2The addition of the other two elements Cu and Sn does not change the phase structure of the base material; also proves that two transition metal elements of Cu and Sn are uniformly dispersed in FeSe2In the material, no pile-up is formed to change the base material FeSe2The phase structure of (1).
3) And (3) electrochemical performance testing: the iron-copper-tin ternary selenide nano-material prepared in the embodiment is used as an electrode to assemble a sodium ion battery. The general process of assembling the cell is as follows: directly taking an iron-copper-tin ternary selenide nano material as an electrode material, dissolving the material in an N-methyl pyrrolidone solvent to form slurry, and 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; NaCF3SO3Dissolving in N-methylpyrrolidone (DIGLYME) solvent to obtain solution as electrolyte, and assembling into 2032 type button cell in glove box.
Through electrochemical performance tests, the electrochemical performance of the sodium ion battery assembled by the electrode material prepared in the embodiment is basically consistent, and the yield and repeatability of the product are good. The following gives the detailed performance index of example 1.
Fig. 3 is an 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 cycle performance diagram under a current density of 1C, the initial specific capacity is 470 mAh/g, the initial specific capacity can reach 512mAh/g after 1000 cycles because of the activation of the electrode material, and then the initial specific capacity is kept stable, and the initial specific capacity can still reach 506mAh/g after 10000 cycles of cycle, which shows that the electrode material not only has very high specific capacity, but also has ultra-long cycle life; the coulombic efficiency is more than 98% in all electrochemical cycling processes, and the battery has excellent reversible charge-discharge characteristics.
Fig. 5 is a rate performance diagram of the sodium ion battery, which can still stably work under the condition of the ultrahigh current density of 150C, and the specific capacity can still reach 290mAh/g, showing that the sodium ion battery has ultrahigh rate performance and ultrafast charging rate.
Fig. 6 is a high-low temperature performance diagram of the sodium ion battery, which can work at an ultra-wide range temperature of-50 ℃ to 90 ℃, the specific capacity can still be maintained at 310mAh/g at an ultra-low temperature of-50 ℃, and the specific capacity can still reach 340mAh/g at an ultra-high temperature of 90 ℃, so that the high-low temperature performance diagram shows that the high-low temperature performance diagram has extremely excellent high-low temperature performance, and is suitable for extreme working environments such as high cold, high heat and the like.
Claims (8)
1. An iron-copper-tin ternary selenide nano material for a sodium ion battery is characterized in that: the iron-copper-tin ternary selenide nano-material matrix is FeSe2Having FeSe2A phase structure; cu and Sn two transition metal elements are uniformly dispersed in the FeSe2Performing the following steps; the iron-copper-tin ternary selenide nano material is microscopically in the stacked shape of a plurality of nano polyhedrons, and the side length of each nano polyhedron is 500-900 nm; fine nano-particles are attached to the surface of part of the nano polyhedron.
2. The iron-copper-tin ternary selenide nanomaterial for the sodium-ion battery according to claim 1, wherein: in the iron-copper-tin ternary selenide nano material, the molar ratio of Fe to Cu to Sn is (7.7-8.3) to 1.
3. The method for preparing the iron-copper-tin ternary selenide nano-material for the sodium-ion battery as claimed in claim 1 or 2, which is characterized by at least comprising the following steps:
dissolving iron dichloride, copper dichloride and stannic chloride in deionized water, adding citric acid after completely dissolving, and continuously stirring; forming a metal solution;
adding sodium selenite and selenium powder into the metal solution, adding deionized water to form a mixed solution, carrying out ultrasonic stirring for a certain time, keeping stirring, and dropwise adding hydrazine hydrate to form a suspension;
moving the suspension into a reaction kettle, and carrying out parallel hydrothermal reaction; after the reaction is finished, obtaining a reaction product in a centrifugal mode;
and repeatedly cleaning and drying the reaction product by using deionized water and ethanol to obtain the iron-copper-tin ternary selenide nano material.
4. The method for preparing the iron-copper-tin ternary selenide nano-material for the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the step 1), the adding amount of iron dichloride, copper dichloride and tin dichloride is 1.58-1.62 mmol, 0.19-0.21 mmol and 0.19-0.21 mmol respectively; the molar ratio of the three transition metal elements of Fe, Cu and Sn is (7.7-8.3) to 1: 1; adding 1.8-2.1 g of citric acid.
5. The method for preparing the iron-copper-tin ternary selenide nano-material for the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the step 2), adding 2.8-3.2 mmol, 0.9-1.1 mmol and 28-32 mL of deionized water of sodium selenite and selenium powder respectively; ultrasonically stirring for 2-3 hours, and adding 9-11 mL of hydrazine hydrate.
6. The method for preparing the iron-copper-tin ternary selenide nano-material for the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in the step 3), the hydrothermal reaction is carried out at 140-180 ℃ for 12-18 hours.
7. The method for preparing the iron-copper-tin ternary selenide nano-material for the sodium-ion battery according to claim 3, wherein the method comprises the following steps: in step 4), drying was carried out at 70 ℃ for 12 hours.
8. The use of the iron-copper-tin ternary selenide nanomaterial for the sodium-ion battery according to claim 1 or 2, wherein: assembling a sodium ion battery by taking the iron-copper-tin ternary selenide nano material as an electrode material, wherein the internal resistance of the battery is as low as 5 omega; under the current density of 1C, the initial specific capacity reaches 470 mAh/g, and the specific capacity is maintained to be 506mAh/g after circulation for 10000 cycles; the coulombic efficiency in the electrochemical circulation process is more than 98 percent; under the condition of 150C ultrahigh current density, the specific capacity reaches 290 mAh/g; the specific capacity reaches 310mAh/g at the ultra-low temperature of-50 ℃ and reaches 340mAh/g at the ultra-high temperature of +90 ℃.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2921834A (en) * | 1957-01-31 | 1960-01-19 | Merck & Co Inc | Process for preparing metal selenides |
| WO2012001094A1 (en) * | 2010-07-02 | 2012-01-05 | Umicore | Selenide powders and manufacturing process |
| US20130037111A1 (en) * | 2011-08-10 | 2013-02-14 | International Business Machines Corporation | Process for Preparation of Elemental Chalcogen Solutions and Method of Employing Said Solutions in Preparation of Kesterite Films |
| CN103938169A (en) * | 2014-04-09 | 2014-07-23 | 华东师范大学 | Preparation method of copper-ferrum-tin-selenium thin film |
| CN108483412A (en) * | 2018-06-14 | 2018-09-04 | 西南大学 | The method for preparing metal selenide nano material based on one step of hydro-thermal method |
| CN110304612A (en) * | 2019-06-26 | 2019-10-08 | 浙江大学 | A kind of two ferrous selenide nanometer sheets for lithium ion battery negative material |
| US20190319263A1 (en) * | 2018-04-13 | 2019-10-17 | Nanotek Instruments, Inc. | Alkali metal-selenium secondary battery containing a cathode of protected selenium |
| CN110649262A (en) * | 2019-09-29 | 2020-01-03 | 苏州潜寻新能源科技有限公司 | Preparation method and application of nano cubic bimetal selenide material |
| CN110943216A (en) * | 2019-12-20 | 2020-03-31 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt-iron bimetallic selenide sodium-ion battery cathode material |
-
2022
- 2022-03-25 CN CN202210298721.XA patent/CN114671414B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2921834A (en) * | 1957-01-31 | 1960-01-19 | Merck & Co Inc | Process for preparing metal selenides |
| WO2012001094A1 (en) * | 2010-07-02 | 2012-01-05 | Umicore | Selenide powders and manufacturing process |
| US20130037111A1 (en) * | 2011-08-10 | 2013-02-14 | International Business Machines Corporation | Process for Preparation of Elemental Chalcogen Solutions and Method of Employing Said Solutions in Preparation of Kesterite Films |
| CN103938169A (en) * | 2014-04-09 | 2014-07-23 | 华东师范大学 | Preparation method of copper-ferrum-tin-selenium thin film |
| US20190319263A1 (en) * | 2018-04-13 | 2019-10-17 | Nanotek Instruments, Inc. | Alkali metal-selenium secondary battery containing a cathode of protected selenium |
| CN108483412A (en) * | 2018-06-14 | 2018-09-04 | 西南大学 | The method for preparing metal selenide nano material based on one step of hydro-thermal method |
| CN110304612A (en) * | 2019-06-26 | 2019-10-08 | 浙江大学 | A kind of two ferrous selenide nanometer sheets for lithium ion battery negative material |
| CN110649262A (en) * | 2019-09-29 | 2020-01-03 | 苏州潜寻新能源科技有限公司 | Preparation method and application of nano cubic bimetal selenide material |
| CN110943216A (en) * | 2019-12-20 | 2020-03-31 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt-iron bimetallic selenide sodium-ion battery cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115947315A (en) * | 2023-02-20 | 2023-04-11 | 安徽工程大学 | Transition metal selenide for supercapacitor electrode material and preparation method thereof |
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