CN106654192B - Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof - Google Patents
Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof Download PDFInfo
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- CN106654192B CN106654192B CN201610972942.5A CN201610972942A CN106654192B CN 106654192 B CN106654192 B CN 106654192B CN 201610972942 A CN201610972942 A CN 201610972942A CN 106654192 B CN106654192 B CN 106654192B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
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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
- 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
- H01M4/5815—Sulfides
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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
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a tin sulfide/graphene sodium-ion battery composite negative electrode material and a preparation method thereof. The preparation method comprises the following steps: dissolving tin sulfide in an ammonium sulfide solution, adding a graphene oxide solution, performing ultrasonic treatment to uniformly disperse the solution, constructing a three-dimensional porous structure by quick freezing, and freeze-drying for 6-72h to obtain a precursor of the tin sulfide and graphene composite material, wherein the precursor is calcined for 1-24 h at 250-500 ℃ in an inert or reducing atmosphere to obtain the tin sulfide/graphene sodium-ion battery composite negative electrode material. The composite material can be used as a negative electrode material of a sodium ion battery and has a current density of 1Ag‑1The specific capacity can reach 649.5mAh g‑1And the specific capacity retention rate is more than 90% after 300 cycles. Compared with the traditional hydrothermal method and the like, the method has the advantages of short flow, simple process, lower energy consumption, high controllability of material preparation, easiness in realization of large-scale production, more excellent electrochemical performance and the like.
Description
Technical Field
The invention relates to the field of sodium ion battery materials, in particular to a tin sulfide/graphene sodium ion battery composite negative electrode material and a preparation method thereof.
Background
The 'energy crisis' and 'environmental pollution' are two serious problems that human beings must face in the 21 st century, and the development of a large-scale green energy storage power grid is one of approaches for solving the problems. The sodium ion battery is expected to replace a lithium ion battery due to the cost advantage, and becomes the first choice in the field of large-scale energy storage. At present, the cathode materials of the sodium ion battery are mainly various carbon materials, the sodium storage capacity of the carbon cathode materials is limited, the efficiency is extremely low for the first time, the further improvement of the energy density of the sodium ion battery at present is greatly limited, and the performance improvement by simply improving the preparation process is difficult to achieve breakthrough progress. The alloy negative electrode material (tin, antimony, germanium and the like) has high capacity, but the cycle life of the material is poor due to severe volume change in the sodium extraction process. Therefore, it is important to develop an electrode material for a sodium ion battery having a high specific capacity, a high rate, and a long life. Research shows that tin sulfide has larger layer space, is very favorable for storing sodium ions, and has a theoretical capacity up to 1236 mAh g due to conversion reaction and alloy reaction in the process of sodium extraction-1. But sulfide has poor conductivity, and volume change is inevitable in the process of sodium extraction, so that the cycle life of the material is difficult to meet the requirements of practical application. The composite material prepared by compounding the graphene with the graphene is an effective method for effectively improving the electrochemical performance of the tin sulfide material, and the traditional method generally adopts hydrothermal and solid-phase ball milling, so that the preparation process of the material is complex and the controllable preparation of the material is difficult to realize.
The invention provides a preparation method of a tin sulfide/graphene sodium-ion battery composite negative electrode material, which has the following main contents and innovation points: according to the invention, commercial tin sulfide is used as a raw material, a three-step method, namely compounding a room-temperature tin sulfide solution and graphene oxide, rapidly freezing to construct a three-dimensional porous structure, and sintering at a low temperature for crystallization, is adopted to prepare the tin sulfide/graphene composite material which is reliable in appearance, simple in preparation method, easy in obtaining of raw materials and easy for large-scale production. Graphene in the composite material provides a porous structure, sodium ion transmission in the charging and discharging process is facilitated, in addition, the graphene tightly coated on the surface of tin sulfide can improve the electronic conductivity of the whole material, the graphene coated on the surface of tin sulfide can relieve the volume change of antimony sulfide in the charging and discharging process, and the obtained material has high capacity, excellent rate capability and cycle performance, and is particularly suitable for serving as a negative electrode material of a sodium ion secondary battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a tin sulfide/graphene sodium-ion battery composite negative electrode material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a tin sulfide/graphene sodium-ion battery composite negative electrode material comprises the following steps:
(1) stirring and dissolving tin sulfide in an ammonium sulfide solution to form a stable and transparent yellow solution;
(2) adding 0.1-30 mg ml of the solution obtained in the step (1)-1Carrying out ultrasonic treatment on the graphene oxide solution until the graphene oxide solution is uniformly dispersed;
(3) rapidly freezing the solution obtained in the step (2), and drying to obtain a three-dimensional porous tin sulfide and graphene composite material precursor;
(4) subjecting the composite material precursor to an inert or reducing atmosphere at a temperature of 250-500 DEG CoAnd C, calcining for 1-24 hours to obtain the tin sulfide/graphene sodium-ion battery composite negative electrode material.
Further, the mass concentration of the ammonium sulfide solution in the step (1) is 0.5-20%, preferably 1-20 wt%, and tin sulfide and ammonium sulfide are subjected to a complex reaction to form [ SnS [2]2-And dissolved.
Furthermore, the molar ratio of the tin sulfide to the ammonium sulfide in the step (1) is (0.001-4): 1.
Further, the mass ratio of the graphene oxide to the tin sulfide in the graphene oxide solution in the step (2) is (0.001-0.5): 1.
Further, the time of the ultrasound in the step (2) is 1-600 min.
Further, the quick freezing method in the step (3) is one or more of liquid nitrogen freezing, dry ice freezing and laser freezing.
Further, the freeze drying time in the step (3) is 6-72 h.
Further, the drying in the step (3) is one or more of freeze drying, vacuum freeze drying and microwave vacuum freeze drying.
The purpose of quick freezing in the step (3) is to construct a three-dimensional porous structure, and meanwhile, the porous structure is not damaged through freeze drying.
Further, the inert or reducing atmosphere in the step (4) is nitrogen, argon, hydrogen or a mixture gas thereof.
The tin sulfide/graphene sodium-ion battery composite negative electrode material prepared by the preparation method is formed by compounding tin sulfide and graphene.
Compared with the prior art, the invention has the following advantages and technical effects:
1) the tin sulfide/graphene sodium-ion battery composite negative electrode material is obtained by a three-step method, namely (1) compounding tin sulfide and graphene oxide in an aqueous solution at room temperature, (2) rapidly freezing to construct a three-dimensional structure, (3) and sintering at low temperature.
2) The graphene in the composite material provided by the invention provides a porous three-dimensional structure, which is beneficial to the transmission of sodium ions in the charging and discharging process, in addition, the graphene tightly coated on the surface of the tin sulfide can improve the electronic conductivity of the whole material, the graphene coated on the surface of the tin sulfide plays a role in stabilizing the structure, the volume change in the charging and discharging process of the tin sulfide can be relieved, and the obtained material has high capacity, excellent rate capability and cycle performance.
Drawings
Fig. 1 is an XRD pattern of the tin sulfide/graphene composite material of example 1;
a and b in fig. 2 are SEM images of the tin sulfide/graphene composite material prepared in example 1;
FIG. 3 is a graph of the current density of the tin sulfide/graphene composite material prepared in example 1 being 0.1A g-1A time first charge-discharge curve chart;
a and b in fig. 4 are SEM and TEM images of the tin sulfide/graphene composite material prepared in example 2, respectively;
FIG. 5 shows the tin sulfide/graphene composite material prepared in example 2 at a current density of 1A g-1A time cycle performance map;
FIG. 6 shows the tin sulfide/graphene composite material prepared in example 3 at a current density of 3A g-1Time cycle performance diagram.
Detailed Description
The invention is further described with reference to the following figures and detailed description. The following examples are intended to illustrate the invention without further limiting it.
Example 1:
0.01 g of commercial tin sulfide was dissolved with stirring in 372.7 g of a 1 wt.% ammonium sulfide solution (molar ratio of tin sulfide to ammonium sulfide: 0.001: 1), to which was added 0.1 mg ml-1The graphene oxide solution has a mass ratio of graphene oxide to tin sulfide of 0.001: 1, carrying out ultrasonic treatment for 1 min to fully and uniformly disperse the precursor, then rapidly freezing the precursor by using liquid nitrogen, and carrying out freeze drying for 6 h to obtain the precursor. The precursor is placed in a nitrogen atmosphere 250oAnd C, sintering for 24 hours to obtain the tin sulfide/graphene composite material. Physical and chemical properties of the tin sulfide/graphene composite material are shown in the figure 1 and the figure 2. After comparison with a standard reference card, XRD shows that the tin sulfide/graphene composite material synthesized by the method is consistent with the standard card. SEM watchThe composite material is loose and porous, and tin sulfide particles are very fine and are uniformly compounded with graphene. The obtained product is assembled into a button cell to measure the charge and discharge capacity of the button cell, and the charge and discharge are carried out within the range of 0.01-2.5V. As shown in fig. 3, the current density is 0.1A g-1The first charging and discharging curve of the process does not have a charging and discharging platform of graphene, and the coating layer does not participate in sodium deintercalation. Meanwhile, the capacity of the composite material reaches 744.3 mAh g-1。
Example 2:
40 mmol of commercial tin sulfide were dissolved with stirring in 3.4 g of a 20 wt.% ammonium sulfide solution (molar ratio of tin sulfide to ammonium sulfide: 4: 1), to which was added 30 mg ml-1The graphene oxide solution has a mass ratio of graphene oxide to tin sulfide of 0.5: 1, and performing ultrasonic treatment for 600 min to ensure that the mixture is fully and uniformly dispersed. And (4) rapidly refrigerating the solution after ultrasonic treatment by using dry ice, and then carrying out vacuum freeze drying for 36 h to obtain a precursor. Then the precursor is put in an argon atmosphere 500oAnd C, sintering for 1 h to obtain the tin sulfide/graphene composite material. Physical and chemical properties of the tin sulfide/graphene composite material are shown in fig. 4 and fig. 5. SEM and TEM results in FIG. 4 show that tin sulfide is more uniformly compounded with graphene. FIG. 5 shows that the current density is 1A g-1The figure shows that the current density specific capacity of the composite material is 1A g-1The time capacity is as high as 649.5mAh g-1And the capacity retention rate after 300 cycles is 90.7%.
Example 3:
4 mmol of commercial tin sulfide were dissolved with stirring in 13.68 g of 11.5 wt.% ammonium sulfide solution (molar ratio of tin sulfide to ammonium sulfide: 2: 1), and 15 mg ml of the solution was added-1The mass ratio of the graphene oxide to the tin sulfide in the graphene oxide solution is 0.25:1, the graphene oxide and the tin sulfide are subjected to ultrasonic treatment for 300 min to be fully and uniformly dispersed, and the graphene oxide solution is frozen by a laser rapid refrigeration technology and then is subjected to microwave vacuum freeze drying for 72h to obtain a precursor. The precursor is added to the reaction solution at 3% vol2/N2Atmosphere 375oAnd C, sintering for 5 hours to obtain the tin sulfide/graphene material. Assembling the obtained product into button cell to measure charge and dischargeCapacity, 3A g in the range of 0.01-2.5V-1The cycle life test under the condition obtains that the current density of the tin sulfide/graphene material is 3A g as shown in figure 6-1The following cycle charge and discharge curves show that the capacity retention rate of the composite material can still approach 100% after 100 cycles.
Claims (9)
1. A preparation method of a tin sulfide/graphene sodium-ion battery composite negative electrode material is characterized by comprising the following steps:
(1) stirring and dissolving tin sulfide in an ammonium sulfide solution to form a stable transparent solution, wherein the molar ratio of the tin sulfide to the ammonium sulfide is (0.001-4) to 1;
(2) adding 0.1-30 mg ml of the solution obtained in the step (1)-1Carrying out ultrasonic treatment on the graphene oxide solution until the graphene oxide solution is uniformly dispersed;
(3) rapidly freezing the solution obtained in the step (2), and then drying to obtain a three-dimensional porous tin sulfide and graphene composite material precursor;
(4) and calcining the precursor of the tin sulfide and graphene composite material for 1-24 hours at 250-500 ℃ in an inert or reducing atmosphere to obtain the tin sulfide/graphene sodium-ion battery composite negative electrode material.
2. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, characterized by comprising the following steps: the mass concentration of the ammonium sulfide solution in the step (1) is 0.5-20%.
3. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, characterized by comprising the following steps: the mass ratio of the graphene oxide to the tin sulfide in the graphene oxide solution in the step (2) is (0.001-0.5): 1.
4. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, characterized by comprising the following steps: and (3) the ultrasonic treatment time in the step (2) is 1-600 min.
5. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, characterized by comprising the following steps: and (3) the quick freezing method in the step (3) is one or more of liquid nitrogen freezing, dry ice freezing and laser freezing.
6. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, characterized by comprising the following steps: and (3) drying is one or more of freeze drying, vacuum freeze drying and microwave vacuum freeze drying.
7. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, wherein the drying time in the step (3) is 6-72 hours.
8. The preparation method of the tin sulfide/graphene sodium-ion battery composite anode material according to claim 1, wherein the inert or reducing atmosphere in the step (4) is nitrogen, argon, hydrogen or a mixture of nitrogen, argon and hydrogen.
9. The tin sulfide/graphene sodium-ion battery composite negative electrode material prepared by the preparation method of any one of claims 1 to 8 is characterized in that the composite material is prepared by compounding tin sulfide and graphene.
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| CN107316989B (en) * | 2017-05-17 | 2020-05-22 | 华南理工大学 | Tin sulfide/sulfur/few-layer graphene composite material and preparation method and application thereof |
| CN107895779B (en) * | 2017-10-09 | 2020-04-24 | 中国科学院化学研究所 | High-capacity potassium ion battery negative electrode material and preparation method and application thereof |
| CN107910536A (en) * | 2017-12-27 | 2018-04-13 | 东北师范大学 | A kind of selenium/graphene nanocomposite material prepares and its application |
| CN108448078A (en) * | 2018-02-11 | 2018-08-24 | 常熟理工学院 | A kind of preparation method of tinbase/carbon lithium ion cell negative electrode material |
| CN109713255B (en) * | 2018-12-06 | 2022-05-10 | 盐城工学院 | High-performance two-dimensional metal element doped SnS2-graphene-S composite material and preparation method and application thereof |
| CN109728283A (en) * | 2018-12-29 | 2019-05-07 | 桑德集团有限公司 | The preparation method and negative electrode material of composite material with graphene coated layer |
| CN111446447A (en) * | 2020-04-03 | 2020-07-24 | 浙江长兴绿色电池科技有限公司 | Method for preparing sulfur stannide/carbon composite material by supercritical carbon dioxide fluid and application |
| CN112786858A (en) * | 2021-01-19 | 2021-05-11 | 安徽光特新材料科技有限公司 | SnS2Preparation method of nano-sheet loaded graphene-based nano composite material |
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| CN105406034A (en) * | 2015-10-27 | 2016-03-16 | 浙江大学 | Three-dimensional porous graphene-supported carbon-coated lithium sulfide cathode material as well as preparation method and application thereof |
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