CN112490430A - Preparation method of high-performance negative electrode material for lithium/sodium ion battery - Google Patents

Preparation method of high-performance negative electrode material for lithium/sodium ion battery Download PDF

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CN112490430A
CN112490430A CN202011418017.0A CN202011418017A CN112490430A CN 112490430 A CN112490430 A CN 112490430A CN 202011418017 A CN202011418017 A CN 202011418017A CN 112490430 A CN112490430 A CN 112490430A
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lithium
ion battery
sodium ion
sns
mixed solution
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李彦娟
吴志荣
闫霄
刘子豪
贾宏鹏
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Jiangsu Normal University
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Jiangsu Normal 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 preparation method of a high-performance negative electrode material for a lithium/sodium ion battery, which specifically comprises the following steps: dispersing a tin source, sulfur powder and a carbon source into a certain aqueous solvent, and stirring to form a mixed solution; then the mixed solution is put into a reaction kettle, and the temperature and the time are set for carrying out the solvothermal reaction; then cleaning and drying the mixed solution after the solvothermal reaction to obtain a precursor tin-based chalcogenide; and finally, carrying out high-temperature heat treatment on the precursor tin-based chalcogenide in a certain sintering atmosphere to obtain the SnS/NC/SnS composite material with the multiphase structure. The preparation method of the high-performance cathode material for the lithium/sodium ion battery has simple process, avoids the complex process of the traditional preparation, and prepares the cathode material with a multiphase structure and has good electrochemical performance.

Description

Preparation method of high-performance negative electrode material for lithium/sodium ion battery
Technical Field
The invention relates to the field of battery cathode materials, in particular to a preparation method of a high-performance cathode material for a lithium/sodium ion battery.
Background
Rechargeable lithium/sodium ion batteries (LIBs/SIBs) play an important role in mitigating energy crisis and controlling environmental pollution. The cathode material is used as a key component of the battery and has important significance for the development of high-performance batteries.
Stannous sulfide (SnS) is a relatively abundant and non-toxic material, in which Sn-S bonds in layers are tightly combined in a covalent bond form to keep the layers stable in the presence of atmospheric water and oxygen, and the layers are connected by weak van der Waals force, and is suitable for Li+/Na+Because of the insertion/extraction, the SnS electrode as a negative electrode material can exhibit good charge-discharge cycle performance and high storage capacity, but poor cycle stability (LIBs-242%, NIBs-420%) due to volume expansion when the SnS electrode is used still hinders its practical use.
The most effective solution in the prior art is to compound an SnS material and a carbon source to reduce capacity attenuation, and nitrogen-doped carbon can improve the electrical conductivity of electrons and can adapt to larger storage capacity, so that the composite material is widely applied; however, the general SnS/C material composition cannot maintain the structural integrity for a long time, and is difficult to meet the requirements of practical application, and the bare outer layer carbon cannot essentially ensure the rapid transmission of electrons and ions in the electrode material, and the electrochemical performance is poor, while some studies show that the construction of the multiphase structure composite material can expand the lattice space, is beneficial to the insertion/desorption of Li +/Na +, and resists the volume expansion/shrinkage, so as to realize better electrochemical performance.
Disclosure of Invention
The invention provides a preparation method of a high-performance cathode material for a lithium/sodium ion battery, which is simple in process, not only avoids the complex process of the traditional preparation, but also prepares the cathode material with a sandwich structure and has good electrochemical performance.
In order to achieve the purpose, the preparation method of the high-performance anode material for the lithium/sodium ion battery specifically comprises the following steps:
step 1: dispersing a tin source, sulfur powder and a carbon source into a certain aqueous solvent, and stirring to form a mixed solution;
step 2: putting the mixed solution obtained in the step 1 into a reaction kettle, and setting the temperature and time to carry out solvothermal reaction;
and step 3: cleaning and drying the mixed solution reacted in the step 2 to obtain a precursor tin-based chalcogenide;
and 4, step 4: and (3) carrying out high-temperature heat treatment on the precursor tin-based chalcogenide in the step (3) in a certain sintering atmosphere to obtain the SnS/NC/SnS composite material with the multiphase structure.
Further, in the step 1, the carbon source is one or more of triethylene diamine, dodecylamine, dimethyl imidazole and dimethylamine.
Further, the carbon source in the step 1 is dimethyl imidazole.
Further, the reaction temperature in the step 2 is 130-180 ℃, and the reaction time is 0.5-10 days.
Further, the sintering temperature in the step 4 is 400-1000 ℃, the sintering time is 1-4h, and the sintering atmosphere is one or more of nitrogen, argon and argon/hydrogen mixed atmosphere.
Further, when the sintering atmosphere is argon/hydrogen, the corresponding volume ratio is 95/5.
Further, the mixed solution after the reaction in the step 3 is centrifugally washed by water for 2 to 5 times and then dried at a temperature of between 60 and 90 ℃ in a vacuum atmosphere.
Compared with the prior art, according to the preparation method of the high-performance cathode material for the lithium/sodium ion battery, a mixed solution is formed by a tin source, sulfur powder and a carbon source to carry out solvothermal reaction, a precursor tin-based chalcogenide is obtained by cleaning and drying, and the sandwich structure SnS/NC/SnS composite material is obtained by sintering the precursor tin-based chalcogenide at high temperature, so that on one hand, the method is simpler in preparation method and adjustable in intermediate carbon source, the traditional complex process of firstly preparing N-doped carbon and then reacting with the Sn source and the sulfur source is avoided, the fine regulation and control of the SnS and carbon multiphase structure are realized, and the large-scale production is easy to realize;
on the other hand, compared with the traditional SnS/C material obtained by coating carbon on the outer layer or directly compounding the carbon material, the product structure obtained by the method can change the internal conductivity of the material, firstly, the product grows in situ, the tight combination of SnS and carbon can be realized, secondly, the conductivity can be improved by NC, the product becomes an ion capture center, and finally, the structure enlarges the interlayer spacing of SnS, the lithium/sodium ion transmission is facilitated, the buffer volume expands, and the material finally shows excellent electrochemical performance.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the product SnS/NC/SnS/composite obtained according to the present invention;
FIG. 2 shows the cycle performance of the product SnS/NC/SnS/composite material obtained by the method as a lithium ion battery;
FIG. 3 shows the cycle performance of the product SnS/NC/SnS/composite material obtained by the method as a sodium-ion battery;
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
The preparation method of the high-performance negative electrode material for the lithium/sodium ion battery comprises the following specific steps:
(1) dispersing a tin source and sulfur powder into water, adding a carbon source, and rapidly stirring to form a mixed solution;
(2) putting the mixed solution into a reaction kettle, setting the temperature at 130-180 ℃, and the reaction time at 0.5-10 days to perform solvothermal reaction on the mixed solution in the reaction kettle;
(3) cooling the reaction kettle in the step (2) to room temperature, opening the reaction kettle, centrifugally washing with water for 2-5 times, and drying at 60-90 ℃ in a vacuum atmosphere to obtain a precursor tin-based chalcogenide;
(4) sintering the precursor tin-based chalcogenide compound obtained in the step (3) in a sintering atmosphere, wherein the sintering temperature is set to be 400-1000 ℃, and the sintering time is 1-4h, so as to obtain a high-performance cathode material, namely an SnS/NC/SnS/composite material with a multiphase structure;
further, the carbon source can be one or more of triethylene diamine, dodecylamine, dimethyl imidazole and dimethylamine;
furthermore, the sintering atmosphere is one or more of nitrogen, argon and argon/hydrogen mixed atmosphere.
Example 2
The preparation method of the high-performance negative electrode material for the lithium/sodium ion battery comprises the following specific steps:
(1) dispersing 5.7mmol of crystalline tin tetrachloride and 14mmol of sulfur powder in 16ml of water, adding 106.5mmol of dimethylimidazole, and rapidly stirring to form a mixed solution;
(2) putting the mixed solution obtained in the step (1) into a 100ml reaction kettle, placing the reaction kettle in a high-temperature oven, and carrying out solvothermal reaction at the temperature of 180 ℃ for 7 days;
(3) taking out the reaction kettle in the step (2), cooling to room temperature, opening the reaction kettle, centrifugally washing with water for 3 times, and drying at 70 ℃ in a vacuum atmosphere to obtain a precursor tin-based chalcogenide;
(4) sintering the precursor tin-based chalcogenide obtained in the step (3) for 2 hours at 700 ℃ in the mixed atmosphere of argon gas/hydrogen gas (volume ratio 95/5) to obtain a high-performance negative electrode material, namely an SnS/NC/SnS/composite material with a multiphase structure;
as shown in fig. 1, 2, and 3, characterization tests were performed on the SnS/NC/SnS/composite material obtained in step (4) in example 1 to determine the purity of the crystalline phase of SnS prepared using triethylene diamine, dodecylamine, dimethyl imidazole, dimethylamine as a carbon source:
and when the carbon source is triethylene diamine, obtaining Sn in SnS: s ≠ 1: 1, the dodecylamine obtains SnS peak type deviation, dimethylamine can not synthesize pure phase SnS, and the material prepared by using dimethylimidazole as a carbon source has the purest crystallinity;
the SnS/NC/SnS/composite material obtained in the step (4) in the example 1 is subjected to electrochemical performance test, and the optimality of the composite material as a negative electrode material of a lithium/sodium ion battery is judged. The counter electrode tested was a lithium/sodium metal sheet, and the electrolytes were 1MLiPF each6Dissolving in ethylene carbonate/methyl carbonate/diethyl carbonate (volume ratio of 1: 1: 1) and 1M NaPF6Dissolved in ethylene carbonate/dimethyl carbonate (volume ratio 1/1). The SnS/NC/SnS material with the dimethyl imidazole as the carbon source shows the best cycle performance, rate performance and high rate cycle performance, so the preferable carbon source is the dimethyl imidazole;
according to the preparation method of the high-performance cathode material for the lithium/sodium ion battery, a mixed solution is formed by a tin source, sulfur powder and a carbon source to carry out solvothermal reaction, a precursor tin-based chalcogenide is obtained by cleaning and drying, and the sandwich structure SnS/NC/SnS composite material is obtained by sintering the precursor tin-based chalcogenide at high temperature, so that on one hand, the method is simpler in preparation method, and the intermediate carbon source is adjustable, and the traditional complex process that N-doped carbon is prepared and then reacts with the Sn source and the sulfur source is avoided;
on the other hand, compared with the traditional SnS/C material obtained by coating carbon on the outer layer or directly compounding the carbon material, the product structure obtained by the method can change the internal conductivity of the material, firstly, the product grows in situ, the tight combination of SnS and carbon can be realized, secondly, the conductivity can be improved by NC, the product becomes an ion capture center, and finally, the structure enlarges the interlayer spacing of SnS, the lithium/sodium ion transmission is facilitated, the buffer volume expands, and the material finally shows excellent electrochemical performance.

Claims (7)

1. A preparation method of a high-performance negative electrode material for a lithium/sodium ion battery is characterized by comprising the following steps:
step 1: dispersing a tin source, sulfur powder and a carbon source into a certain aqueous solvent, and stirring to form a mixed solution;
step 2: putting the mixed solution obtained in the step 1 into a reaction kettle, and setting the temperature and time to carry out solvothermal reaction;
and step 3: cleaning and drying the mixed solution reacted in the step 2 to obtain a precursor tin-based chalcogenide;
and 4, step 4: and (3) carrying out high-temperature heat treatment on the precursor tin-based chalcogenide in the step (3) in a certain sintering atmosphere to obtain the SnS/NC/SnS composite material with the multiphase structure.
2. The method for preparing a high-performance anode material for a lithium/sodium ion battery according to claim 1, wherein the carbon source in the step 1 is one or more of triethylene diamine, dodecylamine, dimethyl imidazole and dimethylamine.
3. The method for preparing a high-performance anode material for a lithium/sodium ion battery according to claim 2, wherein the carbon source in the step 1 is dimethyl imidazole.
4. The method as claimed in any one of claims 1 to 3, wherein the reaction temperature in step 2 is 130-180 ℃, and the reaction time is 0.5-10 days.
5. The method for preparing a high-performance anode material for a lithium/sodium ion battery as claimed in claim 4, wherein the sintering temperature in the step 4 is 400-.
6. The method for preparing a high-performance anode material for a lithium/sodium ion battery according to claim 5, wherein when the sintering atmosphere is argon/hydrogen, the corresponding volume ratio is 95/5.
7. The method for preparing a high-performance anode material for a lithium/sodium ion battery according to claim 4, wherein the mixed solution after the reaction in the step 3 is washed by water centrifugation for 2-5 times and then dried at 60-90 ℃ in a vacuum atmosphere.
CN202011418017.0A 2020-12-07 2020-12-07 Preparation method of high-performance negative electrode material for lithium/sodium ion battery Pending CN112490430A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097484A (en) * 2021-04-01 2021-07-09 陕西科技大学 Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105514356A (en) * 2015-12-25 2016-04-20 东莞威胜储能技术有限公司 Composite cathode material for sodium battery and preparation method of composite cathode material
CN106099069A (en) * 2016-08-15 2016-11-09 华南理工大学 A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof
CN106887578A (en) * 2017-04-01 2017-06-23 中南大学 A kind of artificial gold/CNT composite Nano negative material and preparation method thereof
CN110336011A (en) * 2019-07-10 2019-10-15 陕西科技大学 A method of preparing the flower-shaped N-doped C/SnS lithium ion battery negative material of tree peony
CN111710849A (en) * 2020-07-08 2020-09-25 广西师范大学 ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105514356A (en) * 2015-12-25 2016-04-20 东莞威胜储能技术有限公司 Composite cathode material for sodium battery and preparation method of composite cathode material
CN106099069A (en) * 2016-08-15 2016-11-09 华南理工大学 A kind of sodium-ion battery negative pole SnS/C composite and preparation method thereof
CN106887578A (en) * 2017-04-01 2017-06-23 中南大学 A kind of artificial gold/CNT composite Nano negative material and preparation method thereof
CN110336011A (en) * 2019-07-10 2019-10-15 陕西科技大学 A method of preparing the flower-shaped N-doped C/SnS lithium ion battery negative material of tree peony
CN111710849A (en) * 2020-07-08 2020-09-25 广西师范大学 ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113097484A (en) * 2021-04-01 2021-07-09 陕西科技大学 Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof

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Inventor after: Li Yanjuan

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Inventor after: Yan Xiao

Inventor after: Liu Zihao

Inventor after: Jia Hongpeng

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Application publication date: 20210312