CN112599753A - Preparation and application of SnS @ C graded ball with S defects - Google Patents

Preparation and application of SnS @ C graded ball with S defects Download PDF

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CN112599753A
CN112599753A CN202110016728.3A CN202110016728A CN112599753A CN 112599753 A CN112599753 A CN 112599753A CN 202110016728 A CN202110016728 A CN 202110016728A CN 112599753 A CN112599753 A CN 112599753A
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sns
defects
graded
preparation
graded ball
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CN112599753B (en
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魏明灯
王建标
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Fuzhou University
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Fuzhou 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a preparation method and application of an S-defect SnS @ C graded ball. The SnS @ C graded ball has S defects, and the structure is favorable for relieving volume expansion caused by materials in the process of intercalation and deintercalation of lithium ions.

Description

Preparation and application of SnS @ C graded ball with S defects
Technical Field
The invention belongs to the field of all-solid-state lithium ion batteries, and particularly relates to preparation of a SnS @ C graded ball with an S defect and application of the SnS @ C graded ball as an all-solid-state lithium ion battery cathode material.
Background
So far, lithium ion batteries have been widely studied and applied. However, as lithium ion batteries are applied to large electric vehicles, the safety problem of the lithium ion batteries becomes more and more prominent, and sometimes spontaneous combustion events of electric vehicles occur. This has become an important factor limiting the development of lithium ion batteries. The development of lithium ion batteries with high safety and high performance is not slow, and the development strategy is also in line with the energy development strategy of China. The sulfide-based solid electrolyte has lithium ion conductivity matched with the organic liquid electrolyte, has no conductivity, avoids self-discharge phenomenon, and has better ductility and is widely applied to all-solid-state lithium ion batteries. However, finding electrode materials that match them remains a challenging issue.
At present, no related patent report that the SnS @ C composite with the S defects is applied to the all-solid-state lithium ion battery exists.
Disclosure of Invention
The invention aims to provide a preparation method of a SnS @ C graded ball with S defects and an application of the SnS @ C graded ball as a cathode material of an all-solid-state lithium ion battery. The SnS @ C graded ball has S defects, and the structure is favorable for relieving volume expansion caused by materials in the process of intercalation and deintercalation of lithium ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an SnS @ C graded ball with S defects comprises the steps of preparing a precursor by a simple one-step solvothermal method, and calcining at 400 ℃ for 1 hour to obtain the graded ball consisting of SnS nanosheets. The method specifically comprises the following steps:
(1) adding stannous chloride into a mixed solvent of isopropanol and ethanol, stirring for ten minutes, then adding thioacetamide and glucose, stirring uniformly, transferring into a reaction kettle, and placing in an oven for reaction;
(2) taking out, cooling to room temperature, washing with deionized water and ethanol for several times, and drying in a vacuum oven; (3) and calcining the obtained product in an argon protective atmosphere to obtain the SnS @ C graded ball material with S defects.
Preferably, the reaction temperature in the oven in the step (1) is 200 ℃, and the reaction time is 24 h.
Preferably, the drying temperature of the vacuum oven in the step (2) is 80 ℃.
Preferably, the calcining temperature in the step (3) is 400 ℃, and the calcining time is 1 h.
The application of the SnS @ C graded ball with the S defect comprises the following steps: the SnS @ C graded ball with the S defect is used as an all-solid-state lithium ion battery negative electrode material and is applied to preparation of an all-solid-state lithium ion battery.
The invention has the following remarkable advantages: the SnS @ C graded ball has S defects, and the structure is favorable for relieving volume expansion caused by materials in the process of intercalation and deintercalation of lithium ions. The SnS graded ball with the S defect is applied to the all-solid-state lithium ion battery for the first time, and has guiding significance for applying sulfide as a lithium ion battery cathode material to the all-solid-state battery.
Drawings
Figure 1 is an XRD pattern of SnS @ C graded spheres with S defects;
FIG. 2 is a scanning electron micrograph of a SnS @ C graded ball with S defects;
FIG. 3 is a Mapping spectrum of a SnS @ C graded sphere with S defects;
FIG. 4 is a graph of the electrochemical performance of SnS @ C graded spheres with S defects at a current density of 0.2A/g.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1 preparation of SnS @ C graded balls with S defects
A preparation method of SnS @ C graded balls with S defects comprises the steps of adding 0.225 g of stannous chloride into a mixed solvent of 20 ml of isopropanol and 10 ml of ethanol, stirring for ten minutes, then adding 0.155 g of thioacetamide and 0.1 g of glucose into the system, uniformly stirring, transferring into a 50 ml reaction kettle, placing in a 200-DEG oven, and reacting for 24 hours. Taking out, cooling to room temperature, washing with deionized water and ethanol for several times, and drying in 80 deg.C vacuum oven. And calcining the obtained product for one hour at 400 ℃ under the argon protective atmosphere to obtain the SnS @ C graded ball material with S defects.
Fig. 1 is an XRD pattern of the SnS @ C graded sphere, from which it can be concluded that the prepared SnS is a pure phase. FIG. 2 is a scanning electron micrograph of SnS @ C, from which it can be seen that the SnS @ C graded ball is composed of nanosheets. FIG. 3 is a Mapping spectrum of SnS @ C, and from b of FIG. 3, Sn/S is obtained as 3:2, and the existence of S defects is deduced.
Example 2 application of SnS @ C graded ball with S defect in all-solid-state lithium ion battery
The SnS @ C graded ball with the S defects prepared in the example 1 is used for preparing an all-solid-state lithium ion battery, and an electrochemical performance test is carried out.
The preparation method of the all-solid-state lithium ion battery comprises the following steps: 75% Li2S-25%P2S5Grinding under protection of inert atmosphere for 24 hr to obtain solid electrolyte, and mixing 135 mg of the above powder at 300 ton/cm2Under the pressure of the pressure, a film is prepared, SnS powder with S defects is used as a positive electrode material, a LiIn alloy film is used as a negative electrode, and the film is assembled into the all-solid lithium ion battery, and the operations are carried out in a glove box due to the reaction of sulfide solid electrolyte and air. SnS is a negative electrode material, but since the battery is a half-cell, the SnS powder with S defects serves as a positive electrode in the half-cell.
Fig. 4 shows electrochemical performance of a negative electrode material as an electrode material. The capacity remained at 406 mA h/g after 100 cycles at a current density of 0.2A/g.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (6)

1. A preparation method of a SnS @ C graded ball with S defects is characterized by comprising the following steps:
(1) adding stannous chloride into a mixed solvent of isopropanol and ethanol, stirring for ten minutes, then adding thioacetamide and glucose, stirring uniformly, transferring into a reaction kettle, and placing in an oven for reaction;
(2) taking out, cooling to room temperature, washing with deionized water and ethanol for several times, and drying in a vacuum oven; (3) and calcining the obtained product in an argon protective atmosphere to obtain the SnS @ C graded ball material with S defects.
2. The preparation method according to claim 1, wherein the reaction temperature in the oven in step (1) is 200 ℃ and the reaction time is 24 hours.
3. The method according to claim 1, wherein the vacuum oven drying temperature in the step (2) is 80 ℃.
4. The method according to claim 1, wherein the calcination temperature in the step (3) is 400 ℃ and the calcination time is 1 hour.
5. SnS @ C graded ball with S defects prepared by the preparation method of any one of claims 1 to 4.
6. The application of the SnS @ C graded ball with the S defects as the negative electrode material of the all-solid-state lithium ion battery, as claimed in claim 5, wherein the SnS @ C graded ball with the S defects is used for preparing the all-solid-state lithium ion battery.
CN202110016728.3A 2021-01-07 2021-01-07 Preparation and application of SnS @ C graded ball with S defects Active CN112599753B (en)

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Citations (6)

* 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
CN105552366A (en) * 2015-12-17 2016-05-04 长沙理工大学 Preparation method of anode material, namely nitrogen-doped SnS/C composite nanomaterial for lithium battery
CN105800674A (en) * 2016-03-23 2016-07-27 昆明理工大学 Preparation method and application of tin sulfide 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
CN108777294A (en) * 2018-05-28 2018-11-09 福州大学 A kind of porous spherical MoN that the carbon being made of nanometer sheet is supported and its application as negative material in lithium battery
CN112018385A (en) * 2020-09-01 2020-12-01 福州大学 SnS with S-Vacanty2Grading ball and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105552366A (en) * 2015-12-17 2016-05-04 长沙理工大学 Preparation method of anode material, namely nitrogen-doped SnS/C composite nanomaterial for lithium battery
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
CN105800674A (en) * 2016-03-23 2016-07-27 昆明理工大学 Preparation method and application of tin sulfide 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
CN108777294A (en) * 2018-05-28 2018-11-09 福州大学 A kind of porous spherical MoN that the carbon being made of nanometer sheet is supported and its application as negative material in lithium battery
CN112018385A (en) * 2020-09-01 2020-12-01 福州大学 SnS with S-Vacanty2Grading ball and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIANBIAO WANG ETAL: "ration design of hierarchical SnS2 microspheres with S vacancy for enhanced sodium storage performance", 《SUSTAINABLE CHEMISTRY & ENGINEERING》 *
YAOHUI ZHANG ETAL: "Hierarchical assembly and superior lithium/sodium storage properties of a flowerlike C/SnS@C nanocomposite", 《ELECTROCHIMICA ACTA》 *
蒋以号 等: "花状 ＳｎＳ＠ ＣＮＴｓ ／Ｓ 复合正极材料用 于高性能锂硫电池", 《南昌大学学报（工科版）》 *

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