CN111900309B - High-cycle high-capacity performance battery - Google Patents
High-cycle high-capacity performance battery Download PDFInfo
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- CN111900309B CN111900309B CN202010785578.8A CN202010785578A CN111900309B CN 111900309 B CN111900309 B CN 111900309B CN 202010785578 A CN202010785578 A CN 202010785578A CN 111900309 B CN111900309 B CN 111900309B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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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Abstract
The invention discloses a high-cycle high-capacity performance battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is a graphene-sulfur composite positive electrode, the negative electrode is a metal lithium sheet, and the diaphragm preparation process comprises the following steps: (1) weighing zinc salt and thiourea, dissolving in water, adding a certain amount of graphite oxide alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction to obtain S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material; (2) dispersing the composite material prepared in the step (1) and a binder into a solvent, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a membrane substrate, and drying to obtain the composite membrane. By adopting the technical scheme of the invention, the shuttle effect caused by lithium polysulfide in the cycle process of the lithium-sulfur battery can be effectively inhibited, and the capacity performance and the cycle performance of the lithium-sulfur battery are improved.
Description
Technical Field
The invention belongs to the technical field of batteries.
Background
Lithium ion batteries are widely used in the field of people's daily life. With the development of society, the traditional lithium ion battery can not meet the requirement of people on energy storage. Lithium-sulfur batteries (Li-S) are considered to be one of the most promising high-capacity storage systems due to their high theoretical specific capacity and energy density, and the advantages of sulfur, such as low cost and environmental friendliness. However, the commercial application of Li-S batteries still presents some technical challenges, such as the insulating properties of solid sulfides, the shuttling effect of soluble long-chain polysulfides, and the large volume change of sulfur during charging and discharging. These problems often result in low sulfur utilization, poor cycle life, and even a series of safety issues. How to greatly improve the practical energy density and the cycle stability of the Li-S battery has become one of the hot spots of the current research.
The separator is also one of the important components of the battery, and functions to conduct ion transport and prevent short-circuiting of the battery. Commercial PP and PE separators cannot effectively suppress diffusion and shuttling of polysulfides because polysulfides can pass through easily due to their large pore size.
The invention aims to provide a functional composite diaphragm for a lithium-sulfur battery and a preparation method thereof, and aims to solve the problems in the conventional lithium-sulfur battery.
Disclosure of Invention
The invention provides a lithium-sulfur battery diaphragm, which is prepared by the following specific processes:
(1) weighing zinc salt and thiourea, dissolving in water, adding a certain amount of graphite oxide alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction at 90-160 ℃, and reacting for 12-24 hours; obtaining S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material;
(2) dispersing the composite material prepared in the step (1) and a binder into a solvent, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a membrane substrate, and drying to obtain the composite membrane.
The inorganic zinc salt is zinc chloride, zinc sulfate, zinc nitrate or zinc stearate.
The hydrothermal reaction temperature is 60-150 ℃, and the reaction time is 12-24 h.
The molar ratio of the zinc salt to the thiourea is 1 (1.3-1.5).
The diaphragm substrate is a PP diaphragm, a PE diaphragm and a polyimide diaphragm.
The S, N co-doped partially reduced graphite oxide alkyne-ZnS mass ratio is (5-20): (95-80).
Has the advantages that:
(1) the ZnS has certain lithium ion conductivity, is beneficial to improving the ion transfer rate of the battery and can efficiently inhibit shuttling of polysulfide; (2) the reaction condition of the hydrothermal process is mild, partial reduction of the graphite oxide alkyne can be realized, thiourea is used as a sulfur source of ZnS on one hand, and meanwhile, the thiourea can be used as a sulfur source to be doped into the reduced graphite oxide alkyne to improve the active site and the defect degree of the ZnS, the S, N-doped partial reduced graphite oxide alkyne not only improves the conductivity of the ZnS, but also has strong adsorption effect on polysulfide due to alkyne bonds and surface polar functional groups (such as carboxyl, hydroxyl and C-N, C-S bonds), prevents the dissolution of the polysulfide and limitedly inhibits the shuttle effect; (3, a one-step hydrothermal method is adopted, the process is simple, and the operation is simple and convenient.
Detailed Description
Example 1
(1) Weighing 0.05mmol of zinc salt and 0.07mmol of thiourea, dissolving in water, adding oxidized graphite alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction at 90 ℃ for 15 hours; obtaining S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material; s, N the mass ratio of co-doped partially reduced graphite oxide alkyne to ZnS was 18: 82;
(2) dispersing the composite material prepared in the step (1) and a binder into a solvent NMP according to a mass ratio of 90:10, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a PE membrane substrate, and drying to obtain the composite membrane.
Example 2
(1) Weighing 0.06mmol of zinc salt and 0.08mmol of thiourea, dissolving in water, adding a certain amount of graphite oxide alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 10 hours at 120 ℃; obtaining S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material, wherein the mass ratio of S, N co-doped partially reduced graphite oxide alkyne to ZnS is 20: 80;
(2) dispersing the composite material prepared in the step (1) and the adhesive into a solvent NMP according to the mass ratio of 90:10, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a PP membrane substrate, and drying to obtain the composite membrane.
Example 3
(1) Weighing 0.05mmol of zinc salt and 0.08mmol of thiourea, dissolving in water, adding a certain amount of graphite oxide alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 8 hours at 130 ℃; obtaining S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material, wherein the mass ratio of S, N co-doped partially reduced graphite oxide alkyne to ZnS is 15: 85;
(2) dispersing the composite material prepared in the step (1) and the adhesive into a solvent NMP according to a mass ratio of 95:5, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a PP membrane substrate, and drying to obtain the composite membrane.
Comparative example 1: commercial PP separators are directly adopted as lithium-sulfur battery separators.
Comparative example 2: (1) weighing 0.05mmol of zinc salt and 0.08mmol of thiourea, dissolving in water, transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction at 130 ℃, and reacting for 8 hours to obtain ZnS;
(2) dispersing a ZnS material and a binder into a solvent NMP according to a mass ratio of 95:5, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a membrane substrate, and drying to obtain the composite membrane.
Comparative example 3
(1) Dissolving a certain amount of oxidized graphite alkyne, ammonia water and thiourea in water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction at 130 ℃ for 8 hours; obtaining S, N co-doped partially reduced graphite oxide alkyne material;
(2) dispersing the material prepared in the step (1) and a binder into a solvent NMP according to a mass ratio of 95:5, and stirring to obtain uniformly dispersed coating slurry; and coating the composite membrane on the surface of a membrane substrate, and drying to obtain the composite membrane.
The method of assembling the lithium sulfur battery in examples 1 to 3 and comparative examples 1 to 3 was as follows:
the sulfur/graphene composite material is used as a positive electrode material, a metal lithium sheet is used as a negative electrode material, 1M lithium bistrifluoromethane sulfimide electrolyte is dissolved in 1, 3-dioxolane/glycol dimethyl ether mixed solution, and the battery is assembled by the diaphragm prepared by the method.
The cell was charged and discharged at 0.1C with a cut-off voltage of 2.8V for charging and 1.5V for discharging. The initial specific capacity of the battery, the specific capacity after 200 cycles and the coulombic efficiency of the battery are considered. The results of the experiment are shown in table 1.
The result shows that the diaphragm prepared by the invention has higher coulombic efficiency, higher battery capacity and better capacity retention rate when being applied to the lithium-sulfur battery.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A lithium-sulfur battery diaphragm is prepared by the following specific preparation process:
(1) weighing zinc salt and thiourea, dissolving in water, adding a certain amount of graphite oxide alkyne and ammonia water, ultrasonically mixing, transferring into a high-pressure reaction kettle, and carrying out hydrothermal reaction; obtaining S, N co-doped partially reduced graphite oxide alkyne/ZnS composite material;
(2) dispersing the composite material prepared in the step (1) and a binder into a solvent, and stirring to obtain uniformly dispersed coating slurry; the zinc salt-thiourea composite membrane is coated on the surface of a membrane substrate and dried to obtain the composite membrane, wherein the molar ratio of the zinc salt to the thiourea is 1 (1.3-1.5).
2. The lithium sulfur battery separator according to claim 1, wherein the zinc salt is zinc chloride, zinc sulfate, zinc nitrate, or zinc stearate.
3. The lithium-sulfur battery separator according to claim 1, wherein the hydrothermal reaction temperature is 90 to 160 ℃ and the reaction time is 12 to 24 hours.
4. The lithium sulfur battery separator according to claim 1, wherein the separator substrate is a PP separator, a PE separator, a polyimide separator.
5. The lithium sulfur battery separator according to claim 1, wherein the S, N co-doped partially reduced graphite oxide alkyne to ZnS mass ratio is (5-20): (95-80).
6. A lithium-sulfur battery prepared by the separator of any one of claims 1 to 5, comprising a positive electrode and a negative electrode, wherein the positive electrode is a graphene-sulfur composite positive electrode, and the negative electrode is a metal lithium sheet.
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| CN113140871B (en) * | 2021-03-26 | 2022-11-04 | 西安理工大学 | Diaphragm of self-supporting structure for lithium-sulfur battery and preparation method of diaphragm |
| CN113178659B (en) * | 2021-04-26 | 2022-09-20 | 素水新材料(上海)有限公司 | Modified diaphragm, preparation method thereof and lithium-sulfur battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105990550A (en) * | 2015-01-28 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Composite separator membrane, preparation method thereof, and application thereof in lithium ion batteries |
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| CN106848161A (en) * | 2017-01-05 | 2017-06-13 | 清华大学深圳研究生院 | Lithium-sulfur cell barrier film and the lithium-sulfur cell comprising the barrier film |
| CN108963149A (en) * | 2018-05-28 | 2018-12-07 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation and its application of graphite acetylenic material modification diaphragm |
| US10978744B2 (en) * | 2018-06-18 | 2021-04-13 | Global Graphene Group, Inc. | Method of protecting anode of a lithium-sulfur battery |
| CN109768203A (en) * | 2019-01-24 | 2019-05-17 | 吉林大学 | A kind of preparation method of Complex Function diaphragm |
| CN110957455A (en) * | 2019-11-27 | 2020-04-03 | 烟台大学 | Functionalized diaphragm for lithium-sulfur battery and preparation method thereof |
| CN111403658A (en) * | 2020-03-04 | 2020-07-10 | 南昌大学 | Preparation method of diaphragm with electrocatalysis function and application of diaphragm in lithium-sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105990550A (en) * | 2015-01-28 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Composite separator membrane, preparation method thereof, and application thereof in lithium ion batteries |
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