CN108172744B - Sb for lithium-sulfur battery diaphragm2Se3Method for preparing composite material - Google Patents
Sb for lithium-sulfur battery diaphragm2Se3Method for preparing composite material Download PDFInfo
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- CN108172744B CN108172744B CN201711445918.7A CN201711445918A CN108172744B CN 108172744 B CN108172744 B CN 108172744B CN 201711445918 A CN201711445918 A CN 201711445918A CN 108172744 B CN108172744 B CN 108172744B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
Abstract
The invention relates to Sb for a lithium-sulfur battery diaphragm2Se3A method for preparing a composite material. The methodBy introducing rod-like Sb2Se3As a support skeleton of the graphene sheet layer, the structure of the coating substance is modified by adding Sb2Se3Mixing-pvc and graphene oxide at a certain ratio, and reducing the graphene oxide by hydrazine hydrate to obtain Sb2Se3Dispersion of-pvc and reduced graphene oxide, spray-drying the dispersion to obtain a solid powder, and bonding with Celgard2400 membrane via a binder to prepare Sb2Se3-a composite membrane of pvc-rGO. The invention improves the electrochemical performance of the lithium-sulfur battery by a simple and cheap method.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery diaphragm materials, in particular to Sb for a lithium-sulfur battery diaphragm2Se3A method for preparing a composite material to improve the electrochemical performance of a lithium-sulfur battery.
Background
The rapid development of global economy results in the constant consumption of non-renewable energy sources, which causes an energy crisis. In order to solve the energy crisis problem, it is urgent to develop and utilize renewable energy sources represented by solar energy and wind energy for power generation. However, these natural energy sources, including solar energy, wind energy, tidal energy, etc., are intermittent, and the amount of electric energy generated is heavily dependent on natural factors such as weather, season, time, and place. These unstable electrical energy, if incorporated directly into the grid, can severely interfere with the normal operation of the grid. The adoption of a large-scale energy storage system can effectively solve the problem, and intermittent energy generated by renewable natural resources can be accessed into a power grid through the storage and release of the energy storage system. High safety, low cost, long life and large scale energy storage technologies for large scale energy storage applications have become a worldwide research hotspot. At present, the main energy storage technologies include electrochemical energy storage, mechanical energy storage, electromagnetic energy storage, phase change energy storage and the like. Compared with other energy storage modes, the electrochemical energy storage technology has the characteristics of high efficiency, low investment, safe use, flexible application and the like, and the secondary battery is most convenient to use and maintain in various electrochemical energy storage. The lithium-sulfur battery is a clean, environment-friendly and low-cost lithium secondary battery, and is expected to replace a lithium ion battery to become a main commercial secondary battery in the market. At present, the theoretical specific capacity of the commercialized lithium ion battery is limited by the theoretical specific capacity of 300 mAh/g, and obviously cannot meet the requirement on the practical application quality of the lithium ion battery, and the theoretical specific capacity of the novel lithium-sulfur battery is about five times of the theoretical specific capacity of the commercial lithium ion battery (the theoretical specific capacity is 1675mAh/g, and the specific energy is 2600 Wh/kg), and is considered to be one of the high-energy batteries with the most development potential.
Currently, the major battery separators on the market include polypropylene, polyethylene, and composite forms thereof. However, when these separators are used in assembled batteries, the disadvantages of these films are significant, such as poor charge and discharge performance at high temperature or high current density, which results in a large safety hazard, and poor lyophilic and low ionic conductivity, and especially these separators cannot effectively inhibit polysulfide, so that the development of high-performance separators is an important aspect for improving the performance of high-sulfur batteries.
In response to the above problems, many scholars have proposed solutions. For example, carbon nanotubes, ordered mesoporous carbon nanoparticles, carbon nanospheres, and graphene are doped into a sulfur positive electrode, and these methods can provide smooth electron transfer channels to the electrode, and at the same time, can inhibit the shuttling effect of polysulfide to some extent in the initial stage. However, since these materials are mostly open systems, polysulfides cannot be effectively adsorbed in the positive electrode after the battery is cycled for a long time.
Disclosure of Invention
The invention aims to provide Sb for a lithium-sulfur battery diaphragm aiming at the defects in the prior art2Se3A method for preparing a composite material. The method is to introduce rod-shaped Sb2Se3As a support skeleton of the graphene sheet layer, the structure of the coating substance is modified by adding Sb2Se3Mixing-pvc and graphene oxide at a certain ratio, and reducing the graphene oxide by hydrazine hydrate to obtain Sb2Se3Dispersion of-pvc and reduced graphene oxide, spray-drying the dispersion to obtain a solid powder, and bonding with Celgard2400 membrane via a binder to prepare Sb2Se3-pvc-rGO composite separator to improve the electrochemical performance of lithium sulfur batteries in a simple, inexpensive way.
The technical scheme of the invention is as follows:
sb for lithium-sulfur battery diaphragm2Se3The preparation method of the composite material comprises the following steps:
first step, preparation of Sb2Se3-pvp-rGO：
(1) Sb is weighed respectively2Se3And pvp, Sb mixed in a ratio of 4-6:12Se3-pvc powder was added to deionized water to make Sb2Se3Magnetic stirring for 1-2h at room temperature under the condition that the mass concentration of the aqueous phase suspension is 0.1-1%, and then carrying out ultrasonic dispersion by a cell crusher to obtain Sb2Se3-a pvc dispersion;
(2) mixing the graphene oxide dispersion liquid with Sb2Se3Mixing the PVC dispersion liquid, and performing ultrasonic dispersion again through a cell crusher to obtain a mixed liquid; wherein the mass concentration of the graphene oxide dispersion liquid is 1-3 mg/mL; mass ratio Sb2Se3-pvc powder: graphene oxide ═ 1: 1-2;
(3) adding hydrazine hydrate into the mixed liquid, dropwise adding ammonia water to adjust the pH value of the solution to 10-12, heating by an oil bath at the temperature of 80-100 ℃, and continuously stirring for 30-90 min by magnetic force; spray drying the liquid, setting the air inlet temperature at 180 ℃ and the feeding speed at 3-8mL/min and the atomization pressure at 0.8MPa, collecting powder after the spray drying is finished to obtain Sb2Se3-pvp-rGO; wherein, 10-50 μ L of hydrazine hydrate is added into every 100-250mL of mixed liquid;
second step, preparation of a composition having Sb2Se3-a pvc-rGO coated separator:
the obtained Sb2Se3Mixing the-pvc-rGO powder with a polyvinylidene fluoride (PVDF) binder, grinding for 1-3 hours, and then dropwise adding N-methyl pyrrolidone while grinding to dissolve the materials; continuously grinding for 20min-50min to form a bright and uniform black slurry, and coating the black slurry on a Celgard2400 diaphragm with the thickness of 5-15 μm; vacuum drying at 60 ℃ for 12h to obtain Sb2Se3-a composite membrane of pvc and graphene;
wherein the mass ratio Sb2Se3-pvc-rGO powder: binder PVDF is 7-10: 1;
the Sb2Se3Application of composite membrane of pvp with graphene, tailored for CR2025 type cells.
The above-mentioned starting materials are all commercially available and the equipment and processes used are well known to those skilled in the art.
The invention has the substantive characteristics that:
sb used in the present invention2Se3Physical and chemical properties are stable, and the pvc is used as a dispersant to prevent Sb2Se3Stacking between monomers, so that the composite Sb2Se3The dispersion of-pvp is good. Sb2Se3The pvp does not have any chemical reaction with components such as positive and negative electrode materials, electrolyte and the like in the battery pack, and the unique rod-shaped structure can be used as a support structure substance of the graphene sheet layer. Meanwhile, the reduced graphene oxide with stable property and better conductivity can be obtained by effectively reducing the graphene oxide with hydrazine hydrate, and Sb with uniform dispersion and small solid particle size can be obtained by spray drying2Se3And the modified diaphragm coating of the lithium-sulfur battery with a compact and uniform microstructure can be prepared by-pvc-rGO, so that the phenomenon of stacking and laminating graphene sheets on the diaphragm coating can be effectively prevented in the repeated charging and discharging process of the lithium-sulfur battery, and the loose structure of the diaphragm coating can be maintained.
Meanwhile, in the charge-discharge cycle of the lithium-sulfur battery, the solid polysulfide of the discharge product is an insulator of ions and electrons, the coulombic efficiency and the rate capability of the battery can be seriously influenced by a large amount of accumulation, and the soluble polysulfide can generate a shuttle effect, so that the loss of active substances of positive and negative electrode materials is caused, and the specific capacity of the battery is influenced. Sb prepared by the invention2Se3The composite material diaphragm of-pvc-rGO is a diaphragm coating with stable structure, good conductivity and loose structure, so that polysulfide can be continuously adsorbed in long-time charge and discharge cycles of the lithium-sulfur battery, shuttle effect is effectively avoided, polysulfide content in electrolyte after long-time cycles is reduced, and electrochemical performance of the lithium-sulfur battery is improved.
The invention has the following beneficial effects:
compared with the prior art, the method has the following prominent substantive characteristics:
(1) the diaphragm added with the modified substance can adsorb polysulfide generated in the charging and discharging process of the lithium-sulfur battery, and the cycle performance and the rate performance of the lithium-sulfur battery are enhanced. Sb2Se3The rod-like structure can support the lamellar structure of graphene, reduce the pile up of graphite alkene layer in long-time charge-discharge circulation, keep the original lamellar structure of diaphragm coating in long-time charge-discharge circulation, be favorable to continuously adsorbing polysulfide, improve lithium sulfur battery's electrochemical performance. The graphene coating with the supporting structure is different from a coating diaphragm formed by a pure carbon material in patent CN106450102A, the defect of poor cycle performance and the defect of low capacity under large-current charge-discharge cycle are overcome, and the lithium-sulfur battery has better long cycle performance.
(2) The prior art CN106410098A also prepares a membrane coating material with a special laminated structure through electrostatic spinning. However, the technical process of the patent is complex, and the doped organic thin film covers the surface of the graphene in a lamellar form, so that graphene lamellar layers are mutually dispersed and cannot be effectively connected, and the conductivity of the whole battery system is influenced. In the composite material prepared by the invention, the graphene sheet layers are still connected with each other, and Sb2Se3The rod-shaped structure only enters the gaps of the graphene in an embedded mode, and the conductivity of the system cannot be influenced.
(3) The method creatively prepares the Sb with high yield, simple and convenient process and stable structure by selecting and proportionally regulating raw materials and controlling the design and implementation process of the preparation process2Se3The graphene structure is supported, so that the industrial applicability is strong; by repeated ultrasonic and spray drying, Sb is realized2Se3The structure which is uniformly compounded with graphene improves the utilization rate of active substances under the condition of not changing the anode material of the existing lithium-sulfur battery, effectively avoids the shuttle effect of polysulfide and the volume expansion effect of the lithium-sulfur battery, has excellent electrochemical performance andthe circulation stability is good.
Drawings
FIG. 1 shows Sb prepared in example 12Se3-X-ray diffraction pattern of pvp-rGO material.
FIG. 2 shows Sb prepared in example 12Se3First charge-discharge curve at 0.1C for the-pvc-rGO material as separator.
Detailed Description
Example 1
The invention will be further described with reference to specific embodiments:
sb used in the present invention2Se3The pvp and GO suspensions were all commercially available.
First step, preparation of Sb2Se3-pvp-rGO：
Weighing Sb2Se30.20g of powder is weighed, 0.05g of pvp is weighed and poured into a beaker, 49.75mL of deionized water is added to prepare 0.5 mass percent of Sb2Se3The suspension of PVC, stirred for 1h with a magnetic stirrer, then the Sb2Se3And (3) carrying out ultrasonic treatment on the PVC suspension on an ultrasonic cell crusher for 30min to uniformly disperse the PVC suspension. Mixing with graphene oxide aqueous solution according to Sb2Se3The mass ratio of-pvc to graphene oxide is 1:1, 125mL of graphene oxide aqueous phase dispersion liquid (the concentration is 2mg/mL) is measured, and Sb is prepared2Se3Magnetically stirring the mixed dispersion liquid of-pvc-GO for 1h, then carrying out ultrasonic treatment for 20min by using an ultrasonic cell crusher, standing for 30min, and repeating for three times to obtain suspension liquid without layering after standing. The solution was poured into a round bottom flask, 25 μ L hydrazine hydrate (analytical grade) was added as a reducing agent, and ammonia (analytical grade) was added dropwise to adjust the pH of the solution to 11, then the stirrer of the oil bath was adjusted to 92 ℃ and the oil bath was heated for 60 min. Spray drying the completely reacted liquid at the feeding speed of 5mL/min, the air inlet temperature of 200 ℃ and the atomization pressure of 0.8MPa by a spray drying device to obtain Sb with uniform particle size2Se3-pvc-rGO powder.
Second step, preparation of Sb2Se3-a pvc-rGO membrane:
sb obtained in the last step2Se3mixing-pvc-rGO powder with binder PVDF according to a mass ratio of 9:1, grinding for 2 hours using an agate mortar, dropwise adding N-methylpyrrolidone, and then grinding while dropwise adding N-methylpyrrolidone until the material is completely dissolved. Continuously grinding for 30 minutes to form bright black slurry, coating by using a metal scraper, adjusting the scale of the scraper to be 8 mu m, coating on a Celgard2400 diaphragm, and performing vacuum drying at 60 ℃ for 12 hours to obtain the Sb coated uniformly2Se3-a composite membrane of pvp and graphene. The coated separator having a diameter of 19mm was cut out using a cutter.
Step three, preparing the lithium-sulfur battery anode material:
weighing 50mg of graphene oxide powder and 150mg of elemental sulfur, putting the graphene oxide powder and the elemental sulfur into a mortar, and adding CS2Grinding the solvent for 60min, putting the ground solvent into an inner container of a reaction kettle (the process is carried out in a glove box to ensure that the inner container of the reaction kettle is filled with rare gas), then moving the reaction kettle into a constant-temperature oven, doping sulfur by adopting a hot melting method, and heating at 155 ℃ for 12 hours. And cooling to room temperature to obtain the carbon-sulfur composite material.
Fourthly, preparing a battery positive plate and assembling a battery:
placing the prepared carbon-sulfur composite material, a conductive agent (super P-conductive carbon black) and a binder (PVDF-polyvinylidene fluoride) in a mortar according to the mass ratio of 8: 1, grinding and mixing to obtain slurry, using a scraper to adjust the scraping thickness to 15 mu m, uniformly scraping and coating the slurry on a carbon-containing aluminum foil, drying at 60 ℃ for 24h, and pressing into sheets under the pressure of 5MPa by using a tablet press to obtain the positive plate. And adding electrolyte into the carbon-sulfur material serving as a positive electrode and the metal lithium sheet serving as a negative electrode, and assembling the battery in a glove box to obtain the button type CR2025 battery.
Example 2
The other points are the same as example 1 except that Sb is the first step2Se3The mass ratio of the-pvc to the graphene oxide is 1:1.5, and the usage amount of hydrazine hydrate is 37.5 muL.
Example 3
The other points are the same as example 1 except that Sb is the first step2Se3The mass ratio of the-pvc to the graphene oxide is 1:2, and the usage amount of the hydrazine hydrate is 50 mu L.
FIG. 1 shows Sb prepared in example 12Se3-XRD pattern of pvp-rGO material. As can be seen from the figure, there is a distinct graphene peak at 23 deg., demonstrating rGO and Sb2Se3The-pvc material composites very well.
FIG. 2 shows Sb prepared in example 12Se3First charge-discharge curve at 0.1C for the-pvc-rGO material as separator. The test equipment was tested using Newcastle disease Virus BTS-2000 at constant room temperature (25 ℃). The constant-current discharge voltage is set to be 3.0V, and the charging voltage is set to be 1.5V, so that the prepared lithium-sulfur battery works in a voltage range of 1.5-3.0V. As can be seen from the figure, the specific charge and discharge capacity of the 60 th cycle can still reach 1168 and 1082mA · g < -1 >, and the electrochemical performance is better.
The invention is not the best known technology.
Claims (2)
1. Sb for lithium-sulfur battery diaphragm2Se3A method for preparing a composite material, characterized in that the method comprises the steps of:
first step, preparation of Sb2Se3-pvp-rGO：
(1) Sb is weighed respectively2Se3And pvp, Sb mixed in a ratio of 4-6:12Se3Adding the-pvc powder into deionized water to prepare water phase suspension with the mass concentration of 0.1-1%, magnetically stirring for 1-2h at room temperature, and ultrasonically dispersing by a cell crusher to obtain Sb2Se3-a pvc dispersion;
(2) mixing the graphene oxide dispersion liquid with Sb2Se3Mixing the PVC dispersion liquid, and performing ultrasonic dispersion again through a cell crusher to obtain a mixed liquid; wherein the mass concentration of the graphene oxide dispersion liquid is 1-3 mg/mL; mass ratio Sb2Se3-pvc powder: graphene oxide = 1: 1-2;
(3) adding into the mixed liquidAdding hydrazine hydrate, dropwise adding ammonia water to adjust the pH value of the solution to 10-12, heating by an oil bath at the temperature of 80-100 ℃, and continuously stirring for 30-90 min by magnetic force; spray drying the liquid at the air inlet temperature of 180 ℃ and the feeding speed of 3-8mL/min and the atomization pressure of 0.8Mpa, collecting the powder after the spray drying to obtain Sb2Se3-pvp-rGO; wherein, 10-50 μ L of hydrazine hydrate is added into every 100-250mL of mixed liquid;
second step, preparation of a composition having Sb2Se3-a pvc-rGO coated separator:
the obtained Sb2Se3Mixing the pvc-rGO powder with a binder PVDF, grinding for 1-3 hours, continuously grinding, and dropwise adding N-methylpyrrolidone until the materials are completely dissolved; continuously grinding for 20min-50min to form bright black slurry, coating on Celgard2400 diaphragm with thickness of 5-15 μm, and vacuum drying at 60 deg.C for 12h to obtain Sb2Se3-a composite membrane of pvc and graphene;
wherein the mass ratio Sb2Se3-pvc-rGO powder: PVDF = 7-10: 1 as a binder;
Sb2Se3the unique rod-like structures enter the graphene gaps in an embedded form, supporting the lamellar structure of graphene.
2. Sb for lithium-sulfur battery separator according to claim 12Se3Use of a method for the preparation of a composite material, characterised in that the Sb obtained is2Se3Application of composite membrane of pvp with graphene, tailored for CR2025 type cells.
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| CN109346646B (en) * | 2018-09-30 | 2021-12-28 | 肇庆市华师大光电产业研究院 | Novel lithium-sulfur battery diaphragm material, preparation method and application |
| CN110838579B (en) * | 2019-11-19 | 2022-05-31 | 肇庆市华师大光电产业研究院 | Preparation method and application of lithium-selenium battery positive electrode material |
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