CN109346647B - Preparation method and application of lithium-sulfur battery diaphragm - Google Patents
Preparation method and application of lithium-sulfur battery diaphragm Download PDFInfo
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- CN109346647B CN109346647B CN201811184351.7A CN201811184351A CN109346647B CN 109346647 B CN109346647 B CN 109346647B CN 201811184351 A CN201811184351 A CN 201811184351A CN 109346647 B CN109346647 B CN 109346647B
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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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- 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 and application of a multifunctional lithium-sulfur battery diaphragm. The battery diaphragm consists of a diaphragm substrate and a functional coating layer, wherein the functional coating layer is tightly attached to the surface of the diaphragm substrate and is prepared by mixing modified chitosan, a conductive agent and a binder and combining a tape casting forming method. The multifunctional lithium-sulfur battery diaphragm has a physical barrier effect on polysulfide diffusion, has a good conductive network, and can improve the utilization rate of sulfur; meanwhile, the modified chitosan has more polar groups and catalytic units, so that the polysulfide can be effectively subjected to chemical adsorption and conversion promotion, the shuttle effect of the battery is inhibited, and the capacity and the cycling stability of the battery are improved. In addition, the method has the advantages of simple process, low raw material cost and strong practicability, is favorable for promoting the industrialization of the lithium-sulfur battery, and has important economic significance for promoting the development of a high-performance novel energy storage system.
Description
Technical Field
The invention belongs to the technical field of battery materials. More particularly, relates to a preparation method and application of a lithium-sulfur battery separator.
Background
In the past thirty years, lithium ion batteries have been widely researched and applied as common energy storage systems, but limited by the specific capacity of the anode material, the specific energy is difficult to be greatly improved, so that research and development of high-performance lithium ion batteries and development of new energy storage systems have important significance for increasing energy storage requirements. Compared with a lithium ion battery, the lithium-sulfur battery with metal lithium as a negative electrode and elemental sulfur as a positive electrode has higher theoretical capacity (1675mAh/g) and energy density (2600Wh/kg), and the elemental sulfur has the advantages of no pollution, rich source, low cost and the like, and meets the current requirements on power sources of power batteries and electronic products. At present, lithium-sulfur batteries become an international research hotspot and are expected to become a battery energy storage system of the next generation.
However, large-scale application of lithium sulfur batteries still faces problems such as poor conductivity of the active material, shuttle effect caused by polysulfide (intermediate product), low discharge capacity and poor cycle stability in battery performance. In order to solve the above problems, researchers have designed various nanostructured positive hosts (such as carbon materials and conductive polymers) to coat elemental sulfur, but this approach involves a complicated synthetic process and is difficult to commercialize.
The diaphragm is used as an important component of the battery, and plays a role in physically isolating the positive electrode from the negative electrode and avoiding short circuit caused by internal electron transmission. At present, in a lithium sulfur battery, a traditional lithium ion battery polyolefin (PP) diaphragm is still used as a diaphragm, the cost of the diaphragm is low, but polysulfide cannot be prevented from diffusing in the battery cycle process, so that capacity loss is caused, the heat resistance is poor, and the battery is easy to crack and generate short circuit so as to cause safety problems. If the diaphragm is subjected to coating treatment or an intermediate layer is added between the diaphragm and the anode, shuttle of polysulfide can be prevented and the utilization rate of sulfur can be improved, so that the method is simpler and easier to implement than a nano-structure anode host and is easier for large-scale production.
At present, most of materials adopted for coating a diaphragm of the lithium-sulfur battery are nonpolar carbon materials such as graphene, carbon nanotubes and the like, the diaphragm can realize physical barrier and reutilization to polysulfide, but the adopted nonpolar carbon materials have poor barrier effect on polar polysulfide; in addition, some studies use some inorganic substances (such as metal oxides, sulfides, etc.) as the material for coating the separator, which have strong polarity, but tend to have limited adsorption capacity due to low specific surface, and strong chemical adsorption effect on polysulfide is not favorable for subsequent conversion. Therefore, the development of a multifunctional lithium-sulfur battery diaphragm with more excellent performance has great significance for promoting the development of a novel high-performance energy storage system.
Disclosure of Invention
The invention aims to overcome the defects of the existing lithium-sulfur battery diaphragm and provide a preparation method of a multifunctional lithium-sulfur battery diaphragm. The diaphragm prepared by the method can realize better physical barrier and chemical adsorption effects on polysulfide, promote the occurrence of subsequent conversion reaction, improve the conductivity of active material elemental sulfur, and improve the utilization rate of sulfur, so that the discharge capacity of the battery is enlarged, and the cycle stability is improved.
The invention aims to provide a preparation method of a multifunctional lithium-sulfur battery diaphragm.
The invention also aims to provide application of the multifunctional lithium-sulfur battery separator in preparing a multifunctional lithium-sulfur battery.
In order to achieve the purpose, the invention is realized by the following scheme:
the invention provides a preparation method of a multifunctional lithium-sulfur battery diaphragm, which is prepared by taking modified chitosan, a conductive agent and a binder as raw materials.
Wherein, preferably, the modified chitosan is a metal ion-containing modified chitosan.
Preferably, the metal ion is iron, cobalt or nickel.
More preferably, the preparation method of the modified chitosan comprises the following steps: dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan acetic acid solution; then adding a metal salt solution, and carrying out ultrasonic treatment to obtain metal-containing uniform viscous hydrogel; and then dialyzing the hydrogel with deionized water, and freeze-drying to obtain the modified iron-containing chitosan aerogel.
Preferably, the concentration of the acetic acid aqueous solution is 0.1-0.3M.
Preferably, the concentration of chitosan in the chitosan acetic acid solution is 10-30 mg/mL.
Preferably, the concentration of the metal salt solution is 0.25-1.0M.
Preferably, the metal salt of the metal salt solution is potassium ferricyanate, potassium cobaltcyanate or potassium nickel cyanate.
Preferably, the volume ratio of the chitosan acetic acid solution to the metal salt solution is 7-10: 1.
preferably, the time of the ultrasonic treatment is 5-15 min.
Preferably, the dialysis time is 2-3 d.
Preferably, the freeze drying time is 24-48 h.
In addition, preferably, the multifunctional lithium-sulfur battery diaphragm is prepared by using modified chitosan, a conductive agent and a binder as raw materials, and performing ball milling, dispersion, coating of a base film and drying.
More preferably, the preparation of the multifunctional lithium-sulfur battery separator comprises the following steps: mixing the modified chitosan, the conductive agent and the binder, then ball-milling, adding the mixture into the dispersant for dispersion, stirring to obtain slurry, then uniformly coating the slurry on a basement membrane, and drying to obtain the lithium-sulfur battery diaphragm.
Wherein, the conductive agent is preferably Super P, acetylene black, carbon nanotube or Ketjen black.
Preferably, the binder is polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), or carboxymethylcellulose (CMC).
Preferably, the dispersant is nitrogen methyl pyrrolidone or water.
Preferably, the mass ratio of the modified chitosan to the conductive agent to the binder is 2-4: 5-7: 1.
preferably, the ball milling time is 1-6 h.
Preferably, the stirring time is 6-12 h.
Preferably, the coating method is coating with a doctor blade.
More preferably, the thickness of the scraper is 90 to 200 μm.
Preferably, the drying temperature is 50-80 ℃, and the drying time is 12-36 h.
In addition, the multifunctional lithium-sulfur battery separator prepared by the method and the application of the multifunctional lithium-sulfur battery separator as a separator material or in the preparation of a lithium-sulfur battery are also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, chitosan is modified, slurry is formed by the modified chitosan, a conductive agent and a binder, and a tape casting method is combined to prepare the multifunctional lithium-sulfur battery diaphragm, wherein the battery diaphragm can effectively carry out chemical adsorption on polysulfide, promote the conversion of the polysulfide and inhibit the shuttle effect of a battery; the conductive network has good conductivity, and has physical barrier effect on the diffusion of polysulfide, thereby improving the utilization rate of sulfur, and improving the capacity and the cycling stability of the battery. In addition, the lithium-sulfur battery diaphragm disclosed by the invention is simple in preparation process, low in raw material cost, easy for large-scale production and strong in practicability, and is beneficial to promoting the development of the lithium-sulfur battery industry.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of chitosan raw material and modified iron-containing chitosan.
FIG. 2 shows the polysulfide adsorption experiment of chitosan raw material and modified iron-containing chitosan.
FIG. 3 is a surface topography of a coating layer of a multifunctional lithium-sulfur battery separator containing iron-containing chitosan.
FIG. 4 is a cross-sectional view of a multifunctional lithium-sulfur battery separator containing iron-containing chitosan.
Fig. 5 is a test chart of cyclic voltammetry of symmetric batteries corresponding to the iron-containing chitosan multifunctional lithium-sulfur battery diaphragm, the chitosan composite diaphragm and the commercial polyolefin diaphragm.
Fig. 6 is a cycle test chart at a charge-discharge rate of 0.5C when the iron-containing chitosan multifunctional lithium sulfur battery separator, the chitosan composite separator, and the commercial polyolefin separator are used in a lithium sulfur battery.
Fig. 7 is a charge and discharge test chart at different rates when the iron-containing chitosan multifunctional lithium sulfur battery separator, the chitosan composite separator and the commercial polyolefin separator are used in a lithium sulfur battery.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 preparation of modified iron-containing chitosan
Dissolving chitosan in 20mL of 0.1M acetic acid solution to obtain a chitosan acetic acid solution with the concentration of chitosan being 10 mg/mL; adding 2mL of 1.0M potassium ferricyanate solution, and performing ultrasonic treatment for 5min to crosslink the two solutions to obtain metal-containing uniform viscous hydrogel; and then dialyzing the hydrogel with deionized water for 3d, and freeze-drying for 24h to obtain the modified iron-containing chitosan aerogel.
Example 2 preparation of modified cobalt-containing Chitosan
Dissolving chitosan in 15mL of 0.2M acetic acid solution to obtain a chitosan acetic acid solution with the concentration of chitosan being 20 mg/mL; then adding 2mL of 1.0M potassium cobaltocyanate solution, and carrying out ultrasonic treatment for 15min to crosslink the two solutions to obtain metal-containing uniform viscous hydrogel; and then dialyzing the hydrogel for 3d with deionized water, and freeze-drying for 24h to obtain the modified cobalt-containing chitosan aerogel.
Example 3 preparation of modified Nickel-containing Chitosan
Dissolving chitosan in 15mL of 0.3M acetic acid solution to obtain chitosan acetic acid solution with the concentration of chitosan being 30 mg/mL; then adding 2mL of 0.25M potassium nickel cyanate solution, and carrying out ultrasonic treatment for 10min to crosslink the two solutions to obtain metal-containing uniform viscous hydrogel; and then dialyzing the hydrogel with deionized water for 3d, and freeze-drying for 48h to obtain the modified nickel-containing chitosan aerogel.
Example 4 preparation of iron-containing chitosan multifunctional lithium-sulfur battery separator
The iron-containing chitosan aerogel obtained in example 1, carbon nanotubes and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 3: 6: 1, ball-milling for 1h to obtain mixed powder, dispersing 150mg of the mixed powder into 1mL of nitrogen methyl pyrrolidone solvent, and stirring for 12h at room temperature to obtain uniform slurry; and uniformly coating the slurry on a commercial polyolefin diaphragm (PP) by using a scraper with the thickness of 150 mu m, and drying in an oven at the temperature of 70 ℃ for 12h to obtain the multifunctional lithium-sulfur battery diaphragm containing the iron chitosan.
EXAMPLE 5 preparation of cobalt-containing Chitosan multifunctional lithium Sulfur Battery separator
The cobalt-containing chitosan aerogel obtained in example 2, acetylene black and Polytetrafluoroethylene (PTFE) were mixed in a mass ratio of 2: 5: 1, ball-milling for 6 hours to obtain mixed powder, dispersing 150mg of the mixed powder into 1mL of nitrogen methyl pyrrolidone solvent, and stirring for 6 hours at room temperature to obtain uniform slurry; and uniformly coating the slurry on a commercial polyolefin diaphragm (PP) by using a scraper with the thickness of 100 mu m, and drying in an oven at the temperature of 50 ℃ for 36h to obtain the multifunctional lithium sulfur battery diaphragm containing the cobalt chitosan.
Example 6 preparation of a Nickel-containing Chitosan multifunctional lithium Sulfur Battery separator
The nickel-containing chitosan aerogel obtained in example 3, ketjen black, and carboxymethyl cellulose (CMC) were mixed in a mass ratio of 4: 7: 1, ball-milling for 3 hours to obtain mixed powder, dispersing 150mg of the mixed powder into 1mL of nitrogen methyl pyrrolidone solvent, and stirring for 10 hours at room temperature to obtain uniform slurry; and uniformly coating the slurry on a commercial polyolefin diaphragm (PP) by using a scraper with the thickness of 90 mu m, and drying in an oven at the temperature of 80 ℃ for 12h to obtain the multifunctional nickel-containing chitosan lithium-sulfur battery diaphragm.
Example 7 preparation of chitosan composite separator
Referring to the method of example 4, a chitosan composite separator was prepared by replacing the iron-containing chitosan aerogel with chitosan powder.
Example 8 product characterization and Performance testing of multifunctional lithium Sulfur Battery separator
The product characterization and performance test results are given below by taking the modified iron-containing chitosan prepared in examples 1, 4 and 7, the multifunctional lithium-sulfur battery separator and the chitosan composite separator as examples:
(1) FIG. 1 shows the Fourier infrared spectrum characterization of chitosan material and modified chitosan containing iron, and it can be seen from the results that 2114cm of modified chitosan containing iron appears compared with chitosan-1And 2039cm-1Two new peaks, demonstrating iron ion cross-linking into chitosan.
(2) The result of a visualized polysulfide adsorption experiment on the chitosan raw material and the modified chitosan containing iron is shown in fig. 2, and it can be seen that the color change of the solution is small after the chitosan is added; and the modified iron-containing chitosan is added, the color of the solution is changed greatly from orange yellow to light yellow, the iron-containing chitosan on the surface has better adsorption effect on the polysulfide intermediate, and the shuttle of the solution is favorably inhibited.
(3) The characterization graph of a Scanning Electron Microscope (SEM) of the multifunctional lithium-sulfur battery diaphragm containing the iron chitosan is shown in FIG. 3, and the surface morphology result shows that: the coating layer has a more uniform distribution.
(4) The cross-sectional topography of the iron-containing chitosan multifunctional lithium-sulfur battery separator is shown in fig. 4, and the result shows that the thickness of the coating layer is about 15 μm.
(5) The iron-containing chitosan multifunctional lithium-sulfur battery diaphragm, the chitosan composite diaphragm and the commercial polyolefin diaphragm are subjected to polysulfide symmetric battery cyclic voltammetry, and the test result is shown in fig. 5.
(6) The lithium sulfur battery cycle test of the iron-containing chitosan multifunctional lithium sulfur battery diaphragm, the chitosan composite diaphragm and the commercial polyolefin diaphragm is carried out, and the result is shown in fig. 6, which shows that the battery assembled by the iron-containing chitosan multifunctional lithium sulfur battery diaphragm has the highest discharge capacity of 1141mAh/g and the best cycle stability under the charge-discharge rate of 0.5C, and the retention rate is 81% after 100 cycles; the corresponding discharge capacities of the batteries assembled by the chitosan composite membrane and the commercial polyolefin membrane are 898mAh/g and 725mAh/g respectively, and the retention rates of the corresponding capacities are 79% and 74% respectively.
(7) The lithium-sulfur battery rate performance test of the iron-containing chitosan multifunctional lithium-sulfur battery diaphragm, the chitosan composite diaphragm and the commercial polyolefin diaphragm is carried out, the result is shown in fig. 7, the result shows that the battery assembled by the iron-containing chitosan multifunctional lithium-sulfur battery diaphragm has the best rate performance, and the discharge capacity is 882mAh/g under the 2C charge-discharge rate; and the corresponding discharge capacities of the batteries assembled by the chitosan composite membrane and the commercial polyolefin membrane are 569mAh/g and 518mAh/g respectively.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the lithium-sulfur battery diaphragm is characterized in that the lithium-sulfur battery diaphragm is prepared by taking modified chitosan, a conductive agent and a binder as raw materials, wherein the modified chitosan is modified chitosan containing metal ions;
the metal ions are iron, cobalt or nickel;
the preparation method of the modified chitosan comprises the following steps: dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan acetic acid solution; then adding a metal salt solution, and carrying out ultrasonic treatment to obtain metal-containing uniform viscous hydrogel; then dialyzing the hydrogel with deionized water, freezing and drying to obtain modified chitosan aerogel containing metal ions;
the metal salt of the metal salt solution is potassium ferricyanate, potassium cobaltcyanate or potassium nickel cyanate.
2. The preparation method of claim 1, wherein the concentration of the acetic acid aqueous solution is 0.1-0.3M, and the concentration of chitosan in the chitosan acetic acid solution is 10-30 mg/mL.
3. The method according to claim 1, wherein the metal salt solution has a concentration of 0.25 to 1.0M.
4. The preparation method according to claim 1, wherein the volume ratio of the chitosan acetic acid solution to the metal salt solution is 7-10: 1.
5. the method according to any one of claims 1 to 4, wherein the lithium-sulfur battery separator is prepared by the steps of: mixing the modified chitosan, the conductive agent and the binder, then ball-milling, adding the mixture into the dispersant for dispersion, stirring to obtain slurry, then uniformly coating the slurry on a basement membrane, and drying to obtain the lithium-sulfur battery diaphragm.
6. The preparation method according to claim 5, wherein the mass ratio of the modified chitosan to the conductive agent to the binder is 2-4: 5-7: 1.
7. the lithium-sulfur battery separator prepared by the method according to any one of claims 1 to 6.
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