CN112768840A - Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof - Google Patents
Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof Download PDFInfo
- Publication number
- CN112768840A CN112768840A CN202110004149.7A CN202110004149A CN112768840A CN 112768840 A CN112768840 A CN 112768840A CN 202110004149 A CN202110004149 A CN 202110004149A CN 112768840 A CN112768840 A CN 112768840A
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- multifunctional
- lithium
- carbon
- polydopamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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 multifunctional diaphragm of a lithium-sulfur battery, which comprises a diaphragm substrate, wherein at least one surface of the diaphragm substrate is coated with a modified coating, the modified coating is a composite coating containing polydopamine, a carbon material and a catalytic material, and a catalyst is one or more of metal sulfide, metal carbide and metal oxide. The preparation method comprises the steps of preparing a polydopamine/carbon dispersion liquid, then uniformly mixing the polydopamine/carbon dispersion liquid with additives such as a catalytic material and a thickening agent to prepare slurry, finally coating the slurry on the surface of a diaphragm substrate, and drying to obtain the multifunctional diaphragm of the lithium-sulfur battery. The lithium-sulfur battery diaphragm prepared by the invention has the functions of inhibiting shuttling and catalytic conversion of polysulfide, oxygen-containing functional groups in a polydopamine molecular chain inhibit the shuttling of the polysulfide, the polysulfide is adsorbed on the coating layer side of the diaphragm under the action of a catalytic material and a carbon material, and the polysulfide is prevented from shuttling to a negative electrode through the inhibiting-converting function, so that the cycle life of the lithium-sulfur battery is remarkably prolonged.
Description
Technical Field
The invention belongs to the field of new energy materials and devices, and particularly relates to a multifunctional diaphragm of a lithium-sulfur battery and a preparation method thereof.
Background
The electrochemical energy storage system is a key system for realizing conversion, storage and control of renewable clean energy, is characterized by safety, low price, high efficiency and long service life, and realizes the conversion between chemical energy and electric energy. Compared with traditional lead-acid batteries, nickel-hydrogen batteries, nickel-chromium batteries and the like, the current commercial lithium ion batteries have the advantages of light weight, low self-discharge, no memory effect and the like. With the development of the commercialization process, the application field of the lithium ion battery is also expanded from portable electronic goods such as mobile phones and notebook computers to the fields of electric automobiles, electric tools, national defense, aerospace and the like. However, the energy density of the current commercial lithium ion battery is low, and the current commercial lithium ion battery cannot meet the higher requirement of the electric automobile and the like on the endurance mileage of the power battery. Therefore, the search for battery systems with high specific capacity and high energy density is an important goal of research in the field of energy storage.
The lithium-sulfur battery is a battery system with elemental sulfur as a positive electrode material and metal lithium as a negative electrode material. The anode material has the advantages of low elemental sulfur price, environmental friendliness, high specific capacity and the like, and is widely concerned. The theoretical specific capacity of the elemental sulfur electrode is 1675mAh/g, and the lithium sulfur battery with high theoretical specific capacity and high energy density has great potential to become a next-generation power battery and realize commercial application.
The charging and discharging process of the lithium-sulfur battery is a complex phase transfer process from solid phase to liquid phase to solid phase. In the discharging process, elemental sulfur firstly obtains electrons to be reduced to generate soluble polysulfide ion S8 2-Then Li is generated by gradual reduction2S2And Li2And S. An intermediate product polysulfide generated in the charging and discharging processes of the lithium-sulfur battery can be dissolved in the electrolyte, and cannot be completely converted into a final product after the charging and discharging are finished, so that the loss of active substances is caused, and the specific capacity of the battery is reduced. Solid phase Li during charging2S2And Li2S can lose electrons to be oxidized to obtain long-chain polysulfide, and the long-chain polysulfide dissolved in the electrolyte can migrate to the negative electrode under the action of concentration gradient. On the surface of the negative electrode, long-chain polysulfide reacts with metallic lithium to be reduced to obtain short-chain polysulfide, and even insoluble Li is formed2S2And Li2S is deposited on the surface of the negative electrode. This not only corrodes the surface of the lithium electrode to break the SEI film, but also increases the resistance of the surface of the lithium negative electrode to recapture electrons and supply lithium ions, and also increases the loss of active materials. On the other hand, short-chain polysulfide dissolved in the electrolyte returns to the positive electrode under the action of an electric field force, and is further oxidized to obtain long-chain polysulfide, so that a shuttle effect is generated. The shuttle effect not only causes the reduction of the charge and discharge efficiency of the battery, but also makes it difficult to sufficiently utilize the active material. With the progress of charge and discharge reaction, the specific capacity of the battery is continuously lost by the shuttling and deposition actions of polysulfide, and the cycle life of the battery is shortened. Therefore, a separator is required between the positive and negative electrodes of a lithium sulfur battery to block polysulfide shuttling. However, during the charging and discharging of the lithium-sulfur battery, the dissolved polysulfide shuttles back and forth through the pores of the separator, resulting in the battery performanceCan be lowered. Therefore, the shuttle of polysulfide among the membranes can be inhibited by modifying the membranes, and the negative influence caused by the shuttle effect is reduced, so that the cycle life and the charge-discharge efficiency of the battery are improved.
At present, a modified diaphragm of a lithium-sulfur battery is prepared by simply mixing polydopamine and a carbon material to prepare slurry, and then coating the slurry on a matrix diaphragm to prepare the modified diaphragm, however, the polydopamine and the carbon material are difficult to be uniformly dispersed by simply mixing, the modification capability of the diaphragm is limited, and if carbon particles which are not uniformly dispersed do not have the capability of blocking polysulfide, the performance of the lithium-sulfur battery is even deteriorated.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a multifunctional diaphragm of a lithium-sulfur battery and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the multifunctional diaphragm of the lithium-sulfur battery comprises a diaphragm substrate, wherein at least one surface of the diaphragm substrate is covered with a modified coating, the modified coating is a composite coating containing polydopamine, a carbon material and a catalytic material, and the catalyst is one or more of metal sulfide, metal carbide and metal oxide.
In the multifunctional diaphragm, the mass ratio of the polydopamine, the carbon and the catalytic material in the modified coating is preferably 1 (0.000001-0.2) to 0.05-0.2.
Preferably, the thickness of the modified coating is 0.5-50 μm.
Preferably, the metal sulfide is one or more of iron disulfide, titanium disulfide and molybdenum disulfide; the metal carbide is titanium carbide; the metal oxide is one or more of vanadium pentoxide and titanium dioxide.
In the above multifunctional separator, the carbon material is preferably at least one of a zero-dimensional carbon material, a one-dimensional carbon material, a two-dimensional carbon material, and a three-dimensional carbon material.
In the above multifunctional separator, preferably, the carbon material is a carbon material modified by doping one or more elements selected from nitrogen, phosphorus, sulfur and oxygen.
In the above-mentioned multifunctional separator, the separator substrate preferably includes any one of a polyolefin porous membrane, a polyimide porous membrane, a polymethyl methacrylate porous membrane, a polyvinylidene fluoride porous membrane, and a polyacrylonitrile porous membrane.
As a general inventive concept, the present invention also provides a method of preparing the above multifunctional separator, comprising the steps of:
(1) uniformly mixing ammonia water, a carbon material, a surfactant, an organic solvent and deionized water to obtain a solution A;
uniformly mixing dopamine hydrochloride and deionized water to obtain a solution B;
(2) adding the solution B into the solution A under the stirring condition for reaction to obtain a poly-dopamine/carbon suspension;
(3) centrifugally separating and washing the poly-dopamine/carbon suspension, and preparing a washed product and deionized water into a poly-dopamine/carbon dispersion liquid;
(4) uniformly mixing the polydopamine/carbon dispersion liquid, a catalytic material, a thickening agent, a dispersing agent and a binder to obtain multifunctional diaphragm slurry;
(5) and coating the multifunctional diaphragm slurry on the surface of the diaphragm substrate, and drying to obtain the multifunctional diaphragm of the lithium-sulfur battery.
Preferably, in the preparation method, in the step (1), in the solution a, the mass ratio of ammonia water, carbon material, auxiliary agent, organic solvent and deionized water is 1: (0.01-65): (0.325-16.25): (20-95): (45-230); in the solution B, the mass ratio of dopamine hydrochloride to deionized water is 1: (1-50).
In the step (2), the mass ratio of the solution A to the solution B is 1: (5-100).
In the step (4), the dosage of each raw material is respectively as follows by mass: 50-100 parts of polydopamine/carbon dispersion liquid, 0.001-10 parts of catalytic material, 0.0001-0.5 part of thickening agent, 0.0001-1 part of dispersing agent and 0.2-5 parts of binder.
In the preparation method, preferably, in the step (1), the surfactant is one or more of polyether stearate dimethyl siloxane, sodium diisooctyl sulfonate, alkyl naphthalene sulfonate, tertiary alkyl polyol polyvinyl ether, polyether modified silicone oil, polyoxyethylene glycerol ether, polypropylene glycol-ethylene oxide, polyoxyethylene polyoxypropylene pentaerythritol ether and polyoxyethylene polyoxypropylene amine ether; the surfactants have a dispersing effect on raw materials in the solution A, and the particle size and the dispersibility of the polydopamine/carbon composite material can be controlled by controlling the proportion of the surfactants and ammonia water, so that the material with smaller particle size is prepared.
The organic solvent is one or more of methanol, ethanol, isopropanol, N-methyl formamide and N-methyl pyrrolidone;
in the step (4), the thickening agent is one or more of sodium carboxymethylcellulose, methyl hydroxyethyl cellulose, polyethylene oxide, sodium alginate and polyacrylamide;
the dispersing agent is one or more of polyacrylic acid, sodium polyacrylate and sodium dodecyl benzene sulfonate;
the binder is one or more of polyacrylate, polyvinyl alcohol, styrene-butadiene copolymer and ethylene-vinyl acetate copolymer.
In the preparation method, preferably, in the step (2), the reaction time is 10-48 h;
in the step (3), washing is carried out for 3-6 times by using deionized water with 0.5-3% of surfactant by mass; the solid content of the polydopamine/carbon dispersion is 1-20%.
Compared with the prior art, the invention has the advantages that:
(1) the lithium-sulfur battery diaphragm prepared by the invention has the functions of inhibiting shuttling and catalytic conversion of polysulfide, the shuttling of the polysulfide is inhibited through the oxygen-containing functional groups in the polydopamine molecular chain, the polysulfide is adsorbed on the coating layer side of the diaphragm under the action of the catalytic material and the carbon material, and the shuttling of the polysulfide to a negative electrode is effectively prevented through the inhibiting-converting function, so that the cycle life of the lithium-sulfur battery is remarkably prolonged.
(2) The prepared water-based lithium-sulfur battery diaphragm coating slurry is synthesized by a solution method, has good dispersibility, and can improve the dispersion uniformity of polydopamine, carbon and a catalyst in a coating, thereby reducing the battery capacity loss caused by the non-uniform local material of the diaphragm coating.
(3) The spherical poly-dopamine/carbon material with controllable size is synthesized by controlling the raw material proportion and the process, the dispersibility in the slurry is good, the coating can form a uniform close-packed structure by adopting the spherical poly-dopamine/carbon composite material, narrow and tortuous pores are formed, the air permeability of the coating diaphragm is ensured, the path of the polysulfide shuttle is narrower, and the spherical poly-dopamine/carbon material is suitable for the lithium-sulfur battery with high-rate discharge.
(4) The method has the advantages of simple process, easily obtained raw materials, capability of matching with the existing battery coating diaphragm production equipment and easiness in realizing industrial production.
Drawings
Fig. 1 is a surface SEM image of the multifunctional separator in example 1 of the present invention.
Fig. 2 is a cross-sectional SEM image of the multifunctional membrane in example 1 of the present invention.
Fig. 3 is a graph of the cycle curve of a battery prepared with the multifunctional separator of example 1 of the present invention.
Fig. 4 is a surface SEM image of the multifunctional separator in example 2 of the present invention.
Fig. 5 is a cross-sectional SEM image of the multifunctional membrane in example 2 of the present invention.
Fig. 6 is a surface SEM image of the multifunctional membrane in example 3 of the present invention.
Fig. 7 is a cross-sectional SEM image of the multifunctional membrane in example 3 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention discloses a multifunctional diaphragm of a lithium-sulfur battery, which comprises a diaphragm substrate polyethylene porous membrane, wherein two surfaces of the diaphragm substrate are coated with modified coatings, the modified coatings are composite coatings containing polydopamine, nitrogen-doped graphene and titanium carbide, the content ratio of the polydopamine, the nitrogen-doped graphene and the titanium carbide in the modified coatings is about 1:0.15:0.15, and the thickness of the coatings is 2 mu m.
The preparation method of the multifunctional membrane comprises the following steps:
(1) ammonia water, nitrogen-doped graphene, sodium diisooctyl sulfonate, isopropanol and deionized water in a mass ratio of 1:0.01: 16.25: 20: 230 to obtain a solution A;
adding dopamine hydrochloride and deionized water according to a mass ratio of 1: 20 to obtain a solution B;
(2) under the condition of stirring, according to the mass ratio of the solution A to the solution B of 1: 37, slowly adding the solution B into the solution A, and reacting for 10 hours to obtain a poly-dopamine/carbon suspension;
(3) centrifugally separating the poly-dopamine/carbon suspension, washing for 3 times by using deionized water containing 3% polyoxyethylene glyceryl ether, and adding the deionized water to prepare a poly-dopamine/carbon dispersion liquid with the solid content of 1%;
(3) uniformly mixing 100 parts of polydopamine/carbon dispersion liquid, 0.001 part of titanium carbide, 0.5 part of methyl hydroxyethyl cellulose, 0.0001 part of sodium polyacrylate and 5 parts of styrene-butadiene copolymer in parts by mass to obtain multifunctional diaphragm slurry;
(4) and coating the multifunctional diaphragm slurry on two surfaces of the polyethylene porous membrane, drying at 60 ℃, wherein the thickness of the coating after the slurry is dried is 2 mu m, and obtaining the multifunctional diaphragm of the lithium-sulfur battery, wherein SEM photographs of the surface and the cross section of the diaphragm are respectively shown in figure 1 and figure 2.
The lithium-sulfur battery is assembled by taking the metal lithium as a negative electrode and the carbon/sulfur compound as a positive electrode, and the sulfur load of the positive electrode plate is 4.5mg cm for electrical property test of the lithium-sulfur battery-2. The battery prepared by using the multifunctional diaphragm of the lithium-sulfur battery of the embodiment has the cycle performance as shown in fig. 3, and the specific first discharge capacity of 1613.5mAh g under the condition of 0.05C-1The specific cyclic discharge capacity under the 1C condition is 723.5mAh g-1The capacity retention after 50 weeks of cycling was 93.07%, as shown in table 1.
Example 2:
the invention relates to a multifunctional diaphragm of a lithium-sulfur battery, which comprises a diaphragm substrate and a polyimide porous membrane, wherein two surfaces of the diaphragm substrate are coated with modified coatings, the modified coatings are composite coatings containing polydopamine, oxygen-doped carbon nanotubes and molybdenum sulfide, the content ratio of the polydopamine, the oxygen-doped carbon nanotubes and the molybdenum sulfide in the modified coatings is about 1:0.20:0.20, and the thickness of the coatings is 20 mu m.
The preparation method of the multifunctional membrane comprises the following steps:
(1) ammonia water, oxygen-doped carbon nano tubes, ketjen black, sodium diisooctyl sulfonate, methanol and deionized water in a mass ratio of 1: 10:23: 0.325: 95: 150 to obtain a solution A;
adding dopamine hydrochloride and deionized water according to a mass ratio of 1: 1 to obtain a solution B;
(2) according to the mass ratio of the solution A to the solution B of 1: 37, slowly adding the solution B into the solution A under the stirring condition, and reacting for 48 hours to obtain a poly-dopamine/carbon suspension;
(3) centrifugally separating the poly-dopamine/carbon suspension, washing for 6 times by using deionized water containing 0.5% polyoxyethylene polyoxypropylene ether, and adding the deionized water to prepare a poly-dopamine/carbon dispersion liquid with the solid content of 20%;
(4) uniformly mixing 50 parts of polydopamine/carbon dispersion liquid, 10 parts of molybdenum sulfide, 0.0001 part of polyethylene oxide, 1 part of sodium dodecyl benzene sulfonate and 3 parts of polyacrylate according to the mass ratio to obtain multifunctional diaphragm slurry;
(5) and coating the multifunctional diaphragm slurry on two surfaces of the polyimide porous membrane, drying at 80 ℃, wherein the thickness of the coating after the slurry is dried is 20 mu m, and obtaining the multifunctional diaphragm of the lithium-sulfur battery, wherein SEM photographs of the surface and the cross section of the diaphragm are respectively shown in FIG. 4 and FIG. 5.
The lithium-sulfur battery is assembled by taking the metal lithium as a negative electrode and the carbon/sulfur compound as a positive electrode to carry out electrical property test, and the sulfur load of the positive electrode piece is 8mg cm-2. The battery prepared by the multifunctional diaphragm of the lithium-sulfur battery of the embodiment has the specific first discharge capacity of 1532.6mAh g under the condition of 0.05C-1The specific cyclic discharge capacity under the 1C condition is 681.5mAh g-1The capacity retention after 50 weeks of cycling was 90.28%.
Example 3:
the invention discloses a multifunctional diaphragm of a lithium-sulfur battery, which comprises a diaphragm substrate, namely a polyvinylidene fluoride porous membrane, wherein two surfaces of the diaphragm substrate are coated with modified coatings, the modified coatings are composite coatings containing polydopamine, fullerene and vanadium pentoxide, the mass ratio of the polydopamine, the fullerene and the vanadium pentoxide in the modified coatings is about 1:0.01:0.20, and the thickness of the coatings is 10 micrometers.
The preparation method of the multifunctional membrane comprises the following steps:
(1) ammonia water, fullerene, polyoxyethylene polyoxypropylene pentaerythritol ether, ethanol, isopropanol and deionized water are mixed according to a mass ratio of 1: 65: 13.5: 30:20: 45 to obtain a solution A;
adding dopamine hydrochloride and deionized water according to a mass ratio of 1: 50 to obtain a solution B;
(2) slowly adding the solution B into the solution A according to a proportion under the condition of stirring, and reacting for 24 hours to obtain a poly-dopamine/carbon suspension;
(3) centrifugally separating the poly-dopamine/carbon suspension, washing the suspension for 5 times by using deionized water containing 2% of polyether modified silicone oil, and adding the deionized water to prepare a poly-dopamine/carbon dispersion liquid with the solid content of 15%;
(4) uniformly mixing 70 parts of polydopamine/carbon dispersion liquid, 5 parts of vanadium pentoxide, 0.3 part of sodium alginate, 0.7 part of polyacrylic acid and 0.2 part of ethylene-vinyl acetate copolymer according to the mass ratio to obtain multifunctional diaphragm slurry;
(5) and coating the multifunctional diaphragm slurry on two surfaces of the polyvinylidene fluoride porous membrane, drying at 50 ℃, wherein the thickness of the coating after the slurry is dried is 10 mu m, so as to obtain the multifunctional diaphragm of the lithium-sulfur battery, and SEM photographs of the surface and the screenshot are respectively shown in figures 6 and 7.
The lithium-sulfur battery is assembled by taking the metal lithium as a negative electrode and the carbon/sulfur compound as a positive electrode to carry out electrical property test, and the sulfur load of the positive electrode piece is 6mg cm-2. The battery prepared by the multifunctional diaphragm of the lithium-sulfur battery of the embodiment has the specific first discharge capacity of 1583.7mAh g under the condition of 0.05C-1The specific cyclic discharge capacity under the 1C condition is 706.9mAh g-1The capacity retention after 50 weeks of cycling was 92.55%, as shown in table 1.
Table 1 electrochemical cycling performance of the cells of examples 1, 2 and 3
| Sulfur loading capacity | Specific capacity of 0.05C for first discharge | Specific capacity of 1C initial discharge | Capacity retention at 50 weeks | |
| Example 1 | 4.5mg cm-2 | 1613.5mAh g-1 | 723.5mAh g-1 | 93.07％ |
| Example 2 | 8mg cm-2 | 1532.6mAh g-1 | 681.5mAh g-1 | 90.28％ |
| Example 3 | 6mg cm-2 | 1583.7mAh g-1 | 706.9mAh g-1 | 92.55％ |
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The multifunctional diaphragm of the lithium-sulfur battery comprises a diaphragm substrate and is characterized in that at least one surface of the diaphragm substrate is coated with a modified coating, the modified coating is a composite coating containing polydopamine, a carbon material and a catalytic material, and the catalyst is one or more of metal sulfide, metal carbide and metal oxide.
2. The multifunctional membrane of claim 1 wherein said modified coating has a thickness of 0.5 to 50 μm.
3. The multifunctional membrane of claim 1, wherein the metal sulfide is one or more of iron disulfide, titanium disulfide, molybdenum disulfide; the metal carbide is titanium carbide; the metal oxide is one or two of vanadium pentoxide and titanium dioxide.
4. The multifunctional membrane according to claim 1, wherein the carbon material is at least one of a zero-dimensional carbon material, a one-dimensional carbon material, a two-dimensional carbon material, and a three-dimensional carbon material.
5. The multifunctional membrane according to claim 1, wherein the carbon material is a carbon material modified by doping with one or more elements selected from nitrogen, phosphorus, sulfur, and oxygen.
6. The multifunctional membrane according to any one of claims 1 to 5, wherein said membrane substrate comprises any one of a polyolefin porous membrane, a polyimide porous membrane, a polymethyl methacrylate porous membrane, a polyvinylidene fluoride porous membrane, and a polyacrylonitrile porous membrane.
7. A method of making the multifunctional membrane of any one of claims 1 to 6 comprising the steps of:
(1) uniformly mixing ammonia water, a carbon material, a surfactant, an organic solvent and deionized water to obtain a solution A;
uniformly mixing dopamine hydrochloride and deionized water to obtain a solution B;
(2) adding the solution B into the solution A under the stirring condition for reaction to obtain a poly-dopamine/carbon suspension;
(3) centrifugally separating and washing the poly-dopamine/carbon suspension, and preparing a washed product and deionized water into a poly-dopamine/carbon dispersion liquid;
(4) uniformly mixing the polydopamine/carbon dispersion liquid, a catalytic material, a thickening agent, a dispersing agent and a binder to obtain multifunctional diaphragm slurry;
(5) and coating the multifunctional diaphragm slurry on the surface of the diaphragm substrate, and drying to obtain the multifunctional diaphragm of the lithium-sulfur battery.
8. The method according to claim 7, wherein in the step (1), the mass ratio of the ammonia water, the carbon material, the surfactant, the organic solvent and the deionized water in the solution A is 1: (0.01-65): (0.325-16.25): (20-95): (45-230); the mass ratio of the dopamine hydrochloride to the deionized water in the solution B is 1: (1-50);
in the step (2), the mass ratio of the solution A to the solution B is 1: (5-100);
in the step (4), the dosage of each raw material is respectively as follows by mass: 50-100 parts of polydopamine/carbon dispersion liquid, 0.001-10 parts of catalytic material, 0.0001-0.5 part of thickening agent, 0.0001-1 part of dispersing agent and 0.2-5 parts of binder.
9. The method according to claim 7, wherein in the step (1), the surfactant is one or more selected from the group consisting of polyether stearate dimethyl siloxane, sodium diisooctyl sulfonate, alkyl naphthalene sulfonate, tertiary alkyl polyol polyvinyl ether, polyether modified silicone oil, polyoxyethylene glycerol ether, polypropylene glycol-ethylene oxide, polyoxyethylene polyoxypropylene pentaerythritol ether, and polyoxyethylene polyoxypropylene amine ether;
the organic solvent is one or more of methanol, ethanol, isopropanol, N-methyl formamide and N-methyl pyrrolidone;
in the step (4), the thickening agent is one or more of sodium carboxymethylcellulose, methyl hydroxyethyl cellulose, polyethylene oxide, sodium alginate and polyacrylamide;
the dispersing agent is one or more of polyacrylic acid, sodium polyacrylate and sodium dodecyl benzene sulfonate;
the binder is one or more of polyacrylate, polyvinyl alcohol, styrene-butadiene copolymer and ethylene-vinyl acetate copolymer.
10. The method according to claim 7, wherein in the step (2), the reaction time is 10 to 48 hours;
in the step (3), washing is carried out for 3-6 times by using deionized water with 0.5-3% of surfactant by mass; the solid content of the polydopamine/carbon dispersion is 1-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110004149.7A CN112768840A (en) | 2021-01-04 | 2021-01-04 | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110004149.7A CN112768840A (en) | 2021-01-04 | 2021-01-04 | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112768840A true CN112768840A (en) | 2021-05-07 |
Family
ID=75699117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110004149.7A Pending CN112768840A (en) | 2021-01-04 | 2021-01-04 | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112768840A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725558A (en) * | 2021-07-29 | 2021-11-30 | 长沙矿冶研究院有限责任公司 | Modified diaphragm of lithium-sulfur battery and preparation method thereof |
| CN113851696A (en) * | 2021-09-14 | 2021-12-28 | 中山大学 | C4N quantum dot material, preparation method thereof and lithium-sulfur battery diaphragm |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN115504473A (en) * | 2022-09-22 | 2022-12-23 | 南京大学 | MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489818A (en) * | 2015-12-29 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | Preparation method for modified diaphragm for lithium-sulfur battery, modified diaphragm and lithium-sulfur battery adopting modified diaphragm |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| CN106935773A (en) * | 2015-12-31 | 2017-07-07 | 中国人民解放军63971部队 | A kind of interlayer for lithium-sulfur cell |
| CN107442084A (en) * | 2017-07-26 | 2017-12-08 | 华南理工大学 | A kind of poly-dopamine pitch base composite porous carbon adsorbing material of Preferential adsorption ethane and preparation method and application |
| US20180198156A1 (en) * | 2016-01-28 | 2018-07-12 | Lg Chem, Ltd. | Lithium-sulfur battery separation film having composite coating layer including polydopamine, manufacturing method therefor, and lithium-sulfur battery comprising same |
| CN109786748A (en) * | 2018-12-29 | 2019-05-21 | 桑德集团有限公司 | A kind of lithium-sulphur cell positive electrode piece and preparation method thereof, lithium-sulfur cell |
| CN110707269A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for lithium-sulfur battery, application of diaphragm slurry, diaphragm for lithium-sulfur battery and lithium-sulfur battery |
-
2021
- 2021-01-04 CN CN202110004149.7A patent/CN112768840A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489818A (en) * | 2015-12-29 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | Preparation method for modified diaphragm for lithium-sulfur battery, modified diaphragm and lithium-sulfur battery adopting modified diaphragm |
| CN106935773A (en) * | 2015-12-31 | 2017-07-07 | 中国人民解放军63971部队 | A kind of interlayer for lithium-sulfur cell |
| US20180198156A1 (en) * | 2016-01-28 | 2018-07-12 | Lg Chem, Ltd. | Lithium-sulfur battery separation film having composite coating layer including polydopamine, manufacturing method therefor, and lithium-sulfur battery comprising same |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| CN107442084A (en) * | 2017-07-26 | 2017-12-08 | 华南理工大学 | A kind of poly-dopamine pitch base composite porous carbon adsorbing material of Preferential adsorption ethane and preparation method and application |
| CN109786748A (en) * | 2018-12-29 | 2019-05-21 | 桑德集团有限公司 | A kind of lithium-sulphur cell positive electrode piece and preparation method thereof, lithium-sulfur cell |
| CN110707269A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for lithium-sulfur battery, application of diaphragm slurry, diaphragm for lithium-sulfur battery and lithium-sulfur battery |
Non-Patent Citations (2)
| Title |
|---|
| 董国君、苏玉、王桂香: "《表面活性剂化学》", 31 August 2009, 北京理工大学出版社 * |
| 贾瑛、许国根、侯立安: "《过渡金属氧化物在环境保护中的应用》", 30 September 2016, 中国环境出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113725558A (en) * | 2021-07-29 | 2021-11-30 | 长沙矿冶研究院有限责任公司 | Modified diaphragm of lithium-sulfur battery and preparation method thereof |
| CN113851696A (en) * | 2021-09-14 | 2021-12-28 | 中山大学 | C4N quantum dot material, preparation method thereof and lithium-sulfur battery diaphragm |
| CN113851696B (en) * | 2021-09-14 | 2024-04-23 | 中山大学 | C4N quantum dot material, preparation method thereof and lithium-sulfur battery diaphragm |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN115504473A (en) * | 2022-09-22 | 2022-12-23 | 南京大学 | MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof |
| CN115504473B (en) * | 2022-09-22 | 2023-08-04 | 南京大学 | MXene-based composite material for improving performance of lithium-sulfur battery diaphragm and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108598390B (en) | Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery | |
| CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN110104630B (en) | Porous carbon composite material for battery diaphragm and preparation method and application thereof | |
| CN112768840A (en) | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN110600707A (en) | High-capacity electrode material for high-nitrogen-doped carbon-coated metal sodium sulfide secondary battery and application of high-capacity electrode material | |
| CN110854379B (en) | Silicon-carbon composite negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery | |
| CN111211273A (en) | Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof | |
| CN103855363A (en) | Long-service-life and high-specific-capacity poly-dopamine-coated hollow sulfur microsphere composite positive electrode material and preparation method thereof | |
| CN111129504A (en) | Preparation method of modified current collector, electrode plate and lithium battery | |
| CN114497549B (en) | Method for electrochemically preparing positive electrode lithium supplement material, lithium supplement material and lithium supplement slurry | |
| CN114122368A (en) | Lithium supplement material, manufacturing method thereof, negative pole piece and battery | |
| CN110061202B (en) | Preparation method of ternary battery positive pole piece and ternary battery | |
| CN113611854B (en) | Prussian blue derived core-shell cubic material, and preparation method and application thereof | |
| CN106684367B (en) | Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof | |
| CN112290162A (en) | Cobalt-doped carbon nanotube composite diaphragm and preparation method thereof | |
| CN109546153B (en) | Preparation method of porous copper current collector, negative electrode and battery | |
| CN111628150A (en) | Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof | |
| CN116799210A (en) | Composite lithium supplementing material and preparation method thereof, lithium supplementing coating and preparation method thereof, and lithium battery | |
| CN115036502A (en) | Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application | |
| CN114824168A (en) | Lithium supplement agent and method for lithium ion battery anode, anode plate, lithium supplement slurry and battery | |
| CN109671932B (en) | Aluminum-carbon composite material, preparation method thereof, negative electrode, secondary battery and electric equipment | |
| CN113161603A (en) | Novel potassium ion battery and preparation method thereof | |
| CN110783553A (en) | Lithium ion battery anode material and preparation method thereof | |
| CN110600672A (en) | Flexible self-supporting three-dimensional porous electrode and preparation method thereof | |
| Zhang et al. | A Li+-conductive Porous Carbon/Polyacrylonitrile/Sulfur Composite for Li-S Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210507 |
|
| RJ01 | Rejection of invention patent application after publication |