WO2020124392A1 - 锂硫电池隔膜及其制备方法、锂硫电池和电子装置 - Google Patents

锂硫电池隔膜及其制备方法、锂硫电池和电子装置 Download PDF

Info

Publication number
WO2020124392A1
WO2020124392A1 PCT/CN2018/121862 CN2018121862W WO2020124392A1 WO 2020124392 A1 WO2020124392 A1 WO 2020124392A1 CN 2018121862 W CN2018121862 W CN 2018121862W WO 2020124392 A1 WO2020124392 A1 WO 2020124392A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
sulfur battery
boron
separator
doped diamond
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.)
Ceased
Application number
PCT/CN2018/121862
Other languages
English (en)
French (fr)
Inventor
唐永炳
王陶
陈波
欧学武
徐阳
孟醒
黄磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Institute of Advanced Technology of CAS
Original Assignee
Shenzhen Institute of Advanced Technology of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Institute of Advanced Technology of CAS
Priority to PCT/CN2018/121862 priority Critical patent/WO2020124392A1/zh
Publication of WO2020124392A1 publication Critical patent/WO2020124392A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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

Definitions

  • the present application relates to the technical field of lithium-sulfur batteries, in particular, to a lithium-sulfur battery separator and a preparation method thereof, a lithium-sulfur battery, and an electronic device.
  • a lithium-sulfur battery is a type of lithium-ion battery that uses sulfur as the battery positive electrode and metallic lithium as the negative electrode.
  • Lithium-sulfur batteries that use sulfur as a cathode material have a theoretical specific capacity of sulfur and a theoretical specific energy of 1675mAh/g and 2600Wh/kg, respectively, which are much higher than other commercial lithium-ion batteries currently in commercial use.
  • elemental sulfur has abundant reserves in the earth, and by-products of petroleum smelting can provide abundant sulfur, so sulfur is cheap and easily available as a raw material. Therefore, lithium-sulfur batteries have outstanding advantages of high specific energy, cheap raw materials, and environmental friendliness, and are expected to become a new generation of high-energy battery systems.
  • lithium-sulfur batteries have good application prospects, there are still some defects: for example, the intermediate products generated by sulfur in the discharge reaction of lithium-sulfur batteries are easily soluble in the electrolyte, so that part of the sulfur cannot be converted into the final product. As a result, sulfur cannot fully release energy, and the mass specific capacity of the lithium-sulfur battery is much lower than the theoretical capacity; on the other hand, the active material is lost, which makes the cycle characteristics of the lithium-sulfur battery poor.
  • the defects of the lithium-sulfur battery such as poor cycle characteristics and large capacity loss, have become the main obstacles restricting its practicality and commercialization.
  • the first object of the present application is to provide a lithium-sulfur battery separator having a high specific mass capacity and excellent cycle characteristics, which can effectively improve at least one of the above technical problems.
  • the second object of the present application is to provide a method for preparing a lithium-sulfur battery separator.
  • the method is simple in process and convenient in operation, and is suitable for industrial mass production.
  • the third object of the present application is to provide a lithium-sulfur battery including the above-mentioned lithium-sulfur battery separator.
  • the fourth object of the present application is to provide an electronic device including the above lithium-sulfur battery.
  • This application provides a lithium-sulfur battery separator, including:
  • a layer of boron-doped diamond composite material is formed on the surface of the diaphragm substrate.
  • the thickness of the boron-doped diamond composite material layer is 20-50 ⁇ m, preferably 22-45 ⁇ m, further preferably 25-40 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent and dispersant;
  • the mass ratio of the boron-doped diamond, binder, conductive agent and dispersant is (2-10): (0.5-2): (0-4): (1-3), preferably (3-8) :(0.8-1.5):(1-3):(1-2).
  • the doping concentration of boron in the boron-doped diamond is 500-5000 ppm, preferably 800-4500 ppm;
  • the boron-doped diamond is boron-doped diamond powder, and the particle size of the boron-doped diamond is 100-200 nm, preferably 120-180 nm.
  • the binder includes any one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene or styrene-butadiene rubber, preferably polyvinylidene fluoride;
  • the dispersant includes any one of N-methylpyrrolidone, N-dimethylamide, N-diethylamide or dimethyl sulfoxide, preferably N-methylpyrrolidone;
  • the conductive agent includes any one or more of conductive carbon black, carbon fiber, carbon nanotube, graphene or nitrogen-doped graphene, preferably conductive carbon black.
  • the thickness of the separator substrate is 12-32 ⁇ m, preferably 12-30 ⁇ m, further preferably 12-20 ⁇ m;
  • the membrane substrate is any one of polyolefin microporous membrane, ceramic membrane or glass fiber membrane;
  • the separator substrate is preferably a polyolefin microporous separator
  • the polyolefin microporous separator includes polyethylene microporous separator and/or polypropylene microporous separator.
  • This application also provides a method for preparing the above lithium-sulfur battery separator, including the following steps:
  • the method for preparing a lithium-sulfur battery separator includes the following steps:
  • mixture A Mixing boron-doped diamond, binder, dispersant and optionally conductive agent to obtain mixture A;
  • the method for preparing a lithium-sulfur battery separator includes the following steps:
  • mixture A Mixing boron-doped diamond, binder, dispersant and optionally conductive agent to obtain mixture A;
  • the supernatant of the suspension made of the mixture A was separated by a separator substrate, and the separator substrate obtained after the separation was dried to obtain a lithium-sulfur battery separator.
  • the coating thickness of the slurry is 20-50 ⁇ m;
  • the suspension made of the mixture A is allowed to stand, and the supernatant after standing is filtered and separated by a diaphragm substrate, the thickness of the diaphragm substrate is 12-20 ⁇ m;
  • drying the separator substrate obtained after separation drying to vacuum drying, drying temperature to 60-90°C, and drying time to 20-30h.
  • the present application also provides a lithium-sulfur battery including the above-mentioned lithium-sulfur battery separator or a lithium-sulfur battery manufactured by using the above-mentioned method for preparing the lithium-sulfur battery separator.
  • the present application also provides an electronic device including the above lithium-sulfur battery.
  • the lithium-sulfur battery separator provided by the present application, its preparation method and the lithium-sulfur battery have the following beneficial effects:
  • the present application provides a lithium-sulfur battery separator including a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate, wherein the boron-doped diamond composite material layer has many active sites on the surface and has conductivity On the one hand, it can absorb the polysulfide of the intermediate product of the lithium-sulfur battery electrode reaction, preventing it from dissolving in the electrolyte, so that the sulfur releases more energy, on the other hand, it can conduct electrons, so that the intermediate product adsorbed on it is further converted Is the final product.
  • the lithium-sulfur battery separator can effectively improve the mass specific capacity and cycle characteristics of the lithium-sulfur battery, and improve the defects of the existing lithium-sulfur battery with poor cycle characteristics and large capacity loss.
  • a typical preparation method is to separate a suspension made by mixing boron-doped diamond, a binder, a dispersant, and optionally a conductive agent through a separator substrate, and then drying the separator substrate obtained after separation
  • a lithium-sulfur battery separator with a boron-doped diamond composite material layer formed on the surface of the separator substrate can form a better adhesion between the boron-doped diamond composite layer and the diaphragm substrate.
  • the present application provides a lithium-sulfur battery including the above-mentioned lithium-sulfur battery separator or a lithium-sulfur battery separator produced by using the above-mentioned method for preparing the lithium-sulfur battery separator.
  • the lithium-sulfur battery containing it also has the same advantages, so that the mass-specific capacity and cycle characteristics of the lithium-sulfur battery are effectively improved, and the electrochemical performance of the lithium-sulfur battery is improved. performance.
  • the present application provides an electronic device including the above lithium-sulfur battery.
  • the same effect can also be obtained in electronic devices including the above-mentioned lithium-sulfur battery.
  • FIG. 1 is a process flow diagram of a method for preparing a lithium-sulfur battery separator provided in this application;
  • Example 2 is a lithium-sulfur battery separator provided in Example 3 of this application;
  • FIG. 3 is a lithium-sulfur battery separator provided in Example 11 of the present application.
  • a lithium-sulfur battery separator including:
  • the boron-doped diamond composite material layer is formed on the surface of the diaphragm substrate.
  • the type of the separator substrate is not specifically limited, and the separator substrate material commonly used in the art may be selected, such as polyolefin, polyimide, or glass fiber.
  • the boron-doped diamond composite material layer in this application mainly refers to a layered structure formed by the composite of boron-doped diamond and other materials.
  • boron-doped diamond refers to doping a certain amount of boron in diamond. The doping of boron will change the thermal, chemical, electrical and mechanical properties of diamond.
  • Other materials mainly refer to substances that can bond boron-doped diamond to the surface of the diaphragm substrate to form a coating.
  • other materials may include substances that promote the conductive properties of the coating, such as conductive materials commonly used in the art.
  • the surface of the boron-doped diamond composite layer has many active sites and conductivity, on the one hand, it can absorb the polysulfide of the intermediate product of the lithium-sulfur battery electrode reaction and prevent it from dissolving in the electrolyte , So that sulfur releases more energy, on the other hand, it can conduct electrons, so that the intermediate product adsorbed on it is further converted into the final product.
  • the boron-doped diamond composite material layer is provided on the surface of the separator substrate and applied to the lithium-sulfur battery, which can effectively solve the problem of the intermediate product dissolving in the electrolyte and improve the mass specific capacity and cycle characteristics of the lithium-sulfur battery.
  • the doping amount of boron in boron-doped diamond is not specifically limited, and can be set according to actual needs.
  • the preparation method of boron-doped diamond is not specifically limited, and preparation methods commonly used in the art, such as chemical vapor deposition, etc. may be used.
  • the thickness of the boron-doped diamond composite layer is 20-50 ⁇ m, preferably 22-45 ⁇ m, further preferably 25-40 ⁇ m, and the typical but non-limiting thickness of the boron-doped diamond composite layer It is 20 ⁇ m, 22 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 44 ⁇ m, 45 ⁇ m, 48 ⁇ m or 50 ⁇ m.
  • the thickness of the boron-doped diamond composite layer should not be too thin. If the thickness is too thin, the amount of polysulfide adsorbed on the intermediate product will be reduced, and the capacity will not be greatly increased, but the thickness of the boron-doped diamond composite layer should not be too thick, too thick Will reduce the transmission efficiency of lithium ions. Therefore, the thickness of the boron-doped diamond composite material layer needs to be within an appropriate range.
  • the specific composition of the boron-doped diamond composite layer can be set according to actual needs.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent, and dispersant;
  • the binder can adhere components such as boron-doped diamond and/or conductive agent together to form a coating on the surface of the separator substrate.
  • the addition of conductive agent can enhance the conductive properties of the boron-doped diamond composite layer.
  • the addition of the conductive agent is not necessary, and can be selectively added according to actual needs.
  • the dispersant is mainly to dissolve the boron-doped diamond, conductive agent, binder and other components to form a slurry, thereby facilitating the coating on the surface of the diaphragm substrate.
  • the ratio between boron-doped diamond, binder, conductive agent and dispersant will directly affect the performance of boron-doped diamond composite layer.
  • the mass ratio of boron-doped diamond, binder, conductive agent and dispersant is (2-10):(0.5-2):(0-4):(1-3 ), preferably (3-8): (0.8-1.5): (1-3): (1-2); mass ratio of typical but non-limiting boron-doped diamond, binder, conductive agent and dispersant 2:0.5:4:1, 5:0.8:2:1, 6:1:2:1, 6:1:3:1.5, 7:1:2:2, 8:2:0:1.5, 8 :1:1:1, 9:2:0:2, 9:2:1:2, 9:1:3:2, etc.
  • the formed boron-doped diamond composite material layer has good ion transmission and electron conductivity, and at the same time can be Good adhesion is formed on the surface of the substrate.
  • the doping concentration of boron in boron-doped diamond is 500-5000 ppm, preferably 800-4500 ppm; typical but non-limiting boron doping concentration is, for example, 500 ppm, 800 ppm, 1000 ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm or 5000ppm.
  • the doping concentration of boron in boron-doped diamond directly affects the electrical conductivity of the boron-doped diamond composite layer.
  • the boron doping concentration is higher, the corresponding boron-doped diamond composite material layer has higher conductivity.
  • the boron-doped diamond powder is boron-doped diamond powder
  • the particle size of the boron-doped diamond powder is 100-200 nm, preferably 120-180 nm.
  • Typical but non-limiting particle sizes of boron-doped diamond powder are 100 nm, 120 nm, 140 nm, 150 nm, 160 nm, 180 nm or 200 nm.
  • the particle size of the boron-doped diamond powder should be controlled within a certain range.
  • the preparation method of the boron-doped diamond powder includes the following steps:
  • the ball milling materials include stainless steel balls, agate balls or tungsten carbide One or more of the balls, the ball grinding time is 3-7h;
  • the difference in thermal expansion coefficient between copper foil and diamond is used, so that the deposited film will naturally fall off from the substrate, without using hydrofluoric acid to corrode the substrate, and the production process is safe.
  • the binder includes polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene or styrene-butadiene rubber, preferably polyvinylidene fluoride;
  • the dispersant includes any one of N-methylpyrrolidone, N-dimethylamide, N-diethylamide, or dimethyl sulfoxide;
  • the conductive agent includes any one or more of conductive carbon black, carbon fiber, carbon nanotube, graphene or nitrogen-doped graphene, preferably conductive carbon black.
  • each component has good compatibility, which is beneficial to improve the electrochemical performance of the formed boron-doped diamond composite layer.
  • the thickness of the diaphragm substrate is 12-32 ⁇ m, preferably 12-30 ⁇ m, further preferably 12-20 ⁇ m, and the thickness of a typical but non-limiting line of the diaphragm substrate is 12 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 28 ⁇ m, 30 ⁇ m or 32 ⁇ m.
  • the thickness of the separator substrate should not be too thick, otherwise it will cause a large internal resistance of the battery, and the thickness of the separator substrate should not be too thin, otherwise the mechanical properties will be affected, which is easy to be punctured by large particles, pole burrs and dendrites, resulting in The battery safety factor is reduced. Therefore, the thickness of the diaphragm substrate needs to be controlled within an appropriate range.
  • the separator substrate has a direct influence on the final performance of the lithium-sulfur battery separator.
  • the separator substrate is a polyolefin microporous separator. Because the polyolefin microporous separator has excellent mechanical properties, chemical stability, and relatively low cost, it is selected as the separator substrate.
  • the material of the diaphragm substrate should have good insulation, film-forming performance, mechanical properties and easy addition.
  • the separator substrate is any one of polyolefin microporous separator, ceramic separator or glass fiber separator.
  • the separator substrate is a polyolefin microporous separator
  • the polyolefin microporous separator is preferably a polyethylene microporous separator and/or a polypropylene microporous separator.
  • Polyethylene microporous membranes and polypropylene microporous membranes are the main categories of polyolefin microporous membranes.
  • the polyolefin microporous separator may be one of polyethylene microporous separator or polypropylene microporous separator, or may be a polyethylene microporous separator and a polypropylene microporous separator to form a multilayer composite separator substrate.
  • a method for preparing the above-mentioned lithium-sulfur battery separator including the following steps:
  • the boron-doped diamond composite material layer is formed on the separator substrate to obtain a lithium-sulfur battery separator.
  • the preparation method has simple process and convenient operation, and is suitable for industrial production and large-scale industrial use.
  • a method for preparing a lithium-sulfur battery separator includes the following steps:
  • mixture A Mixing boron-doped diamond, binder, dispersant and optionally conductive agent to obtain mixture A;
  • the method for preparing a lithium-sulfur battery separator includes the following steps:
  • mixture A Mixing boron-doped diamond, binder, dispersant and optionally conductive agent to obtain mixture A;
  • the supernatant of the suspension made of the mixture A was separated by a separator substrate, and the separator substrate obtained after the separation was dried to obtain a lithium-sulfur battery separator.
  • the mixture A is provided on the separator substrate, different methods can be used for processing, one of which is to directly apply the mixture A on the separator substrate, and the other method is to apply the mixture A
  • the prepared suspension is separated by a membrane base material.
  • the separation is common filtration or suction filtration in the art, and the membrane base material plays the role of filter paper in this separation process.
  • Adopting the above-mentioned preparation method of the present application can form a better adhesion between the boron-doped diamond composite material layer and the separator substrate.
  • the slurry coating thickness is 20-50 ⁇ m; the typical but non-limiting slurry coating thickness is 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m or 50 ⁇ m.
  • the thickness of the boron-doped diamond composite material layer finally formed on the surface of the separator substrate is within a suitable thickness range.
  • the suspension made of the mixture A is allowed to stand, and the supernatant after standing is filtered and separated by a diaphragm substrate, the thickness of the diaphragm substrate is 12-20 ⁇ m; typical but not The thickness of the restrictive separator substrate is 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 18 ⁇ m or 20 ⁇ m.
  • the resistance during the filtration process can be controlled by controlling the thickness of the membrane substrate.
  • the drying is vacuum drying, the drying temperature is 60-90°C, and the drying time is 20-30h.
  • Typical but non-limiting drying temperatures are 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, typical but non-limiting drying times are 20h, 22h, 24h, 25h, 26h, 28h Or 30h.
  • the slurry on the separator substrate can form a boron-doped diamond composite material layer in a short time, and the formed boron-doped diamond composite material layer is not easy to crack.
  • FIG. 1 a method for preparing a lithium-sulfur battery separator, the schematic process diagram is shown in FIG. 1 and includes the following steps:
  • mixture A After mixing boron-doped diamond, binder and optionally conductive agent, then add dispersant to obtain mixture A;
  • the mixture A is ground, and the slurry formed after the grinding is coated on one side of the separator substrate to obtain a separator to be treated, wherein the thickness of the separator substrate is 12-32 ⁇ m, and the coating thickness of the slurry is 20-50 ⁇ m ;
  • the separator to be treated is vacuum dried, the vacuum drying temperature is 60-90°C, and the vacuum drying time is 20-30h to obtain a lithium-sulfur battery separator.
  • the preparation method of the lithium-sulfur battery separator includes the following steps:
  • mixture A After mixing boron-doped diamond, binder and optionally conductive agent, then add dispersant to obtain mixture A;
  • the mixture A is subjected to ultrasound, and the suspension obtained after the ultrasound is allowed to stand, and then the supernatant is taken, and suction filtration is performed using the membrane substrate as filter paper to obtain a membrane to be treated, wherein the thickness of the membrane substrate is 12-20 ⁇ m;
  • the separator to be treated is vacuum dried, the vacuum drying temperature is 60-90°C, and the vacuum drying time is 20-30h to obtain a lithium-sulfur battery separator.
  • the prepared lithium-sulfur battery separator has excellent electrochemical performance and excellent processability.
  • a lithium-sulfur battery including the above-mentioned lithium-sulfur battery separator or a lithium-sulfur battery manufactured by using the above-mentioned method for preparing the lithium-sulfur battery separator.
  • the lithium-sulfur battery containing it also has the same advantages, so that the mass-specific capacity and cycle characteristics of the lithium-sulfur battery are effectively improved, and the electrochemical performance of the lithium-sulfur battery is improved. performance.
  • an electronic device an electric tool, an electric vehicle, or an electric power storage system including the above lithium-sulfur battery.
  • the same effect can be obtained in electronic devices, power tools, electric vehicles, and power storage systems using the lithium ion battery of the embodiment of the present application.
  • the electronic device is an electronic device that performs various functions (for example, playing music) using a lithium ion battery as a power source for operation.
  • a power tool is a power tool that uses a lithium ion battery as a driving power source to move parts (for example, a drill).
  • the electric vehicle is an electric vehicle that runs on a lithium ion battery as a driving power source, and may be an automobile (including a hybrid vehicle) equipped with other driving sources in addition to the lithium ion battery.
  • the power storage system is a power storage system that uses a lithium ion battery as a power storage source. For example, in a home power storage system, power is stored in a lithium ion battery used as a power storage source, and the power stored in the lithium ion battery is consumed as necessary to be able to use various devices such as home electronic products.
  • a lithium-sulfur battery separator provided in this embodiment includes a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate;
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 12 ⁇ m;
  • the thickness of the boron-doped diamond composite layer is 30 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder and dispersant, and the quality of boron-doped diamond, binder and dispersant The ratio is 5:0.8:1;
  • the particle size of boron-doped diamond is 100nm, and the doping concentration of boron in boron-doped diamond is 500ppm;
  • the binder is polyvinylidene fluoride, and the dispersant is N-dimethylamide.
  • the lithium-sulfur battery separator provided in this embodiment includes a conductive agent in addition to the slurry used to form the boron-doped diamond composite layer, the conductive agent is a carbon nanotube, and the boron-doped diamond, binder, conductive agent and dispersant The mass ratio is 5:0.8:1:1, and the remaining components are the same as in Example 1.
  • a lithium-sulfur battery separator provided in this embodiment includes a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate;
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 18 ⁇ m;
  • the thickness of the boron-doped diamond composite layer is 20 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent and dispersant, boron-doped diamond, binder, conductive
  • the mass ratio of agent and dispersant is 8:1:1:1;
  • the particle size of boron-doped diamond is 120nm, and the doping concentration of boron in boron-doped diamond is 1000ppm;
  • the binder is polyvinylidene fluoride
  • the conductive agent is conductive carbon black
  • the dispersant is N-methylpyrrolidone
  • the lithium-sulfur battery separator provided in this embodiment is the same as that in Embodiment 3 except that the thickness of the boron-doped diamond composite material layer is 45 ⁇ m.
  • the lithium-sulfur battery separator provided in this embodiment is the same as that in Embodiment 3 except that the thickness of the boron-doped diamond composite material layer is 15 ⁇ m.
  • the lithium-sulfur battery separator provided in this embodiment is the same as that in Embodiment 3 except that the doping concentration of boron in boron-doped diamond is 5000 ppm.
  • a lithium-sulfur battery separator provided in this embodiment includes a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate;
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 30 ⁇ m;
  • the thickness of the boron-doped diamond composite layer is 50 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent and dispersant, boron-doped diamond, binder, conductive
  • the mass ratio of the agent and the dispersant is 6:3:1:2;
  • the particle size of boron-doped diamond is 150nm, and the doping concentration of boron in boron-doped diamond is 2000ppm;
  • the binder is polyvinylidene fluoride
  • the conductive agent is conductive carbon black
  • the dispersant is N-methylpyrrolidone
  • the lithium-sulfur battery separator provided in this embodiment is the same as that in Embodiment 7 except that the particle size of the boron-doped diamond is 300 nm.
  • a lithium-sulfur battery separator provided in this embodiment includes a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate;
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 24 ⁇ m;
  • the thickness of the boron-doped diamond composite layer is 40 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent and dispersant, boron-doped diamond, binder, conductive
  • the mass ratio of the agent and the dispersant is 4:1:2:1.5;
  • the particle size of boron-doped diamond is 200nm, and the doping concentration of boron in boron-doped diamond is 3000ppm;
  • the binder is polyvinyl alcohol
  • the conductive agent is graphene
  • the dispersing agent is N-methylpyrrolidone
  • the preparation method of the lithium-sulfur battery separator provided in Examples 1-9 includes the following steps:
  • mixture A After mixing the above amount of boron-doped diamond, binder and optional conductive agent, then add a dispersant to obtain mixture A;
  • the coating thickness of the slurry is 30 ⁇ m
  • the separator to be treated is vacuum-dried at a vacuum drying temperature of 80° C. and a vacuum drying time of 24 hours to obtain a lithium-sulfur battery separator.
  • composition parameters of a lithium-sulfur battery separator provided in this embodiment are the same as those in Embodiment 3.
  • mixture A After mixing the formulated amount of boron-doped diamond, binder and optional conductive agent, then add a dispersant to obtain mixture A;
  • the mixture A was sonicated, and the suspension obtained after the sonicating was allowed to stand for 20 hours, and then the supernatant was taken, and the membrane was used as filter paper for suction filtration to obtain a membrane to be treated, in which the ultrasonic time was 12 hours;
  • the separator to be treated is vacuum-dried at a vacuum drying temperature of 80° C. and a vacuum drying time of 24 hours to obtain a lithium-sulfur battery separator.
  • the lithium-sulfur battery separator provided in this embodiment has the same specific composition parameters as Embodiment 3 except that the thickness of the separator substrate is 24 ⁇ m.
  • the preparation method of the lithium-sulfur battery separator provided in this embodiment is the same as that in Embodiment 10.
  • a lithium-sulfur battery separator provided in this embodiment includes a separator substrate and a boron-doped diamond composite material layer formed on the surface of the separator substrate;
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 12 ⁇ m;
  • the thickness of the boron-doped diamond composite layer is 25 ⁇ m.
  • the slurry used to form the boron-doped diamond composite layer includes the following components: boron-doped diamond, binder, conductive agent and dispersant, boron-doped diamond, binder, conductive
  • the mass ratio of agent and dispersant is 4:1:1:1.5;
  • the particle size of boron-doped diamond is 200nm, and the doping concentration of boron in boron-doped diamond is 3000ppm;
  • the binder is polyvinyl alcohol
  • the conductive agent is graphene
  • the dispersing agent is N-methylpyrrolidone
  • mixture A After mixing the formulated amount of boron-doped diamond, binder and optional conductive agent, then add a dispersant to obtain mixture A;
  • the mixture A was subjected to ultrasound, and the suspension obtained after the ultrasound was allowed to stand for 24 hours, and then the supernatant was taken, and suction filtration was performed using the membrane substrate as filter paper to obtain a membrane to be treated, in which the ultrasound time was 10 hours;
  • the separator to be treated is vacuum-dried at a vacuum drying temperature of 70° C. and a vacuum drying time of 30 h to obtain a lithium-sulfur battery separator.
  • a lithium-sulfur battery separator provided in this embodiment except that no conductive agent is added to the slurry used in the boron-doped diamond composite material layer, the remaining specific composition parameters are the same as those in embodiment 12.
  • the lithium-sulfur battery separator provided in this embodiment, except that the mass ratio of boron-doped diamond, binder, conductive agent and dispersant in the boron-doped diamond composite material layer is 10:0.4:1:1.5, the rest is the same as that of embodiment 12. the same.
  • a lithium-sulfur battery separator provided in this embodiment, except that the mass ratio of boron-doped diamond, binder, conductive agent and dispersant in the boron-doped diamond composite layer is 1:1:1:1.5, the rest is the same as that in embodiment 12. the same.
  • a lithium-sulfur battery separator provided in this embodiment, except that the mass ratio of boron-doped diamond, binder, conductive agent and dispersant in the boron-doped diamond composite material layer is 4:1:5:1.5, the rest is the same as that in embodiment 12. the same.
  • This comparative example provides a lithium-sulfur battery separator, which is a comparative experiment of Example 3.
  • the lithium-sulfur battery separator includes a separator substrate and a diamond composite layer formed on the surface of the separator substrate.
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 18 ⁇ m;
  • the thickness of the diamond composite layer is 30 ⁇ m.
  • the slurry used to form the diamond composite layer includes the following components: nano-diamond powder, binder, conductive agent and dispersant, diamond powder, binder, conductive agent and dispersant The mass ratio is 8:1:1:1;
  • the binder is polyvinylidene fluoride
  • the conductive agent is conductive carbon black
  • the dispersant is N-methylpyrrolidone
  • the preparation method of the lithium-sulfur battery separator provided in this comparative example is the same as that in Example 3.
  • This comparative example provides a lithium-sulfur battery separator, which is a comparative experiment of Example 12.
  • the lithium-sulfur battery separator includes a separator substrate and a diamond composite layer formed on the surface of the separator substrate.
  • the diaphragm substrate is a polypropylene microporous diaphragm, and the thickness of the diaphragm substrate is 12 ⁇ m;
  • the thickness of the diamond composite layer is 25 ⁇ m, and the slurry used to form the diamond composite layer includes the following components: nano-diamond powder, binder, conductive agent and dispersant, diamond powder, binder, conductive agent and dispersant
  • the mass ratio is 4:1:1:1.5;
  • the binder is polyvinyl alcohol
  • the conductive agent is graphene
  • the dispersing agent is N-methylpyrrolidone
  • the preparation method of the lithium-sulfur battery separator provided in this comparative example is the same as that in Example 12.
  • the mass specific capacity and cycle characteristics (0.5C rate) of the lithium-sulfur batteries corresponding to the examples and comparative examples were measured, and the pure separator substrate was used as the control group (no composite layer was formed on the surface), and the control group 1 was polyethylene Microporous membrane, the control group 2 is polypropylene microporous membrane, as shown in Table 1.
  • Example 2 is a comparative experiment of Example 1.
  • the slurry used to form the boron-doped diamond composite material layer of Example 2 further includes a conductive agent. It can be seen from the data in Table 1 that the addition of the conductive agent is beneficial to improve the mass specific capacity and cycle characteristics of lithium-sulfur batteries, but the overall improvement is not large.
  • Examples 4-6 are comparative experiments of Example 3. Compared with Example 3, the thickness of the boron-doped diamond composite material layer in Examples 4 and 5 is different. The doping of boron in the boron-doped diamond in Example 6 The impurity concentration is different. Comparing the data in Table 1, it can be seen that the greater the thickness of the boron-doped diamond composite layer is beneficial to the improvement of the cycle characteristics of the lithium-sulfur battery, but the thickness of the boron-doped diamond composite layer should not be too large, as it will reduce the transmission efficiency of lithium ions.
  • the thickness of the boron-doped diamond composite material layer is too thin, the adsorption amount of the intermediate product polysulfide is obviously reduced, which is not conducive to the improvement of the mass specific capacity of the lithium-sulfur battery.
  • the high boron-doped concentration is conducive to improving the mass specific capacity of lithium-sulfur batteries. This is mainly because the higher the boron-doped concentration, the better the conductivity of the boron-doped diamond composite layer. Further conversion of sulfides.
  • Example 8 is a control experiment of Example 7. The difference between the two is the particle size of boron-doped diamond. It can be seen from the data in the table that at a certain scale, the grain size of boron-doped diamond has little effect on the performance of lithium-sulfur batteries.
  • Comparative Example 1 is a comparative experiment of Example 3
  • Comparative Example 2 is a comparative experiment of Example 12. Both sets of comparative examples investigated the effect of whether the diamond composite layer on the surface of the separator substrate was doped with boron on the mass specific capacity and cycle performance of lithium-sulfur batteries. It can be seen from the data in the table that when the diamond composite layer is not doped with boron, the mass specific capacity and cycle performance of the lithium-sulfur battery are significantly reduced, which shows whether the boron-doped diamond composite layer has a mass specific capacity for lithium-sulfur battery and Cycling performance has a direct impact.
  • FIG. 1 of the present application provides two preparation methods of a lithium-sulfur battery separator, and these two preparation methods are mainly reflected in the difference in the treatment method of the mixture A.
  • Figures 2 and 3 are lithium-sulfur battery separators made by two different preparation methods. It can be seen from the data in Table 1 and FIGS. 2-3 that the two preparation methods for the lithium-sulfur battery separator shown in FIG. 1 are both feasible for the preparation of the lithium-sulfur battery separator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

本申请提供了一种锂硫电池隔膜及其制备方法、锂硫电池和电子装置，涉及锂硫电池技术领域。该锂硫电池隔膜包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层，其中，掺硼金刚石复合材料层表面活性位点多且具有导电性，一方面能够吸附锂硫电池电极反应的中间产物多硫化物，阻止其溶于电解液，从而使得硫释放更多的能量，另一方面能够导通电子，使得吸附其上的中间产物进一步转化为终产物，故该锂硫电池隔膜可有效提高锂硫电池的质量比容量和循环特性。本申请还提供了锂硫电池隔膜的制备方法，该方法工艺简单，操作便利，适合工业化生产。本申请还提供了包含上述锂硫电池隔膜的锂硫电池，该锂硫电池具有较高的质量比容量和优良的循环特性。

Description

锂硫电池隔膜及其制备方法、锂硫电池和电子装置 技术领域
本申请涉及锂硫电池技术领域，具体而言，涉及一种锂硫电池隔膜及其制备方法、锂硫电池和电子装置。
背景技术
锂硫电池是锂离子电池的一种，其是以硫元素作为电池正极，金属锂作为负极的一种电池。利用硫作为正极材料的锂硫电池，硫的理论比容量和电池理论比能量分别达到了1675mAh/g和2600Wh/kg，远高于目前商业化的其他锂离子电池。且单质硫在地球中储量丰富，并且石油冶炼的副产物就能提供丰富的硫磺，因此硫作为原料廉价且易得。故锂硫电池具有突出的高比能量优势和原料廉价、环境友好等优点，有望成为新一代高能电池体系。
尽管锂硫电池具有良好的应用前景，但目前还存在着一些缺陷：例如，锂硫电池在放电反应中硫生成的中间产物易溶于电解液中，使得部分硫无法转化为最终产物，一方面导致硫无法充分释放能量，导致锂硫电池的质量比容量远远低于理论容量；另一方面导致活性物质损失，使得锂硫电池的循环特性较差。锂硫电池上述循环特性差、容量损失大的缺陷已经成为制约其实用化、商用化的主要障碍。
有鉴于此，特提出本申请以解决上述技术问题中的至少一个。
发明内容
本申请的第一个目的在于提供一种锂硫电池隔膜，该锂硫电池隔膜具有较高的质量比容量和优良的循环特性，可有效改善上述技术问题中的至少一个。
本申请的第二个目的在于提供一种锂硫电池隔膜的制备方法，该方法工艺简单，操作便利，适合工业上大规模生产。
本申请的第三个目的在于提供一种锂硫电池，包括上述锂硫电池隔膜。
本申请的第四个目的在于提供一种包含上述锂硫电池的电子装置。
为了实现本申请的上述目的，特采用以下技术方案：
本申请提供了一种锂硫电池隔膜，包括：
隔膜基材；和，
掺硼金刚石复合材料层，形成在所述隔膜基材的表面。
进一步的，在本申请技术方案的基础之上，所述掺硼金刚石复合材料层的厚度为20-50μm，优选为22-45μm，进一步优选为25-40μm。
进一步的，在本申请技术方案的基础之上，形成所述掺硼金刚石复合材料层的所用浆 料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂；
所述掺硼金刚石、粘结剂、导电剂和分散剂的质量比为(2-10)：(0.5-2):(0-4):(1-3)，优选为(3-8):(0.8-1.5):(1-3):(1-2)。
进一步的，在本申请技术方案的基础之上，所述掺硼金刚石中硼的掺杂浓度为500-5000ppm，优选为800-4500ppm；
和/或，所述掺硼金刚石为掺硼金刚石粉，所述掺硼金刚石的粒度为100-200nm，优选为120-180nm。
进一步的，在本申请技术方案的基础之上，所述粘结剂包括聚偏氟乙烯、聚乙烯醇、聚四氟乙烯或丁苯橡胶中的任意一种，优选为聚偏氟乙烯；
和/或，所述分散剂包括N-甲基吡咯烷酮、N-二甲基酰胺、N-二乙基酰胺或二甲亚砜中的任意一种，优选为N-甲基吡咯烷酮；
和/或，所述导电剂包括导电炭黑、碳纤维、碳纳米管、石墨烯或氮掺杂石墨烯中的任意一种或几种，优选为导电炭黑。
进一步的，在本申请技术方案的基础之上，所述隔膜基材的厚度为12-32μm，优选为12-30μm，进一步优选为12-20μm；
优选地，所述隔膜基材为聚烯烃微孔隔膜、陶瓷隔膜或玻璃纤维隔膜中的任意一种；
优选地，所述隔膜基材优选为聚烯烃微孔隔膜，所述聚烯烃微孔隔膜包括聚乙烯微孔隔膜和/或聚丙烯微孔隔膜。
本申请还提供了上述锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石复合材料层形成于隔膜基材上，得到锂硫电池隔膜；
优选地，所述锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
将混合物A制成的浆料涂覆在隔膜基材上，干燥，得到锂硫电池隔膜；
优选地，所述锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
将混合物A制成的悬浮液的上清液通过隔膜基材进行分离，对分离后得到的隔膜基材进行干燥，得到锂硫电池隔膜。
进一步的，在本申请技术方案的基础之上，将混合物A制成的浆料涂覆在隔膜基材上时，浆料涂覆厚度为20-50μm；
和/或，将混合物A制成的悬浮液静置，静置后的上清液通过隔膜基材进行过滤分离，隔膜基材的厚度为12-20μm；
和/或，将混合物A制成的浆料涂覆在隔膜基材上进行干燥，干燥为真空干燥，干燥温 度为60-90℃，干燥时间为20-30h；
和/或，对分离后得到的隔膜基材进行干燥，干燥为真空干燥，干燥温度为60-90℃，干燥时间为20-30h。
本申请还提供了一种锂硫电池，包含上述锂硫电池隔膜或采用上述锂硫电池隔膜的制备方法制得的锂硫电池。
本申请还提供了包含上述锂硫电池的电子装置。
与现有技术相比，本申请提供的锂硫电池隔膜及其制备方法和锂硫电池具有以下有益效果：
(1)本申请提供了一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层，其中，掺硼金刚石复合材料层表面活性位点多且具有导电性，一方面能够吸附锂硫电池电极反应的中间产物多硫化物，阻止其溶于电解液，从而使得硫释放更多的能量，另一方面能够导通电子，使得吸附其上的中间产物进一步转化为终产物。该锂硫电池隔膜可有效提高锂硫电池的质量比容量和循环特性，改善现有锂硫电池循环特性差、容量损失大的缺陷。
(2)本申请提供的锂硫电池隔膜的制备方法，工艺简单、稳定，适合于工业化生产；
一种典型制备方法，是通过将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合制成的悬浮液通过隔膜基材进行分离，然后分离后得到的隔膜基材进行干燥，得到隔膜基材表面形成有掺硼金刚石复合材料层的锂硫电池隔膜。该方法可使得掺硼金刚石复合材料层与隔膜基材之间形成较好的粘附力。
(3)本申请提供了一种锂硫电池，包含上述锂硫电池隔膜或者采用上述锂硫电池隔膜的制备方法制得的锂硫电池隔膜。鉴于上述锂硫电池隔膜所具有的优势，使得包含其的锂硫电池也具有同样的优势，从而使得该锂硫电池的质量比容量和循环特性得到有效提高，进而提升的锂硫电池的电化学性能。
(4)本申请提供了包含上述锂硫电池的电子装置。鉴于上述锂硫电池所具有的优势，在包含上述锂硫电池的电子装置也可以获得相同的效果。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请提供的锂硫电池隔膜的制备方法的工艺流程图；
图2为本申请实施例3提供的锂硫电池隔膜；
图3为本申请实施例11提供的锂硫电池隔膜。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
根据本申请的第一个方面，提供了一种锂硫电池隔膜，包括：
隔膜基材；和，
掺硼金刚石复合材料层，形成在隔膜基材的表面。
在本申请中隔膜基材的种类不作具体限定，可选择本领域常用的隔膜基材材质即可，例如聚烯烃、聚酰亚胺或者玻璃纤维。
本申请中的掺硼金刚石复合材料层主要是指由掺硼金刚石与其他材料复合形成的层状结构。其中，掺硼金刚石是指在金刚石中掺杂一定量的硼，硼的掺杂会改变金刚石的热学、化学、电学及力学等性质。其他材料主要是指能够将掺硼金刚石粘合在隔膜基体表面从而形成涂层的物质，另外，其他材料还可包括促进涂层导电性质的物质，例如本领域常用的导电材料等。
由于掺硼金刚石表面存在悬键，且这类悬键对多硫化物有很好的吸附作用。鉴于掺硼金刚石本身所具有的上述特性，使得掺硼金刚石复合材料层表面活性位点多且具有导电性，一方面能够吸附锂硫电池电极反应的中间产物多硫化物，阻止其溶于电解液，从而使得硫释放更多的能量，另一方面能够导通电子，使得吸附其上的中间产物进一步转化为终产物。将该掺硼金刚石复合材料层设置于隔膜基材表面并应用于锂硫电池上，可有效解决中间产物溶于电解液的问题，提高了锂硫电池的质量比容量和循环特性。
对于掺硼金刚石中硼的掺杂量不作具体限定，可根据实际需要进行设定。对于掺硼金刚石的制备方法也不作具体限定，可采用本领域常用的制备方法，例如化学气相沉积法等。
作为本申请的一种可选实施方式，掺硼金刚石复合材料层的厚度为20-50μm，优选为22-45μm，进一步优选为25-40μm，掺硼金刚石复合材料层典型但非限制性的厚度为20μm、22μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、44μm、45μm、48μm或50μm。
掺硼金刚石复合材料层的厚度不宜过薄，若厚度太薄，对于中间产物多硫化物的吸附量就会减少，容量提升不大，但掺硼金刚石复合材料层的厚度不宜过厚，过厚会降低锂离子的传输效率。故掺硼金刚石复合材料层的厚度需要在适宜的范围内。
对于掺硼金刚石复合材料层的具体组成可根据实际需要进行设定。作为本申请的一种 可选实施方式，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂；
粘结剂可以将掺硼金刚石和/或导电剂等组分粘附在一起，从而在隔膜基材表面形成涂层。
导电剂的加入可以增强掺硼金刚石复合材料层的导电性能。但需要说明的是，导电剂的加入不是必需的，可根据实际需要选择性添加。
分散剂主要是将掺硼金刚石、导电剂、粘结剂等组分溶解形成浆料，从而有利于在在隔膜基材表面的涂覆。
掺硼金刚石、粘结剂、导电剂和分散剂之间的配比会直接影响掺硼金刚石复合材料层的性能。作为本申请的一种可选实施方式，掺硼金刚石、粘结剂、导电剂和分散剂的质量比为(2-10):(0.5-2):(0-4):(1-3)，优选为(3-8):(0.8-1.5):(1-3):(1-2)；典型但非限制性的掺硼金刚石、粘结剂、导电剂和分散剂的质量比为2:0.5:4:1、5:0.8:2:1、6:1:2:1、6:1:3:1.5，7:1:2:2、8:2:0:1.5、8:1:1:1、9:2:0:2、9:2:1:2、9:1:3:2等。
通过对掺硼金刚石、粘结剂、导电剂和分散剂之间的质量比的限定，使得所形成的掺硼金刚石复合材料层既具有良好的离子传输性和电子导电性，同时又能与隔膜基材表面形成较好的粘结性。
作为本申请的一种可选实施方式，掺硼金刚石中硼的掺杂浓度为500-5000ppm，优选为800-4500ppm；典型但非限制性的硼的掺杂浓度例如为500ppm、800ppm、1000ppm、1500ppm、2000ppm、2500ppm、3000ppm、3500ppm、4000ppm、4500ppm或5000ppm。
掺硼金刚石中硼的掺杂浓度直接影响到掺硼金刚石复合材料层的导电性能。硼的掺杂浓度较高时，相应的掺硼金刚石复合材料层的导电性能也较高。
作为本申请的一种可选实施方式，掺硼金刚石为掺硼金刚石粉，掺硼金刚石粉的粒度为100-200nm，优选为120-180nm。典型但非限制性的掺硼金刚石粉的粒度为100nm、120nm、140nm、150nm、160nm、180nm或200nm。
掺硼金刚石粉的粒度过大，容易造成比表面积低，吸附能力不强，而掺硼金刚石粉的粒度过小，则容易造成掺硼金刚石粉进入隔膜基材的微孔内部，无法发挥吸附作用，甚至会在使用一段时间后到达隔膜基材的负极侧，导致自放电加强甚至短路。故掺硼金刚石粉的粒度应该控制在一定范围内。
掺硼金刚石粉的制备方法较多，可采用热丝化学气相沉积法。作为本申请的一种可选实施方式，掺硼金刚石粉的制备方法，包括以下步骤：
(a)将铜箔用酒精超声清洗20-30min干燥备用；
(b)将清洗后的铜箔置于纳米金刚石粉悬浮液中超声20-40min；
(c)将超声后的铜箔放入热丝化学气相沉积设备中，对热丝进行碳化，向设备中通入氢气、甲烷、硼烷和任选的惰性气体，甲烷气体流量占总气体流量的2-8％，调节真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h，在铜箔表面形成一层厚度为2-12μm的掺硼金刚石薄膜；
(d)真空下随炉冷却，取出铜箔，掺硼金刚石薄膜从铜箔上自然脱落，将脱落的掺硼金刚石薄膜碎片装入球磨设备中球磨，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种，球磨时间为3-7h；
(e)将球磨后的掺硼金刚石粉先在质量分数为3-8％的稀硫酸中清洗5-15min，然后在温度50-70℃、体积比8-10:1的浓硫酸和浓硝酸的混合酸液中浸泡20-40min，再将所得掺硼金刚石粉分散在水中，超声6-12小时，蒸馏后得到掺硼金刚石粉。
该制备方法中，采用铜箔与金刚石之间的热膨胀系数差异，使得沉积完毕后的薄膜自然的从基体上脱落，无需采用氢氟酸腐蚀基体，生产过程安全。
作为本申请的一种可选实施方式，粘结剂包括聚偏氟乙烯、聚乙烯醇、聚四氟乙烯或丁苯橡胶，优选为聚偏氟乙烯；
和/或，分散剂包括N-甲基吡咯烷酮、N-二甲基酰胺、N-二乙基酰胺或二甲亚砜中的任意一种；
和/或，导电剂包括导电炭黑、碳纤维、碳纳米管、石墨烯或氮掺杂石墨烯中的任意一种或几种，优选为导电炭黑。
通过对粘结剂、分散剂和导电剂等具体种类的限定，使得各组分之间具有良好的相容性，有利于提高所形成掺硼金刚石复合材料层的电化学性能。
除了对上述掺硼金刚石复合材料层所用浆料中的组分有具体限定，对于隔膜基材的一些物性参数也有限定。
作为本申请的一种可选实施方式，隔膜基材的厚度为12-32μm，优选为12-30μm，进一步优选为12-20μm，典型但非限制行的隔膜基材的厚度为12μm、14μm、15μm、16μm、18μm、20μm、22μm、24μm、25μm、26μm、28μm、30μm或32μm。
隔膜基材的厚度不宜太厚，否则会造成较大的电池内阻，隔膜基材的厚度不宜太薄，否则力学性能将受到影响，从而容易被大颗粒、极片毛刺和枝晶刺穿，导致电池安全系数降低。故隔膜基材的厚度需控制在适宜的范围内。
隔膜基材的材质对于锂硫电池隔膜的最终性能有直接影响。作为本申请的一种可选实施方式，隔膜基材为聚烯烃微孔隔膜，由于聚烯烃微孔隔膜具有优异的力学性能、化学稳定性和相对廉价的特点，故选用其作为隔膜基材。
隔膜基材的材质应具有良好的绝缘性、成膜性能、力学性能和易于加性。作为本申请的一种可选实施方式，隔膜基材为聚烯烃微孔隔膜、陶瓷隔膜或玻璃纤维隔膜中的任意一种。
优选地，隔膜基材为聚烯烃微孔隔膜，聚烯烃微孔隔膜优选为聚乙烯微孔隔膜和/或聚丙烯微孔隔膜。
聚乙烯微孔隔膜、聚丙烯微孔隔膜为聚烯烃微孔隔膜的主要类别。在本申请中，聚烯烃微孔隔膜可以为聚乙烯微孔隔膜或聚丙烯微孔隔膜的一种，也可以为聚乙烯微孔隔膜和聚丙烯微孔隔膜形成多层复合隔膜基材。
根据本申请中的第二个方面，还提供了上述锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石复合材料层形成于隔膜基材上，得到锂硫电池隔膜。
该制备方法工艺简单，操作便利，适合工业化生产和大规模工业化使用。
作为本申请的一种可选实施方式，锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
将混合物A制成的浆料涂覆在隔膜基材上，干燥，得到锂硫电池隔膜；
或，所述锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
将混合物A制成的悬浮液的上清液通过隔膜基材进行分离，对分离后得到的隔膜基材进行干燥，得到锂硫电池隔膜。
需要说明的是，在将混合物A设置于隔膜基材上时，可采用不同的方法进行处理，其中一种方法为直接将混合物A涂覆在隔膜基材上，另外一种方法为将混合物A制成的悬浮液通过隔膜基材进行分离，此时分离为本领域常见的过滤或者抽滤，隔膜基材在此分离过程中起到的作用相当于滤纸。
采用本申请的上述制备方法可使得掺硼金刚石复合材料层与隔膜基材之间形成较好的粘附力。
作为本申请的一种可选实施方式，将混合物A制成的浆料涂覆在隔膜基材上时，浆料涂覆厚度为20-50μm；典型但非限制性的料浆涂覆厚度为20μm、25μm、30μm、35μm、40μm、45μm或50μm。
通过将浆料的涂覆厚度进行限定，使得最终形成在隔膜基材表面的掺硼金刚石复合材料层的厚度处于适宜厚度范围。
作为本申请的一种可选实施方式，将混合物A制成的悬浮液静置，静置后的上清液通过隔膜基材进行过滤分离，隔膜基材的厚度为12-20μm；典型但非限制性的隔膜基材的厚度为12μm、13μm、14μm、15μm、16μm、18μm或20μm。
由于隔膜基材相当于滤纸的作用，故可通过控制隔膜基材的厚度来控制过滤过程中的阻力大小。隔膜基材越薄，过滤过程阻力越小，越有利于过滤的进行。若隔膜基材过厚，上清液透过隔膜基材的速率会很慢，甚至无法过滤彻底，从而使得处理时间延长，原料损耗严重。
作为本申请的一种可选实施方式，干燥为真空干燥，干燥温度为60-90℃，干燥时间为20-30h。典型但非限制性的干燥温度为60℃、65℃、70℃、75℃、80℃、85℃或90℃，典型但非限制性的干燥时间为20h、22h、24h、25h、26h、28h或30h。
通过对干燥方式，干燥温度以及时间的限定，使得隔膜基材上的浆料在可较短时间内形成掺硼金刚石复合材料层，且所形成的掺硼金刚石复合材料层不易开裂。
作为本申请的一种可选实施方式，锂硫电池隔膜的制备方法，工艺流程简图如图1所示，包括以下步骤：
将掺硼金刚石、粘结剂和任选地导电剂混合后，再加入分散剂，得到混合物A；
将混合物A进行研磨，将研磨后形成的浆料涂覆在隔膜基材的一面上，得到待处理隔膜，其中，隔膜基材的厚度为12-32μm，浆料的涂覆厚度为20-50μm；
将待处理隔膜进行真空干燥，真空干燥温度为60-90℃，真空干燥时间为20-30h，得到锂硫电池隔膜。
或，锂硫电池隔膜的制备方法，包括以下步骤：
将掺硼金刚石、粘结剂和任选地导电剂混合后，再加入分散剂，得到混合物A；
将混合物A进行超声，将超声后得到的悬浮液静置，然后取上清液，以隔膜基材作为滤纸进行抽滤，得到待处理隔膜，其中，隔膜基材的厚度为12-20μm；
将待处理隔膜进行真空干燥，真空干燥温度为60-90℃，真空干燥时间为20-30h，得到锂硫电池隔膜。
通过对锂硫电池隔膜制备方法中各步骤进行具体限定，使得所制备得到的锂硫电池隔膜在具有良好的电化学性能的同时，还具有优异的可加工性。
根据本申请的第三个方面，还提供了一种锂硫电池，包括上述锂硫电池隔膜或采用上述锂硫电池隔膜的制备方法制得的锂硫电池。
鉴于上述锂硫电池隔膜所具有的优势，使得包含其的锂硫电池也具有同样的优势，从而使得该锂硫电池的质量比容量和循环特性得到有效提高，进而提升的锂硫电池的电化学性能。
根据本申请的第四个方面，还提供了包含上述锂硫电池的电子装置、电动工具、电动车辆或电力存储系统。
鉴于上述锂离子电池所具有的优势，在使用本申请实施方式的锂离子电池的电子装置、 电动工具、电动车辆以及电力储存系统中也可以获得相同的效果。
电子装置是使用锂离子电池作为操作的电源执行各种功能(例如，演奏音乐)的电子装置。电动工具是使用锂离子电池作为驱动电源来移动部件(例如，钻头)的电动工具。电动车辆是依靠锂离子电池作为驱动电源运行的电动车辆，并且可以是除了锂离子电池之外还装备有其他驱动源的汽车(包括混合动力车)。电力储存系统是使用锂离子电池作为电力储存源的电力储存系统。例如，在家用电力储存系统中，使电力储存在用作电力储存源的锂离子电池中，并且根据需要消耗储存在锂离子电池中的电力以能够使用诸如家用电子产品的各种装置。
下面结合具体实施例和对比例，对本申请作进一步说明。
实施例1
本实施例提供的一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层；
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为12μm；
掺硼金刚石复合材料层的厚度为30μm，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂和分散剂，掺硼金刚石、粘结剂和分散剂的质量比为5:0.8:1；
掺硼金刚石的粒度为100nm，掺硼金刚石中硼的掺杂浓度为500ppm；
粘结剂为聚偏氟乙烯，分散剂为N-二甲基酰胺。
实施例2
本实施例提供的一种锂硫电池隔膜，除了形成掺硼金刚石复合材料层的所用浆料还包括导电剂，导电剂为碳纳米管，且掺硼金刚石、粘结剂、导电剂和分散剂的质量比为5:0.8:1:1，其余组分与实施例1相同。
实施例3
本实施例提供的一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层；
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为18μm；
掺硼金刚石复合材料层的厚度为20μm，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂，掺硼金刚石、粘结剂、导电剂和分散剂的质量比为8:1:1:1；
掺硼金刚石的粒度为120nm，掺硼金刚石中硼的掺杂浓度为1000ppm；
粘结剂为聚偏氟乙烯，导电剂为导电炭黑，分散剂为N-甲基吡咯烷酮。
实施例4
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层的厚度为45μm，其余与实施例3相同。
实施例5
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层的厚度为15μm，其余与实施例3相同。
实施例6
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石中硼的掺杂浓度为5000ppm，其余与实施例3相同。
实施例7
本实施例提供的一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层；
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为30μm；
掺硼金刚石复合材料层的厚度为50μm，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂，掺硼金刚石、粘结剂、导电剂和分散剂的质量比为6:3:1:2；
掺硼金刚石的粒度为150nm，掺硼金刚石中硼的掺杂浓度为2000ppm；
粘结剂为聚偏氟乙烯，导电剂为导电炭黑，分散剂为N-甲基吡咯烷酮。
实施例8
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石的粒度为300nm，其余与实施例7相同。
实施例9
本实施例提供的一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层；
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为24μm；
掺硼金刚石复合材料层的厚度为40μm，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂，掺硼金刚石、粘结剂、导电剂和分散剂的质量比为4:1:2:1.5；
掺硼金刚石的粒度为200nm，掺硼金刚石中硼的掺杂浓度为3000ppm；
粘结剂为聚乙烯醇，导电剂为石墨烯，分散剂为N-甲基吡咯烷酮。
实施例1-9提供的锂硫电池隔膜的制备方法，包括以下步骤：
将上述配方量的掺硼金刚石、粘结剂和任选地导电剂混合后，再加入分散剂，得到混 合物A；
将混合物A进行研磨，将研磨后形成的浆料涂覆在隔膜基材的一面上，得到待处理隔膜，浆料的涂覆厚度为30μm；
将待处理隔膜进行真空干燥，真空干燥温度为80℃，真空干燥时间为24h，得到锂硫电池隔膜。
实施例10
本实施例提供的一种锂硫电池隔膜具体组成参数与实施例3相同。
本实施例提供的锂硫电池隔膜的制备方法，包括以下步骤：
将配方量的掺硼金刚石、粘结剂和任选地导电剂混合后，再加入分散剂，得到混合物A；
将混合物A进行超声，将超声后得到的悬浮液静置20h，然后取上清液，以隔膜基材作为滤纸进行抽滤，得到待处理隔膜，其中，超声时间为12h；
将待处理隔膜进行真空干燥，真空干燥温度为80℃，真空干燥时间为24h，得到锂硫电池隔膜。
实施例11
本实施例提供的一种锂硫电池隔膜，除了隔膜基材的厚度为24μm，其余具体组成参数与实施例3相同。
本实施例提供的锂硫电池隔膜的制备方法与实施例10相同。
实施例12
本实施例提供的一种锂硫电池隔膜，包括隔膜基材和形成在隔膜基材表面的掺硼金刚石复合材料层；
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为12μm；
掺硼金刚石复合材料层的厚度为25μm，形成掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂，掺硼金刚石、粘结剂、导电剂和分散剂的质量比为4:1:1:1.5；
掺硼金刚石的粒度为200nm，掺硼金刚石中硼的掺杂浓度为3000ppm；
粘结剂为聚乙烯醇，导电剂为石墨烯，分散剂为N-甲基吡咯烷酮。
本实施例提供的锂硫电池隔膜的制备方法，包括以下步骤：
将配方量的掺硼金刚石、粘结剂和任选地导电剂混合后，再加入分散剂，得到混合物A；
将混合物A进行超声，将超声后得到的悬浮液静置24h，然后取上清液，以隔膜基材作为滤纸进行抽滤，得到待处理隔膜，其中，超声时间为10h；
将待处理隔膜进行真空干燥，真空干燥温度为70℃，真空干燥时间为30h，得到锂硫电池隔膜。
实施例13
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层中的所用浆料中未添加有导电剂，其余具体组成参数与实施例12相同。
实施例14
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层中掺硼金刚石、粘结剂、导电剂和分散剂的质量比为10:0.4:1:1.5，其余与实施例12相同。
实施例15
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层中掺硼金刚石、粘结剂、导电剂和分散剂的质量比为1:1:1:1.5，其余与实施例12相同。
实施例16
本实施例提供的一种锂硫电池隔膜，除了掺硼金刚石复合材料层中掺硼金刚石、粘结剂、导电剂和分散剂的质量比为4:1:5:1.5，其余与实施例12相同。
对比例1
本对比例提供了一种锂硫电池隔膜，为实施例3的对比实验，该锂硫电池隔膜包括隔膜基材和形成在隔膜基材表面的金刚石复合材料层。
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为18μm；
金刚石复合材料层的厚度为30μm，形成金刚石复合材料层的所用浆料包括以下组分：纳米金刚石粉、粘结剂、导电剂和分散剂，金刚石粉、粘结剂、导电剂和分散剂的质量比为8:1:1:1；
粘结剂为聚偏氟乙烯，导电剂为导电炭黑，分散剂为N-甲基吡咯烷酮。
本对比例提供的锂硫电池隔膜的制备方法与实施例3相同。
对比例2
本对比例提供了一种锂硫电池隔膜，为实施例12的对比实验，该锂硫电池隔膜包括隔膜基材和形成在隔膜基材表面的金刚石复合材料层。
其中，隔膜基材为聚丙烯微孔隔膜，隔膜基材的厚度为12μm；
金刚石复合材料层的厚度为25μm，形成金刚石复合材料层的所用浆料包括以下组分：纳米金刚石粉、粘结剂、导电剂和分散剂，金刚石粉、粘结剂、导电剂和分散剂的质量比为4:1:1:1.5；
粘结剂为聚乙烯醇，导电剂为石墨烯，分散剂为N-甲基吡咯烷酮。
本对比例提供的锂硫电池隔膜的制备方法与实施例12相同。
为进一步验证上述实施例和对比例的效果，特设以下实验例。
实验例1
将实施例1-16和对比例1、2提供的锂硫电池隔膜制作成锂硫电池，其中，正极为S：导电炭：PVDF＝7:2:1，负极为金属锂片，电解液为商用电解液。
测量各实施例和对比例对应的锂硫电池的质量比容量和循环特性(0.5C倍率)，并以为纯隔膜基材为对照组(表面上未形成任何复合层)，对照组1为聚乙烯微孔隔膜，对照组2为聚丙烯微孔隔膜，具体如表1所示。
表1各实施例和对比例对应的锂硫电池的质量比容量和循环特性
Figure PCTCN2018121862-appb-000001
从表1中可以看出，采用本申请实施例1-16提供的锂硫电池的质量比容量和循环特性整体要优于对比例和对照组。
其中，实施例2为实施例1的对照实验，与实施例1相比，实施例2的形成掺硼金刚石复合材料层的所用浆料中还包括导电剂。通过表1中数据可以看出，导电剂的加入有利于锂硫电池的质量比容量和循环特性提高，但是总体提高程度不大。
实施例4-6均为实施例3的对照实验，与实施例3相比，实施例4和5中的掺硼金刚石复合材料层的厚度不同，实施例6中的掺硼金刚石中硼的掺杂浓度不同。对比表1中数据可知，掺硼金刚石复合材料层的厚度越大，有利于锂硫电池循环特性的提升，但是掺硼金刚石复合材料层的厚度不宜过大，过大会降低锂离子的传输效率。当掺硼金刚石复合材 料层的厚度过薄时，其对于中间产物多硫化物的吸附量明显减少，不利于锂硫电池质量比容量的提升。另外，高的掺硼浓度有利于提高锂硫电池的质量比容量，这主要是由于硼的掺杂浓度越高，掺硼金刚石复合材料层的导电性越好，好的导电性有利于促进多硫化物的进一步转化。
实施例8为实施例7的对照实验，两者不同之处在于掺硼金刚石的粒度不同。由表中数据可以看出，在一定尺度，掺硼金刚石的晶粒大小对锂硫电池性能影响不大。
对比例1为实施例3的对比实验，对比例2为实施例12的对比实验。两组对比例均考察了隔膜基材表面的金刚石复合材料层是否掺硼对于锂硫电池质量比容量和循环性能的影响。由表中数据可以看出，当金刚石复合材料层未掺杂有硼时，锂硫电池质量比容量和循环性能明显下降，这说明金刚石复合材料层中是否掺硼对于锂硫电池质量比容量和循环性能有直接影响。
另外，本申请图1中提供了两种锂硫电池隔膜的制备方法，这两种制备方法主要是体现在混合物A处理方式的不同。图2和图3分别是采用两种不同制备方法制得的锂硫电池隔膜。结合表1中数据和图2-3可以看出，图1中所示的两种锂硫电池隔膜的制备方法对于锂硫电池隔膜的制备均是可行的。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种锂硫电池隔膜，其特征在于，包括：
    隔膜基材；和，
    掺硼金刚石复合材料层，形成在所述隔膜基材的表面。
  2. 根据权利要求1所述的锂硫电池隔膜，其特征在于，所述掺硼金刚石复合材料层的厚度为20-50μm，优选为22-45μm，进一步优选为25-40μm。
  3. 根据权利要求1所述的锂硫电池隔膜，其特征在于，形成所述掺硼金刚石复合材料层的所用浆料包括以下组分：掺硼金刚石、粘结剂、导电剂和分散剂；
    所述掺硼金刚石、粘结剂、导电剂和分散剂的质量比为(2-10):(0.5-2):(0-4):(1-3)，优选为(3-8):(0.8-1.5):(1-3):(1-2)。
  4. 根据权利要求3所述的锂硫电池隔膜，其特征在于，所述掺硼金刚石中硼的掺杂浓度为500-5000ppm，优选为800-4500ppm；
    和/或，所述掺硼金刚石为掺硼金刚石粉，所述掺硼金刚石的粒度为100-200nm，优选为120-180nm。
  5. 根据权利要求1-4任意一项所述的锂硫电池隔膜，其特征在于，所述粘结剂包括聚偏氟乙烯、聚乙烯醇、聚四氟乙烯或丁苯橡胶中的任意一种，优选为聚偏氟乙烯；
    和/或，所述分散剂包括N-甲基吡咯烷酮、N-二甲基酰胺、N-二乙基酰胺或二甲亚砜中的任意一种，优选为N-甲基吡咯烷酮；
    和/或，所述导电剂包括导电炭黑、碳纤维、碳纳米管、石墨烯或氮掺杂石墨烯中的任意一种或几种，优选为导电炭黑。
  6. 根据权利要求1-4任意一项所述的锂硫电池隔膜，其特征在于，所述隔膜基材的厚度为12-32μm，优选为12-30μm，进一步优选为12-20μm；
    优选地，所述隔膜基材为聚烯烃微孔隔膜、陶瓷隔膜或玻璃纤维隔膜中的任意一种；
    优选地，所述隔膜基材为聚烯烃微孔隔膜，所述聚烯烃微孔隔膜包括聚乙烯微孔隔膜和/或聚丙烯微孔隔膜。
  7. 权利要求1-6任意一项所述的锂硫电池隔膜的制备方法，其特征在于，包括以下步骤：
    将掺硼金刚石复合材料层形成于隔膜基材上，得到锂硫电池隔膜；
    优选地，所述锂硫电池隔膜的制备方法，包括以下步骤：
    将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
    将混合物A制成的浆料涂覆在隔膜基材上，干燥，得到锂硫电池隔膜；
    优选地，所述锂硫电池隔膜的制备方法，包括以下步骤：
    将掺硼金刚石、粘结剂、分散剂和任选地导电剂混合，得到混合物A；
    将混合物A制成的悬浮液的上清液通过隔膜基材进行分离，对分离后得到的隔膜基材进行干燥，得到锂硫电池隔膜。
  8. 根据权利要求7所述的锂硫电池隔膜的制备方法，其特征在于，将混合物A制成的浆料涂覆在隔膜基材上时，浆料涂覆厚度为20-50μm；
    和/或，将混合物A制成的悬浮液静置，静置后的上清液通过隔膜基材进行分离，隔膜基材的厚度为12-20μm；
    和/或，将混合物A制成的浆料涂覆在隔膜基材上进行干燥，干燥为真空干燥，干燥温度为60-90℃，干燥时间为20-30h；
    和/或，对分离后得到的隔膜基材进行干燥，干燥为真空干燥，干燥温度为60-90℃，干燥时间为20-30h。
  9. 一种锂硫电池，其特征在于，包含权利要求1-6任意一项所述的锂硫电池隔膜或采用权利要求7或8所述的锂硫电池隔膜的制备方法制得的锂硫电池。
  10. 一种电子装置，其特征在于，包含权利要求9所述的锂硫电池。
PCT/CN2018/121862 2018-12-18 2018-12-18 锂硫电池隔膜及其制备方法、锂硫电池和电子装置 Ceased WO2020124392A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/121862 WO2020124392A1 (zh) 2018-12-18 2018-12-18 锂硫电池隔膜及其制备方法、锂硫电池和电子装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/121862 WO2020124392A1 (zh) 2018-12-18 2018-12-18 锂硫电池隔膜及其制备方法、锂硫电池和电子装置

Publications (1)

Publication Number Publication Date
WO2020124392A1 true WO2020124392A1 (zh) 2020-06-25

Family

ID=71102350

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/121862 Ceased WO2020124392A1 (zh) 2018-12-18 2018-12-18 锂硫电池隔膜及其制备方法、锂硫电池和电子装置

Country Status (1)

Country Link
WO (1) WO2020124392A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115634694A (zh) * 2022-10-17 2023-01-24 江苏正力新能电池技术有限公司 一种多功能电催化复合材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017037618A1 (en) * 2015-08-31 2017-03-09 Leif Nyholm Substrate with doped diamond layer for lithium-based systems
CN106684387A (zh) * 2016-12-20 2017-05-17 深圳先进技术研究院 一种含类金刚石薄膜层的锂离子电池负极及其制备方法和锂离子电池
CN107749475A (zh) * 2017-11-07 2018-03-02 成都新柯力化工科技有限公司 一种用于锂电池的Si/金刚石负极材料及其制备方法
CN107994233A (zh) * 2017-12-15 2018-05-04 深圳先进技术研究院 表面具有金刚石层的铝电极及其制备方法与锂二次电池
CN108550764A (zh) * 2018-03-16 2018-09-18 河南力旋科技股份有限公司 一种超细金刚石涂覆隔离膜及应用此隔离膜的锂离子电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017037618A1 (en) * 2015-08-31 2017-03-09 Leif Nyholm Substrate with doped diamond layer for lithium-based systems
CN106684387A (zh) * 2016-12-20 2017-05-17 深圳先进技术研究院 一种含类金刚石薄膜层的锂离子电池负极及其制备方法和锂离子电池
CN107749475A (zh) * 2017-11-07 2018-03-02 成都新柯力化工科技有限公司 一种用于锂电池的Si/金刚石负极材料及其制备方法
CN107994233A (zh) * 2017-12-15 2018-05-04 深圳先进技术研究院 表面具有金刚石层的铝电极及其制备方法与锂二次电池
CN108550764A (zh) * 2018-03-16 2018-09-18 河南力旋科技股份有限公司 一种超细金刚石涂覆隔离膜及应用此隔离膜的锂离子电池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115634694A (zh) * 2022-10-17 2023-01-24 江苏正力新能电池技术有限公司 一种多功能电催化复合材料及其制备方法和应用

Similar Documents

Publication Publication Date Title
Yan et al. Design, synthesis, and application of metal sulfides for Li–S batteries: progress and prospects
KR102276658B1 (ko) 그래핀-맥신-실리콘 함유 복합소재 이차전지 음극재 및 그 제조방법
KR102276657B1 (ko) 그래핀-탄소나노튜브-실리콘 함유 복합소재 이차전지 음극재 및 그 제조방법
Teng et al. MoS2 nanosheets vertically grown on graphene sheets for lithium-ion battery anodes
JP6732300B2 (ja) 硫黄−炭素複合体、この製造方法及びこれを含むリチウム−硫黄電池
KR102405622B1 (ko) 실리콘-그래핀-탄소나노튜브 코어쉘 복합소재 이차전지 음극재 및 그 제조방법
CN103700859B (zh) 锂硫电池正极用石墨烯基氮掺杂多级孔碳纳米片/硫复合材料及其制备方法和应用
Shi et al. Design of nanostructured hybrid materials based on carbon and metal oxides for Li ion batteries
KR102228769B1 (ko) 그래핀-은나노와이어-실리콘 함유 복합소재 이차전지 음극재 및 그 제조방법
KR102405605B1 (ko) 그래핀-안티몬-실리콘 함유 복합소재 이차전지 음극재 및 그 제조방법
CN111540889B (zh) 一种双层包覆层包覆的硅负极材料及其制备方法和用途
KR102388203B1 (ko) 실리콘-그래핀-맥신 함유 복합소재 이차전지 음극재 및 그 제조방법
CN102306757A (zh) 锂离子电池硅石墨烯复合负极材料及其制备方法
KR102405612B1 (ko) 실리콘-그래핀-은나노와이어 함유 복합소재 이차전지 음극재 및 그 제조방법
CN115911341A (zh) 一种多孔硅碳负极材料、制备方法以及应用
KR102473745B1 (ko) 실리콘／탄소나노튜브／그래핀 복합체 제조방법 및 이를 이용한 이차전지 제조방법
WO2016110108A1 (zh) 一种纳米级锂离子复合正极的等离子喷射制备方法
CN106803569A (zh) 锂离子二次电池及其制备方法
CN107658407A (zh) 一种用于锂硫电池隔膜改性的二维多孔碳片的制备方法
CN107871868A (zh) 一种石墨烯增强的一体化电极及其制备方法和电池
CN106953079B (zh) 一种多级结构碳纳米管/二氧化锡复合材料及其制备方法
CN104247098A (zh) 二次电池用负极及其制造方法以及二次电池
CN118431452A (zh) 负极材料、制备方法及应用
CN111341971B (zh) 锂硫电池隔膜及其制备方法、锂硫电池和电子装置
JP6136326B2 (ja) リチウムイオン二次電池用正極材料及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18943651

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 11-11-2021)

122 Ep: pct application non-entry in european phase

Ref document number: 18943651

Country of ref document: EP

Kind code of ref document: A1