WO2021228082A1 - Porous polymer-sulfur composite material and preparation method therefor and use thereof - Google Patents

Porous polymer-sulfur composite material and preparation method therefor and use thereof Download PDF

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WO2021228082A1
WO2021228082A1 PCT/CN2021/093030 CN2021093030W WO2021228082A1 WO 2021228082 A1 WO2021228082 A1 WO 2021228082A1 CN 2021093030 W CN2021093030 W CN 2021093030W WO 2021228082 A1 WO2021228082 A1 WO 2021228082A1
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porous polymer
sulfur
composite material
lithium
electrolyte
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French (fr)
Chinese (zh)
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曾宪祥
李江玉
张淑
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湖南农业大学
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/30—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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    • C08G12/40—Chemically modified polycondensates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • C—CHEMISTRY; METALLURGY
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of polymer material preparation and electrochemical power supply, and specifically relates to a porous polymer-sulfur composite material and a preparation method and application thereof.
  • Lithium-sulfur battery is a type of secondary battery that uses sulfur or sulfur-containing compound positive electrode to match metal lithium negative electrode and electrolyte.
  • the high theoretical specific capacity of the battery is achieved through the two-electron electrochemical reaction between sulfur and lithium.
  • the use of sulfur or sulfur-containing compounds as cathodes has the advantages of abundant reserves, low cost, and environmental friendliness.
  • the metal lithium secondary battery constructed by this has very important scientific research value and broadness. Application prospects.
  • the current lithium-sulfur battery still has many problems.
  • sulfur as the active material of the positive electrode faces problems such as low conductivity, large volume changes during charge and discharge, and easy dissolution of reaction intermediate products (polysulfides) or shuttle to the negative electrode side to cause side reactions.
  • reaction intermediate products polysulfides
  • shuttle to the negative electrode side to cause side reactions have caused the deactivation of active materials in lithium-sulfur batteries and the low coulombic efficiency of the battery, which severely shortens the service life of the battery.
  • An effective method is to compound the sulfur with the conductive matrix, so that the sulfur is confined in the matrix cavity in an amorphous state (CN201280077418.1; CN201310655174.7; CN201610374022.3; CN201710755681.6), so as to realize the sulfur in a limited space
  • a reversible electrochemical reaction occurs in the battery, which improves the stability and service life of the battery cycle.
  • carbon material is the primary choice of matrix material, and in addition, metal oxide or high molecular polymer modified layer is combined to coat active sulfur.
  • the present invention provides a porous polymer, which has a structure as shown in Formula 1:
  • R 1 , R 2 , R 3 , and R 4 are the same or different, and are each independently selected from H, OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 , R 5 is selected from at least one of B, Al, C, Si, Ge, N, P, As, S, Se, Cl, Br, I, and R 6 is selected from H, OH, -CN, -CF 3 , -CH 3 , -OCH 3 , -OC 2 H 5 , At least one of
  • n, x and y are the same or different, and are independently selected from an integer of 1-8.
  • R 1 and R 2 are selected from R 3 and R 4 are selected from any of the above groups other than Any of the above groups other than those listed above.
  • R 1 and R 2 are independently selected from H, OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 ( CF 3 ), At least one of
  • R 3 and R 4 are independently selected from H, OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 (CF 3 ), At least one of
  • n, x and y are the same or different, and are independently selected from an integer of 1-4.
  • R 1 is selected from H
  • R 2 is selected from H
  • R 3 is selected from H or R 4 is selected from -SO 3 H;
  • the polymerized monomers of the porous polymer include aldehyde monomers and amine monomers, and the aldehyde monomers have a structure as shown in Formula 2:
  • the amine monomer has a structure shown in formula 3:
  • R 1 , R 2 , R 3 , R 4 and n have the meanings as described above.
  • the aldehyde monomer does not contain an amine group substituent, and the amine monomer does not contain an aldehyde group substituent.
  • R 1 and R 2 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 , At least one of
  • R 5 and R 6 have the same meanings as above; n, x and y are the same or different, and are independently selected from an integer of 1-4.
  • R 1 is selected from H
  • R 2 is selected from H
  • R 3 and R 4 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 , At least one of
  • R 5 and R 6 have the same meanings as above; n, x and y are the same or different, and are independently selected from an integer of 1-4.
  • R 3 is selected from H or R 4 is selected from -SO 3 H.
  • the aldehyde monomer may be selected from
  • the amine monomer may be selected from Wait.
  • the specific surface area of the porous polymer is 150-3000m 2 g -1, for example 500-2000m 2 g -1, and if of 1000-1500m 2 g -1, exemplary of 500m 2 g -1, 570m 2 g -1, 583m 2 g -1, 600m 2 g -1, 620m 2 g -1, 750m 2 g -1, 1000m 2 g -1, 1200m 2 g -1, 1500m 2 g - 1. 2000m 2 g -1 .
  • the pore volume of the porous polymer is 0.1-2 cm 3 g -1 , for example, 0.2-1.5 cm 3 g -1 , or 0.5-1.2 cm 3 g -1 , exemplarily 0.5cm 3 g -1 , 0.7cm 3 g -1 , 0.85cm 3 g -1 , 0.9cm 3 g -1 , 0.92cm 3 g -1 , 0.96cm 3 g -1 , 1.1cm 3 g -1 , 1.3 cm 3 g -1 , 1.5cm 3 g -1 .
  • the average pore diameter of the porous polymer is 0.25-5nm, such as 0.5-3nm, or 1-2nm, exemplarily 0.7nm, 0.9nm, 1.2nm, 1.3nm, 1.4nm , 1.5nm, 1.7nm, 2nm.
  • the porous polymer has a morphology substantially as shown in FIG. 1.
  • the present invention also provides a method for preparing the porous polymer, which includes the following steps: reacting raw materials containing amine monomers and aldehyde monomers under vacuum conditions to obtain the porous polymer;
  • the amine monomer and aldehyde monomer have the meanings as described above.
  • the molar ratio of the aldehyde monomer to the amine monomer is (0.1-10):1, preferably (0.2-8):1, more preferably (0.5-5):1
  • Exemplified are 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1.
  • the reaction raw material includes a solvent.
  • the solvent is selected from at least one of butanol, toluene, dichlorobenzene, mesitylene, acetamide, and dioxane acid, and the acid is acetic acid and/or trifluoroacetic acid; the solvent is preferably It is a mixed solvent of butanol, dichlorobenzene and acetic acid.
  • the volume ratio of butanol and dichlorobenzene to acetic acid in the mixed solvent is (2-30):(4-50):1, preferably (3-15):(5-25) ):1, more preferably (2-5):(4-12):1, and exemplary 2:4:1.
  • the temperature of the reaction is 25-200°C, for example 60-200°C, preferably 80-160°C, exemplarily 100°C, 120°C, 150°C.
  • the reaction time is 2-200 hours, such as 5-100 hours, and exemplarily 10 hours, 20 hours, 40 hours, 60 hours, 72 hours.
  • the reaction temperature rising rate is 2-10 °C min -1, e.g. 3-8 °C min -1, for the exemplary 4 °C min -1, 5 °C min -1, 6 °C min - 1 .
  • the method for preparing the porous polymer includes the following steps: dispersing the amine monomer and aldehyde monomer in a mixed solvent of butanol, dichlorobenzene and acetic acid, and under vacuum conditions The next reaction is to obtain the porous polymer.
  • the present invention also provides a porous polymer prepared by the above method.
  • the present invention also provides the application of the porous polymer as a positive electrode matrix material of a lithium-sulfur battery.
  • the present invention also provides a porous polymer-sulfur composite material, which contains any one of the above-mentioned porous polymers and sulfur.
  • the sulfur in the porous polymer-sulfur composite material, is uniformly dispersed in the pores and surface of the porous polymer in at least one of a crystalline state and an amorphous state.
  • the sulfur is uniformly dispersed in the pores and surface of the porous polymer in the form of molecular aggregation.
  • the mass percentage of the sulfur in the porous polymer-sulfur composite material is 50-95%, preferably 60-90%, more preferably 70-80% Exemplified are 50%, 60%, 70%, 71%, 72%, 74%, 75%, 77%, 80%, 90%.
  • the porous polymer-sulfur composite material has a morphology substantially as shown in FIG. 3.
  • the present invention also provides a method for preparing the porous polymer-sulfur composite material, which includes the following steps: dispersing sulfur and the porous polymer in a solvent, heating to evaporate the solvent and vacuum drying to obtain the porous polymer-sulfur composite material .
  • the solvent is carbon disulfide, carbon tetrachloride, ethylene diamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ether and water At least one of; preferably carbon disulfide, ethylenediamine, N-methylpyrrolidone or N,N-dimethylformamide.
  • the mass ratio of the sulfur to the porous polymer is (2-20):1, such as (10-20):1, such as (12-18):1, and exemplarily 5: 2, 12:1, 14:1, 15:1, 17:1, 18:1.
  • the amount of the solvent is not particularly limited, and it is preferable that the sulfur and the porous polymer can be fully dispersed.
  • the amount of the solvent may be 100-500 times the mass of the porous polymer, preferably 200-400 times, and exemplarily 200 times, 300 times, or 400 times.
  • the heating and vacuum drying temperatures are the same or different, for example, the temperature is 50-250°C, preferably 50-180°C, more preferably 80-150°C, exemplarily 60°C, 80°C, 100°C, 120°C.
  • the vacuum drying time is 6-24 hours, preferably 10-12 hours, and exemplarily 10 hours, 12 hours, 15 hours, and 20 hours.
  • the method further includes: after vacuum drying, cooling to obtain the porous polymer-sulfur composite material.
  • the present invention also provides a porous polymer-sulfur composite material prepared by the above method.
  • the present invention also provides the application of the porous polymer-sulfur composite material in a lithium-sulfur battery, preferably as an active material in the positive electrode of a lithium-sulfur battery.
  • the present invention provides a composite electrode, which includes the above-mentioned porous polymer-sulfur composite material.
  • the composite electrode further includes a conductive additive and a binder.
  • the conductive additive is selected from at least one of carbon black, super-P, Ketjen black and carbon nanotubes, preferably carbon black, super-P, Ketjen black or carbon nanotubes.
  • the binder is selected from at least one of polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), styrene butadiene rubber/sodium carboxymethyl cellulose (SBR/CMC), and sodium alginate (SA) Species, preferably styrene-butadiene rubber/sodium carboxymethyl cellulose (SBR/CMC).
  • the mass ratio of the porous polymer-sulfur composite material, the conductive additive and the binder is (4-8):(1-5):1, for example (5-7):(2) -4):1, 6:3:1 as an example.
  • the composite electrode further includes a current collector.
  • the current collector can be selected from current collectors known in the art, for example, selected from aluminum foil, copper foil, carbon-coated aluminum foil, carbon-coated copper foil, tin-plated aluminum foil, copper-plated aluminum foil, or carbon cloth.
  • a mixture of a porous polymer-sulfur composite material, a conductive additive, and a binder is supported on the current collector.
  • the present invention also provides a method for preparing the composite electrode, which includes the following steps: uniformly mixing the porous polymer-sulfur composite material, binder, conductive additive and solvent, and the prepared slurry is coated and dried to obtain The composite electrode.
  • the mass ratio of the porous polymer-sulfur composite material, the binder, and the conductive additive has the meaning as described above.
  • the solvent is at least one of carbon disulfide, ethylenediamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ether and water; Preferably, it is carbon disulfide, ethylenediamine, water, N-methylpyrrolidone or N,N-dimethylformamide. Further, the amount of the solvent can be used to form a slurry with a common concentration in the field.
  • the smearing and drying are operations known in the art.
  • the present invention also provides a lithium-sulfur battery, which includes the above-mentioned composite electrode.
  • the lithium-sulfur battery includes a metal lithium negative electrode, the composite electrode as a positive electrode, and an electrolyte.
  • the electrolyte is selected from liquid electrolytes and/or solid electrolytes.
  • the liquid electrolyte is an ether type electrolyte.
  • the concentration of the ether electrolyte is 0.1-20 mol/L, preferably 1-10 mol/L, and exemplarily 1 mol/L, 3 mol/L, 5 mol/L, 8 mol/L.
  • the solvent in the ether electrolyte is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), fluoroethylene carbonate (FEC), 1,3- At least one of dioxolane (DOL), ethylene glycol dimethyl ether (DME), and triethylene glycol dimethyl ether (TEGDME), such as diethyl carbonate, propylene carbonate, 1,3-di At least one of oxypentane and ethylene glycol dimethyl ether, exemplarily selected from mixed solvents of 1,3-dioxolane and ethylene glycol dimethyl ether, propylene carbonate and ethylene glycol dimethyl ether Mixed solvents.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • 1,3- At least one of dioxolane DOL
  • ethylene glycol dimethyl ether DME
  • TEGDME triethylene glycol dimethyl
  • the solute in the ether electrolyte is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium nitrate (LiNO 3 ), lithium bisoxalate borate (LiBOB), (trifluoromethyl) sulfonate At least one of lithium sulfonate (LiFSI) and lithium bis(trifluoromethyl)sulfonate (LiTFSI); for example, lithium bis(trifluoromethyl)sulfonate, lithium (trifluoromethyl)sulfonate and lithium hexafluorophosphate At least one of; exemplified is lithium bis(trifluoromethyl)sulfonate.
  • the solid electrolyte is selected from at least one of inorganic solid electrolytes and polymer electrolytes.
  • the polymer electrolyte may be a gel polymer electrolyte and/or a solid polymer electrolyte.
  • the inorganic solid electrolyte is selected from at least one solid ceramic electrolyte.
  • the polymer electrolyte is selected from polyethylene oxide (PEO), polyethylene glycol dimethyl ether (PEGDME), copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), ethoxylated
  • PEO polyethylene oxide
  • PEGDME polyethylene glycol dimethyl ether
  • PVDF-HFP copolymer of vinylidene fluoride and hexafluoropropylene
  • ETPTA trimethylolpropane triacrylate
  • the present invention also provides a method for preparing the lithium-sulfur battery, which includes assembling the metal lithium negative electrode, the composite electrode as a positive electrode, and an electrolyte to obtain the lithium-sulfur battery.
  • the invention also provides the application of the lithium-sulfur battery in the preparation of energy storage devices.
  • the present invention also provides an energy storage device, which contains the above-mentioned lithium-sulfur battery.
  • the porous polymer provided by the present invention has a large specific surface area and a high pore volume, so that the sulfur loading in the porous polymer is high. It is obtained by reacting aldehyde and amine monomers in proportions. Using the porous polymer as the matrix material, the solvent-dissolved sulfur is poured into the porous polymer to prepare a porous polymer-sulfur composite material, in which the sulfur is uniformly dispersed in the polymer Because the porous polymer exhibits a strong polysulfide ion adsorption effect on the material pores and surface, it can inhibit the shuttle of polysulfide ions during the charge and discharge process, so that the lithium-sulfur battery has a high coulombic efficiency.
  • the obtained porous polymer-sulfur composite positive electrode and the corresponding lithium-sulfur battery have high specific discharge capacity and excellent cycle stability.
  • the preparation method of the porous polymer and the porous polymer-sulfur composite material provided by the invention is simple, the raw materials are easily available, are suitable for large-scale production, and have a high degree of practicality.
  • the lithium-sulfur battery of the present invention is expected to be a new type of high-energy density energy storage device and has good application prospects.
  • Figure 1 is a scanning electron microscope image of the porous polymer of Example 1 (scale 10 ⁇ m).
  • FIG. 2 is an infrared spectrum diagram of the porous polymer of Example 1.
  • Fig. 3 is a scanning electron micrograph of the porous polymer-sulfur composite material of Example 1 (scale bar 10 ⁇ m).
  • Example 4 is a cyclic voltammetry curve of the lithium-sulfur battery of Example 1 in an ether electrolyte.
  • Fig. 5 is a charging and discharging curve of the lithium-sulfur battery of Example 1 in an ether electrolyte.
  • Fig. 6 shows the cycle stability of the lithium-sulfur battery of Example 1 in an ether electrolyte.
  • the monomer I and monomer II are weighed according to the molar ratio of 1:1, and dispersed in a mixed solvent of butanol, dichlorobenzene and acetic acid with a volume ratio of 2:4:1.
  • the tube is sealed and vacuumed.
  • the temperature was raised to 120°C at 5°C min -1 , and the reaction was kept for 72 hours to obtain a porous polymer (Figure 1).
  • Figure 2 Combined with the analysis of the infrared spectrum ( Figure 2), it is not difficult to find that monomer I reacts with monomer II to form an imine bond to obtain a porous polymer.
  • the specific surface area of the obtained porous polymer is 500 m 2 g -1 , the pore volume is 0.9 cm 3 g -1 , and the pore diameter is 1.4 nm.
  • porous polymer and sulfur were weighed at a mass ratio of 15:1, and dispersed in carbon disulfide ultrasonically for 3 hours, then the solvent was evaporated to dryness at 80°C, and then vacuum dried at 80°C for 10 hours. After cooling, the porous polymer was obtained. -Sulfur composite material ( Figure 3).
  • sulfur is uniformly dispersed in the pores and surfaces of the porous polymer in a molecular aggregate state; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 72%.
  • the porous polymer-sulfur composite material obtained above is mixed with the conductive additive super P, the binder styrene-butadiene rubber/sodium carboxymethyl cellulose at a mass ratio of 6:3:1, and mixed with water to form a slurry.
  • the porous polymer-sulfur composite positive electrode is obtained through treatment processes such as coating and drying.
  • a lithium-sulfur battery is assembled with the porous polymer-sulfur composite positive electrode obtained above, a lithium sheet, and an ether electrolyte (1M LiTFSI+1% LiNO 3 DOL-DME (DOL to DME mass ratio 1:1) solution).
  • the obtained lithium-sulfur battery was subjected to cyclic voltammetry ( Figure 4) and constant current charge-discharge test ( Figure 5) at room temperature.
  • the charge-discharge cut-off voltage was 1.8-2.8V, and the charge-discharge current was based on the theoretical ratio of sulfur mass.
  • the capacity is 1675mA hg -1 calculated.
  • Figure 4 shows the cyclic voltammogram of the lithium-sulfur battery in the ether electrolyte for the first three weeks (the sweep rate is 0.05mV s -1 ). The figure shows two pairs of redox peaks, respectively near 2.05/2.3V and 2.28/2.36V.
  • Figure 6 shows the cycle performance of the lithium-sulfur battery at a rate of 0.5C. After 50 cycles, the battery discharge capacity remains at 901mA h g -1 , indicating that the prepared lithium-sulfur battery has excellent discharge specific capacity and cycle stability sex.
  • the specific surface area of the obtained porous polymer is 620 m 2 g -1 , the pore volume is 0.85 cm 3 g -1 , and the pore diameter is 1.2 nm; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 70%.
  • the prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1608 mA h g -1 , and the specific discharge capacity after 50 cycles was 882 mA h g -1 .
  • the specific surface area of the obtained porous polymer is 570 m 2 g -1 , the pore volume is 0.96 cm 3 g -1 , and the pore diameter is 1.3 nm; the mass percentage of sulfur in the porous polymer-sulfur composite is about 77%.
  • the prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1614 mA h g -1 , and the specific discharge capacity after 50 cycles was 896 mA h g -1 .
  • the specific surface area of the obtained porous polymer is 583 m 2 g -1 , the pore volume is 0.92 cm 3 g -1 , and the pore diameter is 1.5 nm; the mass percentage of sulfur in the porous polymer-sulfur composite is about 74%.
  • the prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1624 mA h g -1 , and the specific discharge capacity after 50 cycles was 906 mA h g -1 .
  • Example 2 Others are the same as Example 1, except that the electrolyte is (8M LiTFSI+1% LiNO 3 PC-DME (PC to DME mass ratio 1:1) solution.
  • the prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1594 mA h g -1 , and the specific discharge capacity after 50 cycles was 884 mA h g -1 .
  • electrolyte is a solid state composed of ether electrolyte (1M LiTFSI+1% LiNO 3 in DOL-DME (DOL to DME ratio 1:1) solution) and PVDF-HFP. Electrolyte.
  • the prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1582 mA h g -1 , and the specific discharge capacity after 50 cycles was 891 mA h g -1 .
  • the lithium-sulfur battery of the present invention has excellent discharge capacity and cycle stability.
  • the monomer I and monomer II are weighed according to the molar ratio of 1:1, and dispersed in a mixed solvent of butanol and dichlorobenzene and acetic acid with a volume ratio of 10:1.
  • the tube is sealed and vacuumed at 5°Cmin. -1
  • the temperature is raised to 120°C, and the reaction is kept for 72 hours to obtain a porous polymer (with a morphology as shown in Fig. 1).
  • infrared characterization proved that monomer I reacted with monomer II to form an imine bond to obtain a porous polymer.
  • sulfur is uniformly dispersed in the pores and surfaces of the porous polymer in a molecular aggregate state; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 71%.
  • the lithium-sulfur battery containing the composite material of this example has a lithium-sulfur battery substantially as in Example 1. The same electrochemical performance as the battery.

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Abstract

A porous polymer-sulfur composite material and a preparation method therefor and use thereof. The porous polymer is obtained by the reaction of aldehyde and amine monomers, and sulfur dissolved in a solvent is poured into the porous polymer to obtain the porous polymer-sulfur composite material, sulfur in the composite material being uniformly dispersed in pore channels and the surface of the polymer. In the use of the porous polymer-sulfur composite material as a positive electrode of a lithium-sulfur battery, the porous polymer shows high sulfur loading amount and strong ion adsorption effect; and a porous polymer-sulfur composite material based positive electrode and a corresponding battery have high specific discharge capacity and excellent cycle stability. The preparation method for the porous polymer-sulfur composite material is simple, has easily-obtainable raw materials, is suitable for large-scale production, and has high practical level.

Description

一种多孔聚合物-硫复合材料及其制备方法和用途Porous polymer-sulfur composite material and preparation method and application thereof
本申请要求申请人于2020年5月12日向中国国家知识产权局提交的专利申请号为202010398795.1，发明名称为“一种多孔聚合物-硫复合材料及其制备方法和用途”的在先申请的优先权。所述在先申请的全文通过引用的方式结合于本申请中。This application requires the applicant to file a patent application number 202010398795.1 with the title of “a porous polymer-sulfur composite material and its preparation method and use” to the State Intellectual Property Office of China on May 12, 2020. priority. The full text of the prior application is incorporated into this application by reference.
技术领域Technical field
本发明属于聚合物材料制备和电化学电源领域，具体涉及一种多孔聚合物-硫复合材料及其制备方法和用途。The invention belongs to the field of polymer material preparation and electrochemical power supply, and specifically relates to a porous polymer-sulfur composite material and a preparation method and application thereof.
背景技术Background technique
锂-硫电池为采用硫或含硫化合物正极匹配金属锂负极和电解质得到的一类二次电池，通过硫与锂之间的二电子电化学反应实现电池高的理论比容量。相比于其他金属或金属氧化物正极，以硫或含硫化合物为正极具有丰富的储量、低的成本、环境友好等优点，以此构建的金属锂二次电池具有非常重要的科研价值和广阔的应用前景。Lithium-sulfur battery is a type of secondary battery that uses sulfur or sulfur-containing compound positive electrode to match metal lithium negative electrode and electrolyte. The high theoretical specific capacity of the battery is achieved through the two-electron electrochemical reaction between sulfur and lithium. Compared with other metal or metal oxide cathodes, the use of sulfur or sulfur-containing compounds as cathodes has the advantages of abundant reserves, low cost, and environmental friendliness. The metal lithium secondary battery constructed by this has very important scientific research value and broadness. Application prospects.
尽管具有上述突出的优点，但目前锂-硫电池还存在多方面的问题。其中，硫作为正极的活性物质面临电导率低、在充放电过程中体积变化大、反应中间产物(多硫化物)易于溶解或穿梭至负极侧发生副反应等难题。这些问题都造成锂-硫电池活性物质失活和电池库伦效率低下，严重缩短电池服役寿命。有效的方法是将硫与导电基体进行复合，使硫以无定形的状态限制在基体腔体中(CN201280077418.1；CN201310655174.7；CN201610374022.3；CN201710755681.6)，从而实现硫在有限的空间中发生可逆的电化学反应，提高了电池循环的稳定性和使用寿命。其中碳材料为基体材料的首要选择，此外结合金属氧化物或者高分子聚合物修饰层进行活性硫的包覆。然而，制备此类 复合材料要么需要经过300℃以上高温转化(如碳化)，要么需要复杂的后处理(去模板)，且这些基体材料(如金属氧化物)在锂-硫电池正极中的占比大，增加了材料和电池制造的成本，限制电池能量密度的提升。因此，从短周期元素出发合成轻质的基体，结合低能耗的材料复合方法，将硫限制在基体的空腔中，制备出具有高能量密度和循环稳定的电极材料和锂-硫电池，对于聚合物材料开发和储能领域的发展都有重要意义。Despite the above-mentioned outstanding advantages, the current lithium-sulfur battery still has many problems. Among them, sulfur as the active material of the positive electrode faces problems such as low conductivity, large volume changes during charge and discharge, and easy dissolution of reaction intermediate products (polysulfides) or shuttle to the negative electrode side to cause side reactions. These problems have caused the deactivation of active materials in lithium-sulfur batteries and the low coulombic efficiency of the battery, which severely shortens the service life of the battery. An effective method is to compound the sulfur with the conductive matrix, so that the sulfur is confined in the matrix cavity in an amorphous state (CN201280077418.1; CN201310655174.7; CN201610374022.3; CN201710755681.6), so as to realize the sulfur in a limited space A reversible electrochemical reaction occurs in the battery, which improves the stability and service life of the battery cycle. Among them, carbon material is the primary choice of matrix material, and in addition, metal oxide or high molecular polymer modified layer is combined to coat active sulfur. However, the preparation of such composite materials either needs to undergo high-temperature conversion (such as carbonization) above 300 ℃, or requires complex post-processing (de-template), and these matrix materials (such as metal oxides) account for the majority of lithium-sulfur battery cathodes. The large ratio increases the cost of materials and battery manufacturing, and limits the increase in battery energy density. Therefore, a lightweight matrix is synthesized from short-period elements, combined with a material composite method with low energy consumption, and sulfur is confined in the cavity of the matrix to prepare electrode materials and lithium-sulfur batteries with high energy density and cycle stability. The development of polymer materials and the development of energy storage are of great significance.
发明内容Summary of the invention
本发明提供一种多孔聚合物，所述聚合物具有如式1所示的结构：The present invention provides a porous polymer, which has a structure as shown in Formula 1:
Figure PCTCN2021093030-appb-000001
Figure PCTCN2021093030-appb-000001
其中，R 1、R 2、R 3、R 4相同或不同，各自独立地选自H、OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
Figure PCTCN2021093030-appb-000002
中的至少一种，其中R 5选自B、Al、C、Si、Ge、N、P、As、S、Se、Cl、Br、I中的至少一种，R 6选自H、OH、-CN、-CF 3、-CH 3、-OCH 3、-OC 2H 5、
Figure PCTCN2021093030-appb-000003
Figure PCTCN2021093030-appb-000004
中的至少一种； Wherein, R 1 , R 2 , R 3 , and R 4 are the same or different, and are each independently selected from H, OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
Figure PCTCN2021093030-appb-000002
R 5 is selected from at least one of B, Al, C, Si, Ge, N, P, As, S, Se, Cl, Br, I, and R 6 is selected from H, OH, -CN, -CF 3 , -CH 3 , -OCH 3 , -OC 2 H 5 ,
Figure PCTCN2021093030-appb-000003
Figure PCTCN2021093030-appb-000004
At least one of
n、x和y相同或不同，彼此独立地选自1-8的整数。n, x and y are the same or different, and are independently selected from an integer of 1-8.
根据本发明的实施方案，R 1与R 2选自除
Figure PCTCN2021093030-appb-000005
之外的任一上述基团，R 3与R 4选自除
Figure PCTCN2021093030-appb-000006
之外的任一上述基团。 According to an embodiment of the present invention, R 1 and R 2 are selected from
Figure PCTCN2021093030-appb-000005
R 3 and R 4 are selected from any of the above groups other than
Figure PCTCN2021093030-appb-000006
Any of the above groups other than those listed above.
根据本发明的实施方案，R 1与R 2彼此独立地选自H、OH、-BO 3H、-SiO 3H、 -PO 4H 2、-SO 3H、-ClO 4、-SO 3(CF 3)、
Figure PCTCN2021093030-appb-000007
中的至少一种； According to an embodiment of the present invention, R 1 and R 2 are independently selected from H, OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 ( CF 3 ),
Figure PCTCN2021093030-appb-000007
At least one of
R 3与R 4彼此独立地选自H、OH、-BO 3H、-SiO 3H、-PO 4H 2、-SO 3H、-ClO 4、-SO 3(CF 3)、
Figure PCTCN2021093030-appb-000008
中的至少一种； R 3 and R 4 are independently selected from H, OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 (CF 3 ),
Figure PCTCN2021093030-appb-000008
At least one of
n、x和y相同或不同，彼此独立地选自1-4的整数。n, x and y are the same or different, and are independently selected from an integer of 1-4.
示例性地，R 1选自H、
Figure PCTCN2021093030-appb-000009
R 2选自H；R 3选自H或
Figure PCTCN2021093030-appb-000010
R 4选自-SO 3H； Exemplarily, R 1 is selected from H,
Figure PCTCN2021093030-appb-000009
R 2 is selected from H; R 3 is selected from H or
Figure PCTCN2021093030-appb-000010
R 4 is selected from -SO 3 H;
n＝1、2或3；x＝1或3；y＝1。n=1, 2 or 3; x=1 or 3; y=1.
根据本发明的实施方案，所述多孔聚合物的聚合单体包括醛类单体和胺类单体，所述醛类单体具有如式2所示的结构：According to an embodiment of the present invention, the polymerized monomers of the porous polymer include aldehyde monomers and amine monomers, and the aldehyde monomers have a structure as shown in Formula 2:
Figure PCTCN2021093030-appb-000011
Figure PCTCN2021093030-appb-000011
所述胺类单体具有如式3所示的结构：The amine monomer has a structure shown in formula 3:
Figure PCTCN2021093030-appb-000012
Figure PCTCN2021093030-appb-000012
其中，R 1、R 2、R 3、R 4以及n具有如上文所述的含义。 Wherein, R 1 , R 2 , R 3 , R 4 and n have the meanings as described above.
根据本发明的优选技术方案，所述醛类单体中不含胺基取代基，所述胺类单体中不含醛基取代基。According to a preferred technical solution of the present invention, the aldehyde monomer does not contain an amine group substituent, and the amine monomer does not contain an aldehyde group substituent.
根据本发明的实施方案，所述醛类单体中，R 1与R 2彼此独立地选自H、-OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
Figure PCTCN2021093030-appb-000013
中的至少一种； According to an embodiment of the present invention, in the aldehyde monomer, R 1 and R 2 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
Figure PCTCN2021093030-appb-000013
At least one of
R 5和R 6具有如上文的含义；n、x和y相同或不同，彼此独立地选自1-4的整数。 R 5 and R 6 have the same meanings as above; n, x and y are the same or different, and are independently selected from an integer of 1-4.
优选地，所述醛类单体中，R 1选自H、
Figure PCTCN2021093030-appb-000014
R 2选自H。 Preferably, in the aldehyde monomer, R 1 is selected from H,
Figure PCTCN2021093030-appb-000014
R 2 is selected from H.
根据本发明的实施方案，所述胺类单体中，R 3与R 4彼此独立地选自H、-OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
Figure PCTCN2021093030-appb-000015
中的至少一种； According to an embodiment of the present invention, in the amine monomer, R 3 and R 4 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
Figure PCTCN2021093030-appb-000015
At least one of
R 5和R 6具有如上文的含义；n、x和y相同或不同，彼此独立地选自1-4的整数。 R 5 and R 6 have the same meanings as above; n, x and y are the same or different, and are independently selected from an integer of 1-4.
优选地，所述胺类单体中，R 3选自H或
Figure PCTCN2021093030-appb-000016
R 4选自-SO 3H。 Preferably, in the amine monomer, R 3 is selected from H or
Figure PCTCN2021093030-appb-000016
R 4 is selected from -SO 3 H.
根据本发明的实施方案，所述醛类单体可以选自
Figure PCTCN2021093030-appb-000017
Figure PCTCN2021093030-appb-000018
According to an embodiment of the present invention, the aldehyde monomer may be selected from
Figure PCTCN2021093030-appb-000017
Figure PCTCN2021093030-appb-000018
根据本发明的实施方案，所述胺类单体可以选自
Figure PCTCN2021093030-appb-000019
Figure PCTCN2021093030-appb-000020
等。 According to an embodiment of the present invention, the amine monomer may be selected from
Figure PCTCN2021093030-appb-000019
Figure PCTCN2021093030-appb-000020
Wait.
根据本发明的实施方案，所述多孔聚合物的比表面积为150-3000m 2g -1，例如为500-2000m 2g -1，又如为1000-1500m 2g -1，示例性为500m 2g -1、570m 2g -1、583m 2g -1、600m 2g -1、620m 2g -1、750m 2g -1、1000m 2g -1、1200m 2g -1、1500m 2g -1、2000m 2g -1。 According to an embodiment of the present invention, the specific surface area of the porous polymer is 150-3000m 2 g -1, for example 500-2000m 2 g -1, and if of 1000-1500m 2 g -1, exemplary of 500m 2 g -1, 570m 2 g -1, 583m 2 g -1, 600m 2 g -1, 620m 2 g -1, 750m 2 g -1, 1000m 2 g -1, 1200m 2 g -1, 1500m 2 g - 1. 2000m 2 g -1 .
根据本发明的实施方案，所述多孔聚合物的孔体积为0.1-2cm 3g -1，例如为0.2-1.5cm 3g -1，又如为0.5-1.2cm 3g -1，示例性为0.5cm 3g -1、0.7cm 3g -1、0.85cm 3g -1、0.9cm 3g -1、0.92cm 3g -1、0.96cm 3g -1、1.1cm 3g -1、1.3cm 3g -1、1.5cm 3g -1。 According to an embodiment of the present invention, the pore volume of the porous polymer is 0.1-2 cm 3 g -1 , for example, 0.2-1.5 cm 3 g -1 , or 0.5-1.2 cm 3 g -1 , exemplarily 0.5cm 3 g -1 , 0.7cm 3 g -1 , 0.85cm 3 g -1 , 0.9cm 3 g -1 , 0.92cm 3 g -1 , 0.96cm 3 g -1 , 1.1cm 3 g -1 , 1.3 cm 3 g -1 , 1.5cm 3 g -1 .
根据本发明的实施方案，所述多孔聚合物的平均孔径为0.25-5nm，例如为0.5-3nm，又如为1-2nm，示例性为0.7nm、0.9nm、1.2nm、1.3nm、1.4nm、1.5nm、1.7nm、2nm。According to an embodiment of the present invention, the average pore diameter of the porous polymer is 0.25-5nm, such as 0.5-3nm, or 1-2nm, exemplarily 0.7nm, 0.9nm, 1.2nm, 1.3nm, 1.4nm , 1.5nm, 1.7nm, 2nm.
根据本发明的实施方案，所述多孔聚合物具有基本如图1所示的形貌。According to an embodiment of the present invention, the porous polymer has a morphology substantially as shown in FIG. 1.
本发明还提供所述多孔聚合物的制备方法，包括如下步骤：含有胺类单体和醛类单体的反应原料在真空条件下反应，得到所述多孔聚合物；The present invention also provides a method for preparing the porous polymer, which includes the following steps: reacting raw materials containing amine monomers and aldehyde monomers under vacuum conditions to obtain the porous polymer;
所述胺类单体和醛类单体具有如上文所述的含义。The amine monomer and aldehyde monomer have the meanings as described above.
根据本发明的实施方案，所述醛类单体和胺类单体的摩尔比为(0.1-10):1，优选为(0.2-8):1，更优选为(0.5-5):1，示例性为0.5:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1。According to an embodiment of the present invention, the molar ratio of the aldehyde monomer to the amine monomer is (0.1-10):1, preferably (0.2-8):1, more preferably (0.5-5):1 Exemplified are 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1.
根据本发明的实施方案，所述反应原料包括溶剂。例如，所述溶剂选自丁醇、甲苯、二氯苯、均三甲苯、乙酰胺、二氧六环酸中的至少一种，所述酸为醋酸和/或三氟乙酸；所述溶剂优选为丁醇、二氯苯和醋酸的混合溶剂。According to an embodiment of the present invention, the reaction raw material includes a solvent. For example, the solvent is selected from at least one of butanol, toluene, dichlorobenzene, mesitylene, acetamide, and dioxane acid, and the acid is acetic acid and/or trifluoroacetic acid; the solvent is preferably It is a mixed solvent of butanol, dichlorobenzene and acetic acid.
根据本发明的实施方案，所述混合溶剂中，丁醇和二氯苯与醋酸的体积比为(2-30):(4-50):1，优选为(3-15):(5-25):1，更优选为(2-5):(4-12):1，示例性为2:4:1。According to an embodiment of the present invention, the volume ratio of butanol and dichlorobenzene to acetic acid in the mixed solvent is (2-30):(4-50):1, preferably (3-15):(5-25) ):1, more preferably (2-5):(4-12):1, and exemplary 2:4:1.
根据本发明的实施方案，所述反应的温度为25-200℃，例如为60-200℃，优选为80-160℃，示例性为100℃、120℃、150℃。According to an embodiment of the present invention, the temperature of the reaction is 25-200°C, for example 60-200°C, preferably 80-160°C, exemplarily 100°C, 120°C, 150°C.
根据本发明的实施方案，所述反应的时间为2-200小时，例如5-100小时，示例性为10小时、20小时、40小时、60小时、72小时。According to an embodiment of the present invention, the reaction time is 2-200 hours, such as 5-100 hours, and exemplarily 10 hours, 20 hours, 40 hours, 60 hours, 72 hours.
根据本发明的实施方案，所述反应的升温速度为2-10℃min -1，例如3-8℃min -1，示例性为4℃min -1，5℃min -1，6℃min -1。 According to an embodiment of the present invention, the reaction temperature rising rate is 2-10 ℃ min -1, e.g. 3-8 ℃ min -1, for the exemplary 4 ℃ min -1, 5 ℃ min -1, 6 ℃ min - 1 .
根据本发明的实施方案，所述多孔聚合物的制备方法，包括如下步骤：将所述胺类单体和醛类单体分散于丁醇、二氯苯和醋酸的混合溶剂中，在真空条件下反应，得到所述多孔聚合物。According to an embodiment of the present invention, the method for preparing the porous polymer includes the following steps: dispersing the amine monomer and aldehyde monomer in a mixed solvent of butanol, dichlorobenzene and acetic acid, and under vacuum conditions The next reaction is to obtain the porous polymer.
本发明还提供由上述方法制备得到的多孔聚合物。The present invention also provides a porous polymer prepared by the above method.
本发明还提供所述多孔聚合物作为锂-硫电池正极基体材料的应用。The present invention also provides the application of the porous polymer as a positive electrode matrix material of a lithium-sulfur battery.
本发明还提供一种多孔聚合物-硫复合材料，其含有上述任一项的多孔聚合物和硫。The present invention also provides a porous polymer-sulfur composite material, which contains any one of the above-mentioned porous polymers and sulfur.
根据本发明的实施方案，所述多孔聚合物-硫复合材料中，所述硫以晶态和无定形态中的至少一种形式均匀分散于所述多孔聚合物的孔道和表面。例如，所述硫以分子聚集态形式均匀分散于所述多孔聚合物的孔道和表面。According to an embodiment of the present invention, in the porous polymer-sulfur composite material, the sulfur is uniformly dispersed in the pores and surface of the porous polymer in at least one of a crystalline state and an amorphous state. For example, the sulfur is uniformly dispersed in the pores and surface of the porous polymer in the form of molecular aggregation.
根据本发明的实施方案，基于所述复合材料，所述硫在所述多孔聚合物-硫复合材料中的质量百分数为50-95％，优选为60-90％，更优选为70-80％，示例性为50％、60％、70％、71％、72％、74％、75％、77％、80％、90％。According to an embodiment of the present invention, based on the composite material, the mass percentage of the sulfur in the porous polymer-sulfur composite material is 50-95%, preferably 60-90%, more preferably 70-80% Exemplified are 50%, 60%, 70%, 71%, 72%, 74%, 75%, 77%, 80%, 90%.
根据本发明的实施方案，所述多孔聚合物-硫复合材料具有基本如图3所示的 形貌。According to an embodiment of the present invention, the porous polymer-sulfur composite material has a morphology substantially as shown in FIG. 3.
本发明还提供所述多孔聚合物-硫复合材料的制备方法，包括如下步骤：将硫与多孔聚合物分散于溶剂中，加热蒸干溶剂后真空干燥，得到所述多孔聚合物-硫复合材料。The present invention also provides a method for preparing the porous polymer-sulfur composite material, which includes the following steps: dispersing sulfur and the porous polymer in a solvent, heating to evaporate the solvent and vacuum drying to obtain the porous polymer-sulfur composite material .
根据本发明的实施方案，所述溶剂为二硫化碳、四氯化碳、乙二胺、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、二甲基乙醚和水中的至少一种；优选为二硫化碳、乙二胺、N-甲基吡咯烷酮或N,N-二甲基甲酰胺。According to an embodiment of the present invention, the solvent is carbon disulfide, carbon tetrachloride, ethylene diamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ether and water At least one of; preferably carbon disulfide, ethylenediamine, N-methylpyrrolidone or N,N-dimethylformamide.
根据本发明的实施方案，所述硫与多孔聚合物的质量比为(2-20):1，比如为(10-20):1，例如(12-18):1，示例性为5:2、12:1、14:1、15:1、17:1、18:1。According to an embodiment of the present invention, the mass ratio of the sulfur to the porous polymer is (2-20):1, such as (10-20):1, such as (12-18):1, and exemplarily 5: 2, 12:1, 14:1, 15:1, 17:1, 18:1.
根据本发明的实施方案，本领域技术人员能够理解，对所述溶剂的用量不做特别限定，以能够充分分散硫和多孔聚合物为佳。例如，所述溶剂的用量可以为所述多孔聚合物质量的100-500倍，优选200-400倍，示例性为200倍、300倍或400倍。According to the embodiments of the present invention, those skilled in the art can understand that the amount of the solvent is not particularly limited, and it is preferable that the sulfur and the porous polymer can be fully dispersed. For example, the amount of the solvent may be 100-500 times the mass of the porous polymer, preferably 200-400 times, and exemplarily 200 times, 300 times, or 400 times.
根据本发明的实施方案，所述加热和真空干燥的温度相同或不同，例如温度为50-250℃，优选50-180℃，更优选为80-150℃，示例性为60℃、80℃、100℃、120℃。According to an embodiment of the present invention, the heating and vacuum drying temperatures are the same or different, for example, the temperature is 50-250°C, preferably 50-180°C, more preferably 80-150°C, exemplarily 60°C, 80°C, 100°C, 120°C.
根据本发明的实施方案，所述真空干燥的时间为6-24小时，优选10-12小时，示例性为10小时、12小时、15小时、20小时。According to an embodiment of the present invention, the vacuum drying time is 6-24 hours, preferably 10-12 hours, and exemplarily 10 hours, 12 hours, 15 hours, and 20 hours.
根据本发明的实施方案，所述方法还包括：真空干燥后，冷却，得到所述多孔聚合物-硫复合材料。According to an embodiment of the present invention, the method further includes: after vacuum drying, cooling to obtain the porous polymer-sulfur composite material.
本发明还提供由上述方法制备得到的多孔聚合物-硫复合材料。The present invention also provides a porous polymer-sulfur composite material prepared by the above method.
本发明还提供所述多孔聚合物-硫复合材料在锂-硫电池中的应用，优选作为锂-硫电池正极中的活性物质。The present invention also provides the application of the porous polymer-sulfur composite material in a lithium-sulfur battery, preferably as an active material in the positive electrode of a lithium-sulfur battery.
本发明提供一种复合电极，其包括上述多孔聚合物-硫复合材料。The present invention provides a composite electrode, which includes the above-mentioned porous polymer-sulfur composite material.
根据本发明的实施方案，所述复合电极中还包括导电添加剂和粘结剂。其中，所述导电添加剂选自炭黑、super-P、科琴黑和碳纳米管中的至少一种，优 选为炭黑、super-P、科琴黑或碳纳米管。其中，所述粘结剂选自聚偏氟乙烯(PVDF)、聚丙烯酸(PAA)、丁苯橡胶/羧甲基纤维素钠(SBR/CMC)、和海藻酸钠(SA)中的至少一种，优选为丁苯橡胶/羧甲基纤维素钠(SBR/CMC)。According to an embodiment of the present invention, the composite electrode further includes a conductive additive and a binder. Wherein, the conductive additive is selected from at least one of carbon black, super-P, Ketjen black and carbon nanotubes, preferably carbon black, super-P, Ketjen black or carbon nanotubes. Wherein, the binder is selected from at least one of polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), styrene butadiene rubber/sodium carboxymethyl cellulose (SBR/CMC), and sodium alginate (SA) Species, preferably styrene-butadiene rubber/sodium carboxymethyl cellulose (SBR/CMC).
根据本发明的实施方案，所述多孔聚合物-硫复合材料、导电添加剂和粘结剂的质量比为(4-8):(1-5):1，例如(5-7):(2-4):1，示例性为6:3:1。According to an embodiment of the present invention, the mass ratio of the porous polymer-sulfur composite material, the conductive additive and the binder is (4-8):(1-5):1, for example (5-7):(2) -4):1, 6:3:1 as an example.
根据本发明的实施方案，所述复合电极还包括集流体。其中，所述集流体可以选自本领域已知的集流体，例如选自铝箔、铜箔、涂炭铝箔、涂炭铜箔、镀锡铝箔、镀铜铝箔或碳布。According to an embodiment of the present invention, the composite electrode further includes a current collector. Wherein, the current collector can be selected from current collectors known in the art, for example, selected from aluminum foil, copper foil, carbon-coated aluminum foil, carbon-coated copper foil, tin-plated aluminum foil, copper-plated aluminum foil, or carbon cloth.
根据本发明的实施方案，所述复合电极中，多孔聚合物-硫复合材料、导电添加剂和粘结剂的混合料负载在所述集流体上。According to an embodiment of the present invention, in the composite electrode, a mixture of a porous polymer-sulfur composite material, a conductive additive, and a binder is supported on the current collector.
本发明还提供所述复合电极的制备方法，包括如下步骤：将所述多孔聚合物-硫复合材料、粘结剂、导电添加剂和溶剂混合均匀，制备得到的浆料经涂片、干燥，得到所述复合电极。The present invention also provides a method for preparing the composite electrode, which includes the following steps: uniformly mixing the porous polymer-sulfur composite material, binder, conductive additive and solvent, and the prepared slurry is coated and dried to obtain The composite electrode.
根据本发明的实施方案，所述多孔聚合物-硫复合材料、粘结剂和导电添加剂的质量比具有如上文所述的含义。According to the embodiment of the present invention, the mass ratio of the porous polymer-sulfur composite material, the binder, and the conductive additive has the meaning as described above.
根据本发明的实施方案，所述溶剂为二硫化碳、乙二胺、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、二甲基乙醚和水中的至少一种；优选为二硫化碳、乙二胺、水、N-甲基吡咯烷酮或N,N-二甲基甲酰胺。进一步地，溶剂的用量以能形成本领域常用浓度的浆料即可。According to an embodiment of the present invention, the solvent is at least one of carbon disulfide, ethylenediamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ether and water; Preferably, it is carbon disulfide, ethylenediamine, water, N-methylpyrrolidone or N,N-dimethylformamide. Further, the amount of the solvent can be used to form a slurry with a common concentration in the field.
根据本发明的实施方案，所述涂片、干燥为本领域已知操作。According to an embodiment of the present invention, the smearing and drying are operations known in the art.
本发明还提供一种锂-硫电池，其包括上述复合电极。The present invention also provides a lithium-sulfur battery, which includes the above-mentioned composite electrode.
根据本发明的实施方案，所述锂-硫电池包括金属锂负极、作为正极的所述复合电极和电解液。According to an embodiment of the present invention, the lithium-sulfur battery includes a metal lithium negative electrode, the composite electrode as a positive electrode, and an electrolyte.
根据本发明的实施方案，所述电解质选自液体电解质和/或固体电解质。According to an embodiment of the present invention, the electrolyte is selected from liquid electrolytes and/or solid electrolytes.
其中，所述液体电解质为醚类电解液。例如，所述醚类电解液的浓度为0.1-20mol/L，优选为1-10mol/L，示例性为1mol/L、3mol/L、5mol/L、8mol/L。Wherein, the liquid electrolyte is an ether type electrolyte. For example, the concentration of the ether electrolyte is 0.1-20 mol/L, preferably 1-10 mol/L, and exemplarily 1 mol/L, 3 mol/L, 5 mol/L, 8 mol/L.
其中，所述醚类电解液中的溶剂选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、丙烯碳酸酯(PC)、氟代亚乙烯碳酸酯(FEC)、1,3-二氧戊烷(DOL)、乙二醇二甲醚(DME)和三乙二醇二甲醚(TEGDME)中的至少一种，例如为碳酸二乙酯、丙烯碳酸酯、1,3-二氧戊烷和乙二醇二甲醚中的至少一种，示例性选自1,3-二氧戊烷和乙二醇二甲醚的混合溶剂、丙烯碳酸酯和乙二醇二甲醚的混合溶剂。Wherein, the solvent in the ether electrolyte is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), fluoroethylene carbonate (FEC), 1,3- At least one of dioxolane (DOL), ethylene glycol dimethyl ether (DME), and triethylene glycol dimethyl ether (TEGDME), such as diethyl carbonate, propylene carbonate, 1,3-di At least one of oxypentane and ethylene glycol dimethyl ether, exemplarily selected from mixed solvents of 1,3-dioxolane and ethylene glycol dimethyl ether, propylene carbonate and ethylene glycol dimethyl ether Mixed solvents.
其中，所述醚类电解液中的溶质选自六氟磷酸锂(LiPF 6)、高氯酸锂(LiClO 4)、硝酸锂(LiNO 3)、双草酸硼酸锂(LiBOB)、(三氟甲基)磺酸锂(LiFSI)和二(三氟甲基)磺酸锂(LiTFSI)中的至少一种；例如为二(三氟甲基)磺酸锂、(三氟甲基)磺酸锂和六氟磷酸锂中的至少一种；示例性为二(三氟甲基)磺酸锂。 Wherein, the solute in the ether electrolyte is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium nitrate (LiNO 3 ), lithium bisoxalate borate (LiBOB), (trifluoromethyl) sulfonate At least one of lithium sulfonate (LiFSI) and lithium bis(trifluoromethyl)sulfonate (LiTFSI); for example, lithium bis(trifluoromethyl)sulfonate, lithium (trifluoromethyl)sulfonate and lithium hexafluorophosphate At least one of; exemplified is lithium bis(trifluoromethyl)sulfonate.
根据本发明的实施方案，所述固体电解质选自无机固态电解质和聚合物电解质中的至少一种。其中，所述聚合物电解质可以为凝胶聚合物电解质和/或固态聚合物电解质。According to an embodiment of the present invention, the solid electrolyte is selected from at least one of inorganic solid electrolytes and polymer electrolytes. Wherein, the polymer electrolyte may be a gel polymer electrolyte and/or a solid polymer electrolyte.
例如，所述无机固态电解质选自至少一种固态陶瓷电解质。For example, the inorganic solid electrolyte is selected from at least one solid ceramic electrolyte.
例如，所述聚合物电解质选自聚环氧乙烷(PEO)、聚乙二醇二甲醚(PEGDME)、偏二氟乙烯与六氟丙烯的共聚物(PVDF-HFP)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)中的至少一种，例如为聚环氧乙烷和/或聚乙二醇二甲醚。For example, the polymer electrolyte is selected from polyethylene oxide (PEO), polyethylene glycol dimethyl ether (PEGDME), copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), ethoxylated At least one of trimethylolpropane triacrylate (ETPTA) is, for example, polyethylene oxide and/or polyethylene glycol dimethyl ether.
本发明还提供所述锂-硫电池的制备方法，所述方法包括将所述金属锂负极、作为正极的所述复合电极和电解液组装，得到所述锂-硫电池。The present invention also provides a method for preparing the lithium-sulfur battery, which includes assembling the metal lithium negative electrode, the composite electrode as a positive electrode, and an electrolyte to obtain the lithium-sulfur battery.
本发明还提供所述锂-硫电池在制备储能器件中的应用。The invention also provides the application of the lithium-sulfur battery in the preparation of energy storage devices.
本发明还提供一种储能器件，其含有上述锂-硫电池。The present invention also provides an energy storage device, which contains the above-mentioned lithium-sulfur battery.
本发明的有益效果：The beneficial effects of the present invention:
本发明提供的多孔聚合物比表面积大、孔体积高，使得硫在多孔聚合物中 的负载量高。其由醛、胺单体按配比反应得到，以该多孔聚合物为基体材料，将溶剂溶解的硫灌入多孔聚合物中，制得多孔聚合物-硫复合材料，其中硫均匀地分散于聚合物孔道和表面，由于多孔聚合物表现出强的多硫离子吸附作用，可以抑制多硫离子在充放电过程中的穿梭，使得锂-硫电池具有高的库伦效率。The porous polymer provided by the present invention has a large specific surface area and a high pore volume, so that the sulfur loading in the porous polymer is high. It is obtained by reacting aldehyde and amine monomers in proportions. Using the porous polymer as the matrix material, the solvent-dissolved sulfur is poured into the porous polymer to prepare a porous polymer-sulfur composite material, in which the sulfur is uniformly dispersed in the polymer Because the porous polymer exhibits a strong polysulfide ion adsorption effect on the material pores and surface, it can inhibit the shuttle of polysulfide ions during the charge and discharge process, so that the lithium-sulfur battery has a high coulombic efficiency.
多孔聚合物-硫复合材料应用于锂-硫电池正极时，获得的多孔聚合物-硫复合正极及对应的锂-硫电池具有高的放电比容量和优异的循环稳定性。例如，所述锂-硫电池在0.5C倍率下的循环性能，经过50圈后，电池放电容量仍保持在901mA h g -1。 When the porous polymer-sulfur composite material is applied to the positive electrode of a lithium-sulfur battery, the obtained porous polymer-sulfur composite positive electrode and the corresponding lithium-sulfur battery have high specific discharge capacity and excellent cycle stability. For example, the cycle performance of the lithium-sulfur battery at a rate of 0.5C, after 50 cycles, the battery discharge capacity remains at 901 mA h g -1 .
本发明提供的多孔聚合物以及多孔聚合物-硫复合材料的制备方法简单，原料易得，适用于大规模生产，实用化程度高。The preparation method of the porous polymer and the porous polymer-sulfur composite material provided by the invention is simple, the raw materials are easily available, are suitable for large-scale production, and have a high degree of practicality.
本发明的锂-硫电池有望作为一种新型的高能量密度储能器件，具有良好的应用前景。The lithium-sulfur battery of the present invention is expected to be a new type of high-energy density energy storage device and has good application prospects.
附图说明Description of the drawings
图1为实施例1的所述多孔聚合物的扫描电镜图(标尺10μm)。Figure 1 is a scanning electron microscope image of the porous polymer of Example 1 (scale 10 μm).
图2为实施例1的所述多孔聚合物的红外光谱图。FIG. 2 is an infrared spectrum diagram of the porous polymer of Example 1. FIG.
图3为实施例1的所述多孔聚合物-硫复合材料的扫描电镜图(标尺10μm)。Fig. 3 is a scanning electron micrograph of the porous polymer-sulfur composite material of Example 1 (scale bar 10 μm).
图4为实施例1的所述锂-硫电池在醚类电解液中的循环伏安曲线。4 is a cyclic voltammetry curve of the lithium-sulfur battery of Example 1 in an ether electrolyte.
图5为实施例1的所述锂-硫电池在醚类电解液中的充放电曲线。Fig. 5 is a charging and discharging curve of the lithium-sulfur battery of Example 1 in an ether electrolyte.
图6为实施例1的所述锂-硫电池在醚类电解液中的循环稳定性。Fig. 6 shows the cycle stability of the lithium-sulfur battery of Example 1 in an ether electrolyte.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are merely illustrative and explanation of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
实施例1Example 1
(一)多孔聚合物的制备(1) Preparation of porous polymer
单体I为醛类单体，R 1与R 2都为H，n＝1
Figure PCTCN2021093030-appb-000021
Monomer I is an aldehyde monomer, R 1 and R 2 are both H, n=1
Figure PCTCN2021093030-appb-000021
单体II为胺类单体，R 3为H，R 4为-SO 3H，n＝1
Figure PCTCN2021093030-appb-000022
Monomer II is an amine monomer, R 3 is H, R 4 is -SO 3 H, n=1
Figure PCTCN2021093030-appb-000022
将单体I与单体II为按照1:1的摩尔比进行称重，分散于体积比为2:4:1的丁醇、二氯苯和醋酸的混合溶剂中，封管抽真空后以5℃min -1升温至120℃，保温反应72小时，得到多孔聚合物(图1)。结合红外谱图(图2)分析不难发现，单体I与单体II反应形成亚胺键，得到多孔聚合物。所得多孔聚合物的比表面积为500m 2g -1，孔体积为0.9cm 3g -1，孔径为1.4nm。 The monomer I and monomer II are weighed according to the molar ratio of 1:1, and dispersed in a mixed solvent of butanol, dichlorobenzene and acetic acid with a volume ratio of 2:4:1. The tube is sealed and vacuumed. The temperature was raised to 120°C at 5°C min -1 , and the reaction was kept for 72 hours to obtain a porous polymer (Figure 1). Combined with the analysis of the infrared spectrum (Figure 2), it is not difficult to find that monomer I reacts with monomer II to form an imine bond to obtain a porous polymer. The specific surface area of the obtained porous polymer is 500 m 2 g -1 , the pore volume is 0.9 cm 3 g -1 , and the pore diameter is 1.4 nm.
(二)多孔聚合物-硫复合材料的制备(2) Preparation of porous polymer-sulfur composite material
将上述多孔聚合物与硫按照15:1的质量比称重，于二硫化碳中进行超声分散3小时，随后于80℃蒸干溶剂，再以80℃进行真空干燥10小时，冷却后得到多孔聚合物-硫复合材料(图3)。The porous polymer and sulfur were weighed at a mass ratio of 15:1, and dispersed in carbon disulfide ultrasonically for 3 hours, then the solvent was evaporated to dryness at 80°C, and then vacuum dried at 80°C for 10 hours. After cooling, the porous polymer was obtained. -Sulfur composite material (Figure 3).
制备的多孔聚合物-硫复合材料中，硫以分子聚集态均匀分散于多孔聚合物孔道和表面；硫在多孔聚合物-硫复合材料中的质量百分数约为72％。In the prepared porous polymer-sulfur composite material, sulfur is uniformly dispersed in the pores and surfaces of the porous polymer in a molecular aggregate state; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 72%.
(三)多孔聚合物-硫复合正极的制备(3) Preparation of porous polymer-sulfur composite cathode
将上述得到的多孔聚合物-硫复合材料与导电添加剂super P、粘结剂丁苯橡胶/羧甲基纤维素钠按质量比6:3:1混匀，与水混合制成浆料，再经涂片、干燥等处理工艺得到多孔聚合物-硫复合正极。The porous polymer-sulfur composite material obtained above is mixed with the conductive additive super P, the binder styrene-butadiene rubber/sodium carboxymethyl cellulose at a mass ratio of 6:3:1, and mixed with water to form a slurry. The porous polymer-sulfur composite positive electrode is obtained through treatment processes such as coating and drying.
(四)锂-硫电池的组装与测试(4) Assembly and testing of lithium-sulfur batteries
将上述获得的多孔聚合物-硫复合正极与锂片、醚类电解液(1M LiTFSI+1％LiNO 3的DOL-DME(DOL与DME的质量比1:1)溶液)组装锂-硫电池。将得到的锂-硫电池在室温下进行循环伏安(图4)和恒流充放电测试(图5)，充放电截止电压为1.8-2.8V，充放电电流均以硫的质量按理论比容量1675mA h g -1进行计算得到。图4所示为锂-硫电池在醚类电解质中前三周的循环伏安图(扫速为0.05mV s -1)，图中显示两对氧化还原峰，分别在靠近2.05/2.3V和2.28/2.36V处。图5为所述锂-硫电池在0.1C、0.2C、0.5C、1C倍率下的充放电曲线，放电比容量分别为1636、1343、1032、841mA h g -1(1C＝1675mA g -1)。图6为所述锂-硫电池在0.5C倍率下的循环性能，经过50圈后，电池放电容量仍保持在901mA h g -1，表明制备的锂-硫电池具有优异的放电比容量和循环稳定性。 A lithium-sulfur battery is assembled with the porous polymer-sulfur composite positive electrode obtained above, a lithium sheet, and an ether electrolyte (1M LiTFSI+1% LiNO 3 DOL-DME (DOL to DME mass ratio 1:1) solution). The obtained lithium-sulfur battery was subjected to cyclic voltammetry (Figure 4) and constant current charge-discharge test (Figure 5) at room temperature. The charge-discharge cut-off voltage was 1.8-2.8V, and the charge-discharge current was based on the theoretical ratio of sulfur mass. The capacity is 1675mA hg -1 calculated. Figure 4 shows the cyclic voltammogram of the lithium-sulfur battery in the ether electrolyte for the first three weeks (the sweep rate is 0.05mV s -1 ). The figure shows two pairs of redox peaks, respectively near 2.05/2.3V and 2.28/2.36V. Figure 5 shows the charging and discharging curves of the lithium-sulfur battery at 0.1C, 0.2C, 0.5C, and 1C rates, and the specific discharge capacities are 1636, 1343, 1032, 841mA h g -1 (1C=1675mA g -1 ) . Figure 6 shows the cycle performance of the lithium-sulfur battery at a rate of 0.5C. After 50 cycles, the battery discharge capacity remains at 901mA h g -1 , indicating that the prepared lithium-sulfur battery has excellent discharge specific capacity and cycle stability sex.
实施例2Example 2
其他与实施例1相同，不同之处在于：Others are the same as Example 1, the difference is:
单体I中R 1为
Figure PCTCN2021093030-appb-000023
R 2为H，n＝1
Figure PCTCN2021093030-appb-000024
 R 1 in monomer I is
Figure PCTCN2021093030-appb-000023
R 2 is H, n=1
Figure PCTCN2021093030-appb-000024
单体II中R 3为H，R 4为-SO 3H，n＝1
Figure PCTCN2021093030-appb-000025
In monomer II, R 3 is H, R 4 is -SO 3 H, n=1
Figure PCTCN2021093030-appb-000025
所得多孔聚合物的比表面积为620m 2g -1，孔体积为0.85cm 3g -1，孔径为1.2nm；硫在多孔聚合物-硫复合材料中的质量百分数约为70％。 The specific surface area of the obtained porous polymer is 620 m 2 g -1 , the pore volume is 0.85 cm 3 g -1 , and the pore diameter is 1.2 nm; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 70%.
所制得的锂-硫电池经实施例1同样的测试方法，0.1C放电比容量为1608mA h g -1，50圈后放电比容量为882mA h g -1。 The prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1608 mA h g -1 , and the specific discharge capacity after 50 cycles was 882 mA h g -1 .
实施例3Example 3
其他与实施例1相同，不同之处在于：Others are the same as Example 1, the difference is:
单体I中R 1为
Figure PCTCN2021093030-appb-000026
R 2为H，n＝1
Figure PCTCN2021093030-appb-000027
 R 1 in monomer I is
Figure PCTCN2021093030-appb-000026
R 2 is H, n=1
Figure PCTCN2021093030-appb-000027
单体II中R 3为H，R 4为-SO 3H，n＝2
Figure PCTCN2021093030-appb-000028
In monomer II, R 3 is H, R 4 is -SO 3 H, n=2
Figure PCTCN2021093030-appb-000028
所得多孔聚合物的比表面积为570m 2g -1，孔体积为0.96cm 3g -1，孔径为1.3nm；硫在多孔聚合物-硫复合材料中的质量百分数约为77％。 The specific surface area of the obtained porous polymer is 570 m 2 g -1 , the pore volume is 0.96 cm 3 g -1 , and the pore diameter is 1.3 nm; the mass percentage of sulfur in the porous polymer-sulfur composite is about 77%.
所制得的锂-硫电池经实施例1同样的测试方法，0.1C放电比容量为1614mA h g -1，50圈后放电比容量为896mA h g -1。 The prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1614 mA h g -1 , and the specific discharge capacity after 50 cycles was 896 mA h g -1 .
实施例4Example 4
其他与实施例1相同，不同之处在于：Others are the same as Example 1, the difference is:
单体I中R 1为
Figure PCTCN2021093030-appb-000029
R 2为H，n＝3
Figure PCTCN2021093030-appb-000030
 R 1 in monomer I is
Figure PCTCN2021093030-appb-000029
R 2 is H, n=3
Figure PCTCN2021093030-appb-000030
单体II中R 3为
Figure PCTCN2021093030-appb-000031
R 4为-SO 3H，n＝1
Figure PCTCN2021093030-appb-000032
 R 3 in monomer II is
Figure PCTCN2021093030-appb-000031
R 4 is -SO 3 H, n=1
Figure PCTCN2021093030-appb-000032
所得多孔聚合物的比表面积为583m 2g -1，孔体积为0.92cm 3g -1，孔径为1.5nm；硫在多孔聚合物-硫复合材料中的质量百分数约为74％。 The specific surface area of the obtained porous polymer is 583 m 2 g -1 , the pore volume is 0.92 cm 3 g -1 , and the pore diameter is 1.5 nm; the mass percentage of sulfur in the porous polymer-sulfur composite is about 74%.
所制得的锂-硫电池经实施例1同样的测试方法，0.1C放电比容量为1624mA h g -1，50圈后放电比容量为906mA h g -1。 The prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1624 mA h g -1 , and the specific discharge capacity after 50 cycles was 906 mA h g -1 .
实施例5Example 5
其他与实施例1相同，不同之处在于电解液为(8M LiTFSI+1％LiNO 3的PC-DME(PC与DME的质量比1:1)溶液。 Others are the same as Example 1, except that the electrolyte is (8M LiTFSI+1% LiNO 3 PC-DME (PC to DME mass ratio 1:1) solution.
所制得的锂-硫电池经实施例1同样的测试方法，0.1C放电比容量为1594mA h g -1，50圈后放电比容量为884mA h g -1。 The prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1594 mA h g -1 , and the specific discharge capacity after 50 cycles was 884 mA h g -1 .
实施例6Example 6
其他与实施例1相同，不同之处在于电解质为含醚类电解液(1M LiTFSI+1％LiNO 3的DOL-DME(DOL与DME的质量比1:1)溶液)与PVDF-HFP组成的固态电解质。 Others are the same as Example 1, but the difference is that the electrolyte is a solid state composed of ether electrolyte (1M LiTFSI+1% LiNO 3 in DOL-DME (DOL to DME ratio 1:1) solution) and PVDF-HFP. Electrolyte.
所制得的锂-硫电池经实施例1同样的测试方法，0.1C放电比容量为1582mA h g -1，50圈后放电比容量为891mA h g -1。 The prepared lithium-sulfur battery was subjected to the same test method as in Example 1, and the specific discharge capacity at 0.1C was 1582 mA h g -1 , and the specific discharge capacity after 50 cycles was 891 mA h g -1 .
综上所述，本发明的锂-硫电池具有优异的放电能力和循环稳定性。In summary, the lithium-sulfur battery of the present invention has excellent discharge capacity and cycle stability.
实施例7Example 7
(一)多孔聚合物的制备(1) Preparation of porous polymer
单体I为醛类单体，R 1与R 2都为H，n＝1
Figure PCTCN2021093030-appb-000033
Monomer I is an aldehyde monomer, R 1 and R 2 are both H, n=1
Figure PCTCN2021093030-appb-000033
单体II为胺类单体，R 3为H，R 4为-SO 3H，n＝1
Figure PCTCN2021093030-appb-000034
Monomer II is an amine monomer, R 3 is H, R 4 is -SO 3 H, n=1
Figure PCTCN2021093030-appb-000034
将单体I与单体II为按照1:1的摩尔比进行称重，分散于丁醇和二氯苯与醋酸体积比为10:1的的混合溶剂中，封管抽真空后以5℃min -1升温至120℃，保温反应72小时，得到多孔聚合物(具有基本如图1所示的形貌)。同样，通过红外表征证明单体I与单体II反应形成亚胺键，得到多孔聚合物。 The monomer I and monomer II are weighed according to the molar ratio of 1:1, and dispersed in a mixed solvent of butanol and dichlorobenzene and acetic acid with a volume ratio of 10:1. The tube is sealed and vacuumed at 5℃min. -1 The temperature is raised to 120°C, and the reaction is kept for 72 hours to obtain a porous polymer (with a morphology as shown in Fig. 1). Similarly, infrared characterization proved that monomer I reacted with monomer II to form an imine bond to obtain a porous polymer.
(二)多孔聚合物-硫复合材料的制备(2) Preparation of porous polymer-sulfur composite material
将上述多孔聚合物与硫按照2:5的质量比称重，于二硫化碳中进行超声分散3小时，随后于80℃蒸干溶剂，再以80℃进行真空干燥10小时，冷却后得到多孔聚合物-硫复合材料(具有基本如图3所示的形貌)。The above porous polymer and sulfur were weighed according to the mass ratio of 2:5, and dispersed in carbon disulfide ultrasonically for 3 hours, then the solvent was evaporated to dryness at 80°C, and then vacuum dried at 80°C for 10 hours. After cooling, the porous polymer was obtained. -Sulfur composite material (has basically the morphology shown in Figure 3).
制备的多孔聚合物-硫复合材料中，硫以分子聚集态均匀分散于多孔聚合物孔道和表面；硫在多孔聚合物-硫复合材料中的质量百分数约为71％。In the prepared porous polymer-sulfur composite material, sulfur is uniformly dispersed in the pores and surfaces of the porous polymer in a molecular aggregate state; the mass percentage of sulfur in the porous polymer-sulfur composite material is about 71%.
参照实施例1中(三)多孔聚合物-硫复合正极的制备和(四)锂-硫电池的组装与测试，含有本实施例复合材料的锂-硫电池具有基本如实施例1锂-硫电池相同的电化学性能。With reference to (3) Preparation of porous polymer-sulfur composite positive electrode and (4) Assembly and test of lithium-sulfur battery in Example 1, the lithium-sulfur battery containing the composite material of this example has a lithium-sulfur battery substantially as in Example 1. The same electrochemical performance as the battery.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。In the foregoing, the embodiments of the present invention have been described. However, the present invention is not limited to the above-mentioned embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种多孔聚合物，其特征在于，所述聚合物具有如式1所示的结构：A porous polymer, characterized in that the polymer has a structure as shown in formula 1:
    Figure PCTCN2021093030-appb-100001
    Figure PCTCN2021093030-appb-100001
    其中，R 1、R 2、R 3、R 4相同或不同，各自独立地选自H、-OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
    Figure PCTCN2021093030-appb-100002
    Wherein, R 1 , R 2 , R 3 , and R 4 are the same or different, and are each independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
    Figure PCTCN2021093030-appb-100002
    其中，R 5选自B、Al、C、Si、Ge、N、P、As、S、Se、Cl、Br、I中的至少一种，R 6选自H、OH、-CN、-CF 3、-CH 3、-OCH 3、-OC 2H 5、
    Figure PCTCN2021093030-appb-100003
    Figure PCTCN2021093030-appb-100004
    中的至少一种；     Wherein, R 5 is selected from at least one of B, Al, C, Si, Ge, N, P, As, S, Se, Cl, Br, and I, and R 6 is selected from H, OH, -CN, -CF 3 , -CH 3 , -OCH 3 , -OC 2 H 5 ,
    Figure PCTCN2021093030-appb-100003
    Figure PCTCN2021093030-appb-100004
    At least one of
    n、x和y相同或不同，彼此独立地选自1-8的整数。n, x and y are the same or different, and are independently selected from an integer of 1-8.
  2. 根据权利要求1所述的多孔聚合物，其特征在于，R 1与R 2选自除
    Figure PCTCN2021093030-appb-100005
    之外的任一上述基团，R 3与R 4选自除
    Figure PCTCN2021093030-appb-100006
    之外的任一上述基团。     The porous polymer of claim 1, wherein R 1 and R 2 are selected from
    Figure PCTCN2021093030-appb-100005
    R 3 and R 4 are selected from any of the above groups other than
    Figure PCTCN2021093030-appb-100006
    Any of the above groups other than those listed above.
    优选地，R 1与R 2彼此独立地选自H、-OH、-BO 3H、-SiO 3H、-PO 4H 2、-SO 3H、-ClO 4、-SO 3(CF 3)、
    Figure PCTCN2021093030-appb-100007
    中的至少一种；     Preferably, R 1 and R 2 are independently selected from H, -OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 (CF 3 ) ,
    Figure PCTCN2021093030-appb-100007
    At least one of
    R 3与R 4彼此独立地选自H、-OH、-BO 3H、-SiO 3H、-PO 4H 2、-SO 3H、-ClO 4、-SO 3(CF 3)、
    Figure PCTCN2021093030-appb-100008
    中的至少一种；     R 3 and R 4 are independently selected from H, -OH, -BO 3 H, -SiO 3 H, -PO 4 H 2 , -SO 3 H, -ClO 4 , -SO 3 (CF 3 ),
    Figure PCTCN2021093030-appb-100008
    At least one of
    n、x和y相同或不同，彼此独立地选自1-4的整数。n, x and y are the same or different, and are independently selected from an integer of 1-4.
    优选地，R 1选自H、
    Figure PCTCN2021093030-appb-100009
    R 2选自H；R 3选自H或
    Figure PCTCN2021093030-appb-100010
    R 4选自-SO 3H；     Preferably, R 1 is selected from H,
    Figure PCTCN2021093030-appb-100009
    R 2 is selected from H; R 3 is selected from H or
    Figure PCTCN2021093030-appb-100010
    R 4 is selected from -SO 3 H;
    n＝1、2或3；x＝1或3；y＝1。n=1, 2 or 3; x=1 or 3; y=1.
  3. 根据权利要求1所述的多孔聚合物，其特征在于，所述多孔聚合物的聚合单体包括醛类单体和胺类单体，所述醛类单体具有如式2所示的结构：The porous polymer of claim 1, wherein the polymerized monomers of the porous polymer include aldehyde monomers and amine monomers, and the aldehyde monomers have a structure as shown in Formula 2:
    Figure PCTCN2021093030-appb-100011
    Figure PCTCN2021093030-appb-100011
    所述胺类单体具有如式3所示的结构：The amine monomer has a structure shown in formula 3:
    Figure PCTCN2021093030-appb-100012
    Figure PCTCN2021093030-appb-100012
    其中，R 1、R 2、R 3、R 4，以及n具有如权利要求1或2所述的含义。 Wherein, R 1 , R 2 , R 3 , R 4 , and n have the meanings described in claim 1 or 2.
    优选地，所述醛类单体中不含胺基取代基，所述胺类单体中不含醛基取代基。Preferably, the aldehyde monomer does not contain an amine group substituent, and the amine monomer does not contain an aldehyde group substituent.
    优选地，所述醛类单体中，R 1与R 2彼此独立地选自H、-OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
    Figure PCTCN2021093030-appb-100013
    中的至少一种；     Preferably, in the aldehyde monomer, R 1 and R 2 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
    Figure PCTCN2021093030-appb-100013
    At least one of
    R 5和R 6具有如权利要求1或2的含义；n、x和y相同或不同，彼此独立地选自1-4的整数。 R 5 and R 6 have the meanings of claim 1 or 2; n, x and y are the same or different, and are independently selected from an integer of 1-4.
    优选地，所述醛类单体中，R 1选自H、
    Figure PCTCN2021093030-appb-100014
    R 2选自H。     Preferably, in the aldehyde monomer, R 1 is selected from H,
    Figure PCTCN2021093030-appb-100014
    R 2 is selected from H.
    优选地，所述胺类单体中，R 3与R 4彼此独立地选自H、-OH、R 5O 3R 6、-PO 4H 2、-ClO 4、
    Figure PCTCN2021093030-appb-100015
    中的至少一种；     Preferably, in the amine monomer, R 3 and R 4 are independently selected from H, -OH, R 5 O 3 R 6 , -PO 4 H 2 , -ClO 4 ,
    Figure PCTCN2021093030-appb-100015
    At least one of
    R 5和R 6具有如权利要求1所述的含义；n、x和y相同或不同，彼此独立地选自1-4的整数。 R 5 and R 6 have the meanings described in claim 1; n, x and y are the same or different, and are independently selected from an integer of 1-4.
    优选地，所述胺类单体中，R 3选自H或
    Figure PCTCN2021093030-appb-100016
    R 4选自-SO 3H。     Preferably, in the amine monomer, R 3 is selected from H or
    Figure PCTCN2021093030-appb-100016
    R 4 is selected from -SO 3 H.
    优选地，所述醛类单体选自
    Figure PCTCN2021093030-appb-100017
    Figure PCTCN2021093030-appb-100018
    Preferably, the aldehyde monomer is selected from
    Figure PCTCN2021093030-appb-100017
    Figure PCTCN2021093030-appb-100018
    优选地，所述胺类单体选自
    Figure PCTCN2021093030-appb-100019
    Figure PCTCN2021093030-appb-100020
    Preferably, the amine monomer is selected from
    Figure PCTCN2021093030-appb-100019
    Figure PCTCN2021093030-appb-100020
    优选地，所述多孔聚合物的比表面积为150-3000m 2g -1。 Preferably, the specific surface area of the porous polymer is 150-3000 m 2 g -1 .
    优选地，所述多孔聚合物的孔体积为0.1-2cm 3g -1。 Preferably, the pore volume of the porous polymer is 0.1-2 cm 3 g -1 .
    优选地，所述多孔聚合物的平均孔径为0.25-5nm。Preferably, the average pore diameter of the porous polymer is 0.25-5 nm.
    优选地，所述多孔聚合物具有基本如图1所示的形貌。Preferably, the porous polymer has a morphology substantially as shown in FIG. 1.
  4. 权利要求1-3任一项所述多孔聚合物的制备方法，其特征在于，所述制备方法包括如下步骤：含有胺类单体和醛类单体的反应原料在真空条件下反应，得到所述多孔聚合物；The preparation method of the porous polymer according to any one of claims 1 to 3, characterized in that, the preparation method comprises the following steps: reacting raw materials containing amine monomers and aldehyde monomers under vacuum conditions to obtain the The porous polymer;
    所述胺类单体和醛类单体具有如权利要求3所述的含义。The amine monomers and aldehyde monomers have the meanings described in claim 3.
    优选地，所述醛类单体和胺类单体的摩尔比为(0.1-10):1。Preferably, the molar ratio of the aldehyde monomer to the amine monomer is (0.1-10):1.
    优选地，所述反应原料包括溶剂。优选地，所述溶剂选自丁醇、甲苯、二氯苯、均三甲苯、二氧六环和酸中的至少一种，所述酸为醋酸和/或三氟乙酸。优选所述溶剂为丁醇、二氯苯和醋酸的混合溶剂。Preferably, the reaction raw material includes a solvent. Preferably, the solvent is selected from at least one of butanol, toluene, dichlorobenzene, mesitylene, dioxane and acid, and the acid is acetic acid and/or trifluoroacetic acid. Preferably, the solvent is a mixed solvent of butanol, dichlorobenzene and acetic acid.
    优选地，所述混合溶剂中，丁醇和二氯苯与醋酸的体积比为(2-30):(4-50):1。Preferably, the volume ratio of butanol and dichlorobenzene to acetic acid in the mixed solvent is (2-30):(4-50):1.
    优选地，所述反应的温度为25-200℃。Preferably, the temperature of the reaction is 25-200°C.
    优选地，所述反应的时间为2-200小时。Preferably, the reaction time is 2-200 hours.
    优选地，所述反应的升温速度为2-10℃min -1。 Preferably, the heating rate of the reaction is 2-10°C min -1 .
  5. 一种多孔聚合物-硫复合材料，其特征在于，所述复合材料含有权利要求 1-3任一项所述多孔聚合物和硫。A porous polymer-sulfur composite material, characterized in that the composite material contains the porous polymer according to any one of claims 1-3 and sulfur.
    优选地，所述多孔聚合物-硫复合材料中，所述硫以晶态和无定形态中的至少一种形式均匀分散于所述多孔聚合物的孔道和表面。Preferably, in the porous polymer-sulfur composite material, the sulfur is uniformly dispersed in the pores and surface of the porous polymer in at least one of a crystalline state and an amorphous state.
    优选地，所述硫在所述多孔聚合物-硫复合材料中的质量百分数为50-95％。Preferably, the mass percentage of the sulfur in the porous polymer-sulfur composite material is 50-95%.
    优选地，所述多孔聚合物-硫复合材料具有基本如图3所示的形貌。Preferably, the porous polymer-sulfur composite material has a morphology substantially as shown in FIG. 3.
  6. 权利要求5所述多孔聚合物-硫复合材料的制备方法，其特征在于，所述制备方法包括如下步骤：将硫与多孔聚合物分散于溶剂中，加热蒸干溶剂后真空干燥，得到所述多孔聚合物-硫复合材料。The preparation method of the porous polymer-sulfur composite material according to claim 5, wherein the preparation method comprises the following steps: dispersing sulfur and the porous polymer in a solvent, heating and evaporating the solvent and then vacuum drying to obtain the Porous polymer-sulfur composite material.
    优选地，所述溶剂为二硫化碳、四氯化碳、乙二胺、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、二甲基乙醚和水中的至少一种。Preferably, the solvent is at least one of carbon disulfide, carbon tetrachloride, ethylenediamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ethyl ether and water .
    优选地，所述硫与多孔聚合物的质量比为(2-20):1，优选(10-20):1。Preferably, the mass ratio of the sulfur to the porous polymer is (2-20):1, preferably (10-20):1.
    优选地，所述加热和真空干燥的温度相同或不同，例如温度为50-250℃。Preferably, the heating and vacuum drying temperatures are the same or different, for example, the temperature is 50-250°C.
    优选地，所述真空干燥的时间为6-24小时。Preferably, the vacuum drying time is 6-24 hours.
    优选地，所述方法还包括：真空干燥后，冷却，得到所述多孔聚合物-硫复合材料。Preferably, the method further includes: after vacuum drying, cooling to obtain the porous polymer-sulfur composite material.
  7. 本发明提供一种复合电极，其特征在于，所述复合电极含有权利要求5所述多孔聚合物-硫复合材料。The present invention provides a composite electrode, characterized in that the composite electrode contains the porous polymer-sulfur composite material of claim 5.
    优选地，所述复合电极中还包括导电添加剂和粘结剂。Preferably, the composite electrode further includes a conductive additive and a binder.
    优选地，所述多孔聚合物-硫复合材料、导电添加剂和粘结剂的质量比为(4-8):(1-5):1。Preferably, the mass ratio of the porous polymer-sulfur composite material, the conductive additive and the binder is (4-8):(1-5):1.
    优选地，所述复合电极还包括集流体。Preferably, the composite electrode further includes a current collector.
    优选地，所述复合电极中，多孔聚合物-硫复合材料、导电添加剂和粘结剂的混合料负载在所述集流体上。Preferably, in the composite electrode, a mixture of a porous polymer-sulfur composite material, a conductive additive, and a binder is supported on the current collector.
  8. 权利要求7所述复合电极的制备方法，其特征在于，所述制备方法包括如下步骤：将多孔聚合物-硫复合材料、粘结剂、导电添加剂和溶剂混合均匀，制备得到的浆料经涂片、干燥，得到所述复合电极。The preparation method of the composite electrode according to claim 7, wherein the preparation method comprises the following steps: uniformly mixing the porous polymer-sulfur composite material, the binder, the conductive additive and the solvent, and the prepared slurry is coated Sheet and drying to obtain the composite electrode.
    优选地，所述溶剂为二硫化碳、四氯化碳、乙二胺、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、二甲基乙醚和水中的至少一种。Preferably, the solvent is at least one of carbon disulfide, carbon tetrachloride, ethylenediamine, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, dimethyl ethyl ether and water .
  9. 一种锂-硫电池，其特征在于，所述锂-硫电池包括权利要求7所述复合电极。A lithium-sulfur battery, wherein the lithium-sulfur battery comprises the composite electrode according to claim 7.
    优选地，所述锂-硫电池包括金属锂负极、作为正极的所述复合电极和电解液。Preferably, the lithium-sulfur battery includes a metal lithium negative electrode, the composite electrode as a positive electrode, and an electrolyte.
    优选地，所述电解质选自液体电解质和/或固体电解质。Preferably, the electrolyte is selected from a liquid electrolyte and/or a solid electrolyte.
    优选地，所述液体电解质为醚类电解液。Preferably, the liquid electrolyte is an ether type electrolyte.
    优选地，所述醚类电解液中的溶剂选自碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、丙烯碳酸酯(PC)、氟代亚乙烯碳酸酯(FEC)、1,3-二氧戊烷(DOL)、乙二醇二甲醚(DME)和三乙二醇二甲醚(TEGDME)中的至少一种。Preferably, the solvent in the ether electrolyte is selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), fluoroethylene carbonate (FEC), 1,3 -At least one of dioxolane (DOL), ethylene glycol dimethyl ether (DME), and triethylene glycol dimethyl ether (TEGDME).
    优选地，所述醚类电解液中的溶质选自六氟磷酸锂(LiPF 6)、高氯酸锂(LiClO 4)、硝酸锂(LiNO 3)、双草酸硼酸锂(LiBOB)、(三氟甲基)磺酸锂(LiFSI)和二(三氟甲基)磺酸锂(LiTFSI)中的至少一种。 Preferably, the solute in the ether electrolyte is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium nitrate (LiNO 3 ), lithium bisoxalate borate (LiBOB), (trifluoromethyl) At least one of lithium sulfonate (LiFSI) and lithium bis(trifluoromethyl)sulfonate (LiTFSI).
    优选地，所述固体电解质选自无机固态电解质和聚合物电解质中的至少一种。其中，所述聚合物电解质为凝胶聚合物电解质和/或固态聚合物电解质。Preferably, the solid electrolyte is selected from at least one of inorganic solid electrolytes and polymer electrolytes. Wherein, the polymer electrolyte is a gel polymer electrolyte and/or a solid polymer electrolyte.
    优选地，所述无机固态电解质选自至少一种固态陶瓷电解质。Preferably, the inorganic solid electrolyte is selected from at least one solid ceramic electrolyte.
    优选地，所述聚合物电解质选自聚环氧乙烷(PEO)、聚乙二醇二甲醚(PEGDME)、偏二氟乙烯与六氟丙烯的共聚物(PVDF-HFP)、乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)中的至少一种。Preferably, the polymer electrolyte is selected from polyethylene oxide (PEO), polyethylene glycol dimethyl ether (PEGDME), copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), ethoxylate At least one of tetramethylolpropane triacrylate (ETPTA).
    优选地，将所述金属锂负极、作为正极的所述复合电极和电解液组装，得到所述锂-硫电池。Preferably, the lithium metal negative electrode, the composite electrode as the positive electrode, and the electrolyte are assembled to obtain the lithium-sulfur battery.
  10. 一种储能器件，其特征在于，所述储能器件含有权利要求9所述锂-硫电池。An energy storage device, characterized in that the energy storage device contains the lithium-sulfur battery of claim 9.
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