WO2021164393A1 - 一种柔性多功能的交联粘接剂及其制备方法和应用 - Google Patents

一种柔性多功能的交联粘接剂及其制备方法和应用 Download PDF

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WO2021164393A1
WO2021164393A1 PCT/CN2020/135981 CN2020135981W WO2021164393A1 WO 2021164393 A1 WO2021164393 A1 WO 2021164393A1 CN 2020135981 W CN2020135981 W CN 2020135981W WO 2021164393 A1 WO2021164393 A1 WO 2021164393A1
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sulfur
flexible
positive electrode
cross
adhesive
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French (fr)
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王久林
陈加航
杨军
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上海交通大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J113/00—Adhesives based on rubbers containing carboxyl groups
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • 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 invention belongs to the technical field of flexible and multifunctional crosslinking adhesive for electrodes, and relates to a flexible and multifunctional crosslinking adhesive for electrodes, a preparation method thereof, and application in secondary batteries.
  • Lithium-sulfur secondary battery refers to a rechargeable battery that uses metal lithium as the negative electrode and sulfur-containing materials (including elemental sulfur, sulfur-based composite materials or organic sulfides) as the positive electrode. It has high energy density (theoretical capacity density is 1672mAh/g) , Long cycle life, high safety, low cost (low price of elemental sulfur) and other advantages are the development direction of next-generation batteries.
  • the positive electrode material is mainly composed of three parts, namely the active material, the binder and the conductive agent.
  • the main function of the binder is to bond and maintain the active material.
  • Adding a suitable amount of good performance binder can obtain a larger capacity and a longer cycle life, and it can also reduce the internal resistance of the battery, which is useful for improving the discharge platform of the battery.
  • high current discharge capacity reduce the internal resistance during low-speed charging, and improve the fast charging capacity of the battery.
  • the selection of the binder is very important.
  • the binder used generally requires low ohmic resistance, stable performance in the electrolyte, no expansion, no looseness, and no powder removal.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC sodium carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • organic binders have poor compatibility with sulfur cathodes and low sulfur utilization; among the commonly used water-based binders, styrene-butadiene rubber (SBR) has poor compatibility with sulfur cathodes when used alone as a binder, and its capacity is exerted. Low; carboxymethyl cellulose (CMC), guar gum (GG), polyacrylic acid (PAA) and other water-based binders rich in polar groups have excellent performance in low sulfur loading systems, but they are used In the high sulfur loading system, satisfactory results cannot be achieved. PAA has a certain degree of flexibility, but the mechanical strength is still poor, which cannot meet the structural stability of the high sulfur loading positive electrode. Only when the lithium-sulfur battery achieves a partial capacity of at least 4.0 mAh/cm 2 can it be competitive with the currently commercialized lithium-ion battery system and be used in the field of hybrid and pure electric vehicles.
  • Electrodes are of great significance for improving the energy density of lithium-sulfur batteries for practical applications.
  • the purpose of the present invention is to provide a flexible and multifunctional cross-linked adhesive and its preparation method and application in order to overcome the defects in the prior art.
  • the cross-linking adhesive uses guar gum and carboxyl styrene butadiene rubber as raw materials, and utilizes the hydroxyl and carboxyl styrene butadiene rubber tapes contained in guar gum. Some carboxyl molecules are formed by intermolecular cross-linking.
  • the crosslinked adhesive forms a flexible multifunctional crosslinked network.
  • the flexible cross-linking binder of the present invention has the characteristics of high flexibility, enhanced mechanical strength, sulfur cathode compatibility, and the like.
  • the cross-linked network structure can effectively accommodate the volume change of the positive electrode, thereby maintaining the stability of the positive electrode structure and high sulfur utilization during the cycle.
  • the mass ratio of the guar gum to the carboxyl styrene butadiene rubber is 9:1 to 1:9.
  • the mass ratio of the guar gum to the carboxyl styrene butadiene rubber is 3:1-1:3.
  • two water-based adhesives with different properties are used for cross-linking to simultaneously exert the advantages of both, such as high viscosity, high flexibility, etc., and to form a cross-linked network structure.
  • a mass ratio that is too large or too small cannot achieve this advantage efficiently.
  • the carboxyl styrene butadiene rubber includes carboxyl styrene butadiene rubber with a degree of carboxylation of 3-20%, and its 50% aqueous solution is milky white liquid, the pH is 6-8, and the viscosity is 20-350mPa ⁇ s, Available grades include AD5009, AD5010, 0125115, 165, 021252 or FSDB50.
  • the second aspect of the present invention provides a method for preparing the flexible and multifunctional cross-linked adhesive, which is prepared by cross-linking guar gum and carboxyl styrene butadiene rubber by adopting a co-solution method.
  • the third aspect of the present invention provides the application of the flexible and multifunctional crosslinking adhesive.
  • the flexible and multifunctional crosslinking adhesive, sulfur-containing material, and conductive agent are in a mass ratio of 7-9:0.5-1.5:0.5. -1.5 is dispersed in water, then coated on a current collector, dried and then compressed to prepare a secondary lithium-sulfur battery positive electrode.
  • the guar gum aqueous solution and the carboxyl styrene butadiene rubber aqueous solution are separately prepared, mixed and stirred according to the proportion to obtain a uniform milky white solution, and the in-situ cross-linking method is adopted to obtain
  • the milky white solution is directly used for the preparation of the positive electrode and forms the flexible and multifunctional cross-linking adhesive, and the intermolecular cross-linking occurs in situ during the drying process of the pole piece.
  • the conductive agent is composed of acetylene black and an alternative carbon material, and the alternative carbon material includes carbon nanotubes, carbon nanofibers, graphene or graphene oxide;
  • the conductive agent is composed of a mixture of alternative carbon materials and acetylene black in a mass ratio of 2:1-1:4;
  • the conductive agent is composed of a mixture of carboxylated carbon nanotubes and acetylene black in a mass ratio of 2:1-1:4.
  • carboxylated carbon nanotubes to partially replace the commonly used conductive agent acetylene black.
  • the introduction of carboxylated carbon nanotubes can build a multi-dimensional electrode structure while using the carboxyl group and the rich hydroxyl group of guar gum for intermolecular force, thereby Further improve the stability of the positive electrode structure.
  • the sulfur-containing material is a sulfur-based composite material, which is mixed with elemental sulfur and polyacrylonitrile in a mass ratio of 4-16:1 and then heated to 250-400°C under the protection of nitrogen or argon and kept warm. Obtained from 1-16h.
  • the molecular weight of the polyacrylonitrile is 10,000-1,000,000.
  • the mass content of sulfur in the sulfur-containing material is 30-70%.
  • the current collector is aluminum foil, aluminum mesh, carbon-coated aluminum foil, carbon-coated aluminum mesh, nickel mesh, or foamed nickel.
  • a single secondary lithium-sulfur battery positive electrode is subjected to a pressure treatment of 0-20MPa to prepare a high-density electrode; the secondary lithium-sulfur battery positive electrode compaction density after different pressure treatments is 0.8-1.6g/ cm 3 , the porosity is 50-10%.
  • Pressure treatment can effectively reduce the thickness of the electrode, make the active material and the substrate contact better, and the sulfur utilization rate is high; especially in the high-load electrode, the time lag of ion conduction and electron conduction decreases with the thickness reduction; the porosity caused by the external pressure A slight reduction in performance can reduce the amount of electrolyte required to wet the electrode while maintaining a high sulfur utilization rate; pressure treatment can reduce the electrode thickness and increase the electrode density, which is beneficial to the increase of the battery's volumetric energy density.
  • the present invention uses water-based guar gum (GG) and carboxyl styrene butadiene rubber (SCR) as raw materials, and utilizes the intermolecular interaction between the hydroxyl groups rich in guar gum and the carboxyl groups of the carboxyl styrene butadiene rubber to form a flexible Multifunctional cross-linked network.
  • GG water-based guar gum
  • SCR carboxyl styrene butadiene rubber
  • Guar gum can effectively bond active materials, conductive carbon and current collectors.
  • it is a rigid glue and has poor flexibility. It cannot effectively buffer the volume effect of sulfur cathodes, causing the cathode structure to collapse.
  • the life is shortened; or the styrene-butadiene rubber itself is a flexible rubber with good flexibility, but it is used in high-load lithium-sulfur batteries, and its electrochemical performance is poor; after the styrene-butadiene rubber is partially carboxylated, it can maintain its flexibility and While having advantages such as mechanical strength, the introduced carboxyl groups can be intermolecularly cross-linked with the hydroxyl groups rich in guar gum, thereby preparing a flexible cross-linked network (AFB). After a certain proportion of cross-linking between the two, they retain their respective advantages, forming a flexible composite adhesive that has strong adhesion, high mechanical strength, and is insoluble in electrolyte.
  • AFB flexible cross-linked network
  • a lithium-sulfur secondary battery composed of a high-load positive electrode (8mg/cm 2 ) made of AFB binder and a metal lithium negative electrode, the first discharge specific capacity is 1962.4mAh/g, tested at 0.1C charge and discharge cycle, the ratio after 100 cycles The capacity is 1447.2mAh/g, the cycle is very stable, and the surface capacity reaches 4.45mAh/cm 2 .
  • the battery performance declines, the battery is disassembled, and the positive structure is complete, without cracks and structural collapse; after replacing the new lithium sheet and electrolyte, the battery performance is restored, indicating that the cross-linking binder can ensure the structure of the sulfur positive electrode in the cycle process Stability, the performance degradation of the battery stems from the side reaction of the lithium negative electrode and the irreversible consumption of the electrolyte.
  • the capacity stabilized at 4.29mAh/cm 2 after 170 cycles at 0.2C charge-discharge cycle test; after 0.5C charge-discharge cycle test, the capacity stabilized at 4.00mAh/cm 2 after 250 cycles.
  • the electrolyte used in the lithium-sulfur secondary battery is 1M LiPF 6 /EC:DMC:FEC (1:1:0.1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate, FEC: fluorocarbonic acid) Vinyl ester), the cut-off voltage in the charge and discharge test is 1-3V (vs. Li/Li + ).
  • carboxylated carbon nanotubes to partially replace the commonly used conductive agent acetylene black.
  • the ratio of carboxylated carbon nanotubes to acetylene black is 2:1. -1:4.
  • the introduction of carboxylated carbon nanotubes can construct a multi-dimensional electrode structure while using the carboxyl groups and the hydroxyl groups rich in guar gum to perform intermolecular forces, thereby further improving the stability of the positive electrode structure.
  • the high-capacity positive electrode (9.5mg/cm 2 ) and the metal lithium negative electrode made by this method constitute a lithium-sulfur secondary battery.
  • the charge and discharge cycle test is carried out at 0.1C. After 200 cycles, the specific capacity is 1420.9mAh/g, and the cycle is very stable. And the surface capacity is 5.19mAh/cm 2 .
  • the water-based adhesive of the present invention is a flexible multifunctional cross-linking adhesive with strong bonding force, high mechanical strength, no cracking due to tensile deformation, insoluble in battery electrolyte, and can effectively accommodate the volume effect of sulfur positive electrodes. It also maintains the complete structure of the positive electrode for cyclic operation, and at the same time has significant advantages such as environmental friendliness and low cost.
  • the compacted sulfur positive electrode has a simple preparation process and has a larger application prospect.
  • FIG. 1 is a graph showing the rate curve of a lithium-sulfur secondary battery made of the flexible and multifunctional cross-linking adhesive AFB for the secondary lithium-sulfur battery obtained in Example 1 and other binders.
  • FIG. 2 is a cycle curve diagram of a lithium-sulfur secondary battery with different loadings made of a secondary lithium-sulfur battery cathode binder obtained in Example 1.
  • FIG. 2 is a cycle curve diagram of a lithium-sulfur secondary battery with different loadings made of a secondary lithium-sulfur battery cathode binder obtained in Example 1.
  • FIG. 3 is a graph showing the cycle performance of a high-load positive electrode made of the secondary lithium-sulfur battery positive electrode binder obtained in Example 1 and other binders.
  • FIG. 5 is a graph showing the cycle performance of a high-load positive electrode made of a secondary lithium-sulfur battery positive electrode binder obtained in Example 1.
  • FIG. 5 is a graph showing the cycle performance of a high-load positive electrode made of a secondary lithium-sulfur battery positive electrode binder obtained in Example 1.
  • Example 6 is an SEM image of the surface of the lithium-sulfur secondary battery made of the secondary lithium-sulfur battery positive electrode binder obtained in Example 1, 176 cycles at a rate of 0.2C and 275 cycles at a rate of 0.5C.
  • Example 7 is a diagram showing the capacity development of the lithium-sulfur secondary battery after the positive electrode made of the secondary lithium-sulfur battery positive electrode binder obtained in Example 1 is folded in half for different times.
  • FIG. 8 is a graph showing the high-rate cycling performance of the high-load positive lithium-sulfur secondary battery obtained in Example 2.
  • FIG. 9 is a cycle curve diagram of a lithium-sulfur secondary battery made of the positive electrode of the secondary lithium-sulfur battery obtained in Example 3.
  • FIG. 9 is a cycle curve diagram of a lithium-sulfur secondary battery made of the positive electrode of the secondary lithium-sulfur battery obtained in Example 3.
  • Example 10 is a diagram showing the relationship between the density of the positive electrode of the secondary lithium-sulfur battery obtained in Example 4 and the applied pressure.
  • Example 11 is a SEM image of the surface and cross-section of the high-pressure compacted sulfur positive electrode obtained in Example 4 without pressure treatment.
  • Example 12 is a diagram showing the relationship between the volume specific capacity and mass specific capacity of the positive electrode of the secondary lithium-sulfur battery obtained in Example 4 and the electrode density.
  • FIG. 13 is a graph showing the relationship between porosity and electrode density of the positive electrode of the secondary lithium-sulfur battery obtained in Example 4.
  • FIG. 14 is a cycle curve diagram of a lithium-sulfur secondary battery made of the positive electrode of the secondary lithium-sulfur battery obtained in Example 5.
  • FIG. 14 is a cycle curve diagram of a lithium-sulfur secondary battery made of the positive electrode of the secondary lithium-sulfur battery obtained in Example 5.
  • Sulfur-based composite material, flexible and multifunctional cross-linking adhesive, and acetylene black are uniformly relaxed and dispersed in deionized water at a mass ratio of 8:1:1, and then evenly coated on the carbon-coated aluminum foil, and then pressed into a tablet after drying a lithium sulfur secondary battery positive electrode, the loading between 1.6-15mg / cm 2; wherein the composite is a group of elemental sulfur with polyacrylonitrile mass ratio of 10: 1 after heating the mixture under nitrogen to 300 deg.] C and incubated 10h owned;
  • the battery assembly and test are as follows: use metal lithium as the negative electrode to assemble a lithium-sulfur secondary battery, the electrolyte is 1M LiPF 6 /EC:DMC:FEC (1:1:0.1 volume ratio, EC: ethylene carbonate, DMC: two Methyl carbonate, FEC: fluoroethylene carbonate); the charge-discharge cut-off voltage is 1-3V (vs. Li/Li + ).
  • the flexible and multifunctional cross-linking adhesive is made by cross-linking water-based GG and carboxyl styrene butadiene rubber SCR (1:1 mass ratio) by the co-solution method.
  • carboxylated styrene butadiene rubber with a degree of carboxylation of 3-20%, its 50% aqueous solution is milky white liquid, PH is 6-8, viscosity is 20-350mPa ⁇ s, and optional grades include AD5009, AD5010, 0125115, 165, 021252 or FSDB50 etc.
  • the specific preparation method is as follows: the guar gum aqueous solution and the carboxyl styrene butadiene rubber aqueous solution are respectively prepared, and the two are stirred at a solute mass ratio of 1:1 for 1-3 hours to obtain a uniform milky white solution.
  • the obtained viscous solution is directly applied to the preparation of the positive electrode, and in-situ intermolecular cross-linking occurs during the high-temperature drying of the pole pieces.
  • the discharge specific capacity of the ordinary positive electrode with a loading capacity of 2.4mg/cm 2 using AFB binder is still 1239.0mAh/g, which is higher than 1053.3mAh/g using GG, as shown in Figure 1. Show.
  • the cycle stability is good, and the sulfur utilization rate is close to or higher than 90%.
  • the sulfur utilization rate is still close to 90%, and the surface capacity is 8.31 mAh/cm 2 , as shown in Figure 2.
  • GG and AFB binder positive electrodes with a loading capacity of 8 mg/cm 2 were respectively prepared and tested for cycle performance.
  • the results show that, at a rate of 0.1C, the reversible specific capacity of the AFB binder positive electrode for 2 cycles is high, reaching 1561.6mAh/g, and the cycle performance is better than that of GG.
  • the capacity is still 1447.2mAh/g, and the capacity retention rate is 92.7. %, and the surface capacity can be maintained at 4.45mAh cm -2 , as shown in Figure 3.
  • the AFB binder positive electrode with a loading capacity of 8 mg/cm 2 was tested for cycling performance at a larger rate.
  • the capacity stabilized at 4.29 mAh/cm 2 after 170 cycles; in the 0.5C charge-discharge cycle test, the capacity stabilized at 4.00 mAh/cm 2 after 250 cycles, as shown in Figure 5.
  • the surface of the sulfur positive electrode after cycling was characterized by SEM, and the surface of the positive electrode of the AFB binder was smooth and crack-free after the long cycle of high magnification, indicating that the AFB binder can effectively maintain the stability of the positive electrode structure, as shown in Figure 6 (0.2C: (A)(b) after 176 laps; 0.5C: (c)(d) after 275 laps; (a)(c): 200 times magnification; (b)(d): 2000 times magnification).
  • the sulfur-based composite material, binder (AFB), and acetylene black are uniformly relaxed and dispersed in deionized water at a mass ratio of 8:1:1, and then evenly coated on the carbon-coated aluminum foil, dried and pressed to obtain lithium sulfur the positive electrode of the secondary battery, contained in an amount of 8mg / cm 2; wherein the composite is a group of elemental sulfur with polyacrylonitrile mass ratio of 10: 1 after heating under nitrogen to 300 deg.] C and mixing the resulting incubated 10h; binder AFB
  • the composition and preparation method are the same as those described in Example 1;
  • Lithium-sulfur secondary battery is assembled with metal lithium as the negative electrode, and the electrolyte is 1M LiPF 6 /FEC:DMC (1:1 volume ratio, DMC: dimethyl carbonate, FEC: fluorocarbonic acid) Vinyl ester); the charge-discharge cut-off voltage is 1-3V (vs. Li/Li + ).
  • the sulfur-based composite material, binder (AFB), acetylene black, and carboxylated carbon nanotubes are uniformly relaxed and dispersed in deionization at a mass ratio of 8:1:0.75:0.25 Then it is evenly coated on the carbon-coated aluminum foil, dried and pressed to obtain the positive electrode of the lithium-sulfur secondary battery with a loading capacity of 9.5mg/cm 2 ; where the sulfur-based composite material is elemental sulfur and polyacrylonitrile in a mass ratio of 10: 1 After mixing, it is heated to 300°C under nitrogen protection and kept for 10 hours; the composition and preparation method of the binder AFB are the same as those described in Example 1;
  • the battery assembly and test are as follows: use metal lithium as the negative electrode to assemble a lithium-sulfur secondary battery, the electrolyte is 1M LiPF 6 /EC:DMC:FEC (1:1:0.1 volume ratio, EC: ethylene carbonate, DMC: two Methyl carbonate, FEC: fluoroethylene carbonate); the charge-discharge cut-off voltage is 1-3V (vs. Li/Li + ).
  • the introduction of carboxylated carbon nanotubes can construct a multi-dimensional electrode structure while using the carboxyl groups and the hydroxyl groups rich in guar gum to perform intermolecular forces, thereby further improving the stability of the positive electrode structure.
  • the high-capacity positive electrode (9.5mg/cm 2 ) and the metal lithium negative electrode made by this method constitute a lithium-sulfur secondary battery.
  • the charge and discharge cycle test is carried out at 0.1C. After 200 cycles, the specific capacity is 1420.9mAh/g, and the cycle is very stable. And the surface capacity reaches 5.19mAh/cm 2 , as shown in Figure 9.
  • the sulfur-based composite material, binder (AFB), and acetylene black are uniformly relaxed and dispersed in deionized water at a mass ratio of 8:1:1, and then evenly coated on the carbon-coated aluminum foil, dried and pressed to obtain lithium sulfur Secondary battery cathode; the load is between 8-10mg/cm 2 ; where the sulfur-based composite material is obtained by mixing elemental sulfur and polyacrylonitrile at a mass ratio of 10:1 and heating to 300°C under nitrogen protection and holding for 10 hours;
  • the composition and preparation method of the binder AFB are the same as those described in Example 1;
  • Positive electrode pressure treatment and battery assembly are as follows: after slurrying, coating, and drying to obtain a secondary lithium-sulfur battery positive electrode, a single pole piece is subjected to pressure treatment of 0-25MPa to prepare a high-pressure compact density electrode.
  • Lithium-sulfur secondary battery is assembled with metal lithium as the negative electrode, the electrolyte is LiPF 6 /EC:DMC:FEC (1:1:0.1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate, FEC: fluorine Substitute ethylene carbonate); the charge-discharge cut-off voltage is 1-3V (vs. Li/Li + ).
  • the porosity of the electrode corresponding to different electrode densities is calculated. Compared with the electrode without pressure treatment (52.7%), the porosity of the sulfur cathode treated with 25MPa pressure is only 13.3%, as shown in Figure 13, which is beneficial to reduce the wettability. The amount of electrolyte required for the wet electrode, thereby improving the quality and energy density of the battery.
  • the sulfur-based composite material, binder (AFB), and acetylene black are uniformly relaxed and dispersed in deionized water at a mass ratio of 8:1:1, and then evenly coated on the carbon-coated aluminum foil, dried and pressed to obtain lithium sulfur the positive electrode of the secondary battery, contained in an amount of 8mg / cm 2; wherein the composite is a group of elemental sulfur with polyacrylonitrile mass ratio of 10: 1 after heating under nitrogen to 300 deg.] C and mixing the resulting incubated 10h; binder AFB
  • the composition and preparation method are the same as those described in Example 1;
  • the battery assembly and test are: lithium-sulfur secondary battery is assembled with metal lithium as the negative electrode, the electrolyte is LiPF 6 /EC:DMC:FEC (1:1:0.1 volume ratio, EC: ethylene carbonate, DMC: dimethyl Carbonate, FEC: fluoroethylene carbonate); the charge-discharge cut-off voltage is 1-3V (vs. Li/Li + ).
  • This embodiment is basically the same as embodiment 1, except that in this embodiment, the flexible and multifunctional cross-linking adhesive AFB is selected to be mixed with the sulfur-based composite material and the conductive agent in a mass ratio of 90:5:5;
  • the composition and preparation method of the agent AFB are the same as those described in Example 1.
  • This embodiment is basically the same as embodiment 1, but the difference is that in this embodiment, the flexible and multifunctional cross-linking adhesive AFB, the sulfur-based composite material, and the conductive agent are mixed with the adhesive AFB according to the mass ratio of 70:15:15.
  • the composition and preparation method are the same as those described in Example 1.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of the polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 10,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 100,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 150,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 300,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 500,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 700,000.
  • This embodiment is basically the same as Embodiment 1, except that the molecular weight of polyacrylonitrile selected for synthesizing the vulcanized polyacrylonitrile positive electrode in this embodiment is 1 million.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 30% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 40% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 45% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 50% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 55% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the sulfur content of the sulfurized polyacrylonitrile positive electrode is selected to be 60% in this embodiment.
  • This embodiment is basically the same as Embodiment 1, except that the current collector in this embodiment is aluminum foil.
  • This embodiment is basically the same as Embodiment 1, except that the current collector in this embodiment is an aluminum mesh.
  • This embodiment is basically the same as Embodiment 1, except that the current collector in this embodiment is an aluminum mesh coated with carbon.
  • This embodiment is basically the same as Embodiment 1, except that the current collector in this embodiment is a nickel mesh coated with carbon.
  • This embodiment is basically the same as Embodiment 1, except that the current collector in this embodiment is foamed nickel.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carboxylated carbon nanotubes and acetylene black is selected to be 2:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carboxylated carbon nanotubes and acetylene black is selected to be 1:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carboxylated carbon nanotubes and acetylene black is selected to be 1:2 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carboxylated carbon nanotubes and acetylene black is selected to be 1:4 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanotubes and acetylene black is selected to be 2:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanotubes and acetylene black is selected to be 1:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanotubes and acetylene black is selected to be 1:2 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanotubes and acetylene black is selected to be 1:3 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanotubes and acetylene black is selected to be 1:4 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanofibers and acetylene black is selected to be 2:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanofibers and acetylene black is selected to be 1:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanofibers and acetylene black is selected to be 1:2 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanofibers and acetylene black is selected to be 1:3 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of carbon nanofibers and acetylene black is selected to be 1:4 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene and acetylene black is selected to be 2:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene and acetylene black is selected to be 1:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene and acetylene black is selected to be 1:2 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene and acetylene black is selected to be 1:3 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene and acetylene black is selected to be 1:4 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene oxide and acetylene black is selected to be 2:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene oxide and acetylene black is selected to be 1:1 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene oxide and acetylene black is selected to be 1:2 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene oxide and acetylene black is selected to be 1:3 in this embodiment.
  • This embodiment is basically the same as Embodiment 3, except that the ratio of graphene oxide and acetylene black is selected to be 1:4 in this embodiment.

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Abstract

一种柔性多功能的交联粘接剂及其制备方法和应用，该粘接剂以瓜尔豆胶和羧基丁苯橡胶为原料，利用瓜尔豆胶富含的羟基和羧基丁苯橡胶带有的羧基分子间交联而成，形成柔性的多功能交联网络。与现有技术相比，所述的水性粘接剂为柔性交联粘结剂，粘结力强，机械强度大，且拉伸形变不开裂，不溶于电池电解液，可以有效容纳硫正极的体积效应，并保持循环操作正极结构完整，同时具有环境友好，成本低廉等显著优势，压实硫正极制备过程简单，具有较大的应用前景。

Description

一种柔性多功能的交联粘接剂及其制备方法和应用 技术领域
本发明属于电极用柔性多功能的交联粘接剂技术领域，涉及一种电极用柔性多功能的交联粘接剂及其制备方法和在二次电池中的应用。
背景技术
锂硫二次电池是指采用金属锂为负极，含硫材料(包括单质硫、硫基复合材料或有机硫化物)为正极的可充电池，具有高能量密度(理论容量密度为1672mAh/g)、长循环寿命、高安全性、低成本(单质硫的价格低廉)等优点，是下一代电池的发展方向。
正极材料主要由三部分组成，分别为活性物质、粘结剂和导电剂。其中，粘结剂的主要作用是粘结和保持活性材料，加入适量性能优良的粘结剂可获得较大容量和较长的循环寿命，而且还能降低电池内阻，对提高电池的放电平台和大电流放电能力、降低低速充电时的内阻、提高电池的快充能力等均有促进作用。在电极的制作过程中，粘结剂的选用十分关键，对使用的粘结剂一般要求欧姆电阻小，在电解液中性能稳定，不膨胀、不松散、不脱粉。目前，常用的粘合剂包括聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)等以酒精做分散剂的粘合剂，以及羧甲基纤维素钠(CMC)和丁苯橡胶(SBR)胶乳等水溶性粘合剂。
上述粘结剂中，有机系粘结剂与硫正极兼容性差，硫利用率低；常用的水系粘结剂中，丁苯橡胶(SBR)单独做粘结剂时与硫正极兼容性差，容量发挥低；羧甲基纤维素钠(CMC)，瓜尔豆胶(GG)，聚丙烯酸(PAA)等富含极性基团的水系粘结剂在低硫载量体系中性能表现优异，但应用于高硫载量体系时，却无法取得令人满意的效果，PAA具有一定的柔性，但机械强度仍较差，无法满足高硫载量正极的结构稳定性。而锂硫电池至少实现4.0mAh/cm 2的局部容量，才具有同现已商业化的锂离子电池体系的竞争能力，并应用于混动和纯电动汽车领域。
发明内容
探究适用于高载量硫正极的高性能新型粘结剂，保证硫正极在循环过程中的结构稳定性，并对硫正极进行适当压力处理，降低电极厚度，制备柔性高载量高压实 密度电极，对提高锂硫电池能量密度，以适于实际应用具有极其重大的意义。
本发明的目的就是为了克服现有技术存在的缺陷而提供一种柔性多功能的交联粘接剂及其制备方法和应用。
本发明的目的可以通过以下技术方案来实现：
本发明一方面提供一种柔性多功能的交联粘接剂，该交联粘接剂以瓜尔豆胶和羧基丁苯橡胶为原料，利用瓜尔豆胶含有的羟基与羧基丁苯橡胶带有的羧基分子进行分子间交联而成。该交联粘接剂形成有柔性的多功能交联网络。
本发明的柔性交联粘结剂具有高柔性、加强的机械强度和硫正极兼容性等特点。其交联构建的网络结构可以有效容纳正极的体积变化，从而保持循环过程中正极结构的稳定性和高硫利用率。
作为优选的技术方案，所述的瓜尔豆胶与羧基丁苯橡胶的质量之比为9:1-1:9。
作为优选的技术方案，所述的瓜尔豆胶与羧基丁苯橡胶的质量之比为3:1-1:3。
本发明中将两种不同性能的水性粘结剂交联使用旨在同时发挥两者的优越性，如高粘性、高柔性等，且形成交联的网络结构。过大或过小的质量比无法高效地实现这一优点。
作为优选的技术方案，所述的羧基丁苯橡胶包括羧基化程度3-20％的羧基丁苯橡胶，其50％的水溶液为乳白色液体，PH为6-8，粘度为20-350mPa·s，可选牌号包括AD5009、AD5010、0125115、165、021252或FSDB50。
本发明第二方面提供所述的柔性多功能的交联粘接剂的制备方法，该交联粘接剂由瓜尔豆胶和羧基丁苯橡胶通过采用共溶液法交联制得。
本发明第三方面提供所述的柔性多功能的交联粘接剂的应用，将柔性多功能的交联粘接剂与含硫材料、导电剂按照质量比7-9:0.5-1.5:0.5-1.5分散于水中，然后涂覆于集流体上，干燥后压片，制备二次锂硫电池正极。
通过分别制备瓜尔豆胶水溶液和羧基丁苯橡胶水溶液，将两者按照配比混合，搅拌(优选1-3小时)得到均匀乳白色溶液，浇筑在四氟乙烯板上加热处理(优选50-90℃处理6-12小时)得到交联的柔性膜。将其应用于二次锂硫电池正极时：
作为优选的技术方案，在二次锂硫电池正极制备过程中，分别配制瓜尔豆胶水溶液和羧基丁苯橡胶水溶液，按配比混合并搅拌得到均匀乳白色溶液，采用原位交联法，将得到的乳白色溶液直接用于正极制备并形成所述的柔性多功能的交联粘接剂，分子间交联在极片干燥过程中原位发生。
作为优选的技术方案，所述的导电剂由乙炔黑和替代碳材料组成，所述的替代碳材料包括碳纳米管、碳纳米纤维、石墨烯或氧化石墨烯；
优选所述的导电剂由替代碳材料和乙炔黑按照质量比2:1-1:4混合组成；
进一步优选所述的导电剂由羧基化的碳纳米管和乙炔黑按照质量比2:1-1:4混合组成。
使用羧基化的碳纳米管部分取代常用导电剂乙炔黑，羧基化的碳纳米管的引入可以在构建多维电极结构的同时，利用羧基和瓜尔豆胶富含的羟基进行分子间作用力，从而进一步提高正极结构稳定性。
作为优选的技术方案，所述的含硫材料为硫基复合材料，由单质硫与聚丙烯腈按质量比4-16:1混合后在氮气或氩气保护下加热至250-400℃并保温1-16h得到。
作为优选的技术方案，所述的聚丙烯腈的分子量为1万-100万。
作为优选的技术方案，所述的含硫材料中硫的质量含量为30-70％。
作为优选的技术方案，所述的集流体为铝箔、铝网、包覆碳的铝箔、包覆碳的铝网、镍网或泡沫镍。
作为优选的技术方案，对单个二次锂硫电池正极进行0-20MPa的压力处理，以制备高压实密度电极；不同压力处理后的二次锂硫电池正极压实密度为0.8-1.6g/cm 3，孔隙率50-10％。
压力处理可以有效降低电极厚度，使活性物质和基底接触更好，硫利用率高；特别是在高载量电极中，离子传导和电子传导的时间滞后随厚度减少而减少；外加压力伴随的多孔性略微减少可以在保持相当高硫利用率的前提下，减少润湿电极所需的电解液数量；进行压力处理可以降低电极厚度并增大电极密度，有利于电池体积能量密度的提升。
本发明的以水性的瓜尔豆胶(GG)和羧基丁苯橡胶(SCR)为原料，利用瓜尔豆胶富含的羟基和羧基丁苯橡胶带有的羧基分子间相互作用，形成柔性的多功能交联网络。
瓜尔豆胶可以有效地粘结活性物质、导电碳和集流体，但是在高载量锂硫电池运行中，其本身为刚性胶，柔韧性差，无法有效缓冲硫正极体积效应，造成正极结构坍塌，寿命减短；或丁苯橡胶本身为柔性胶，柔韧性好，但运用于高载量锂硫电池中，电化学性能差；将丁苯橡胶部分羧基化以后，可以在保持其柔韧性和机械强度等优势的同时，引入的羧基可以和瓜尔豆胶富含的羟基进行分子间交联，从而制 备出柔性的交联网络(AFB)。两者之间通过一定比例交联后保留了各自的优势，形成粘结力强，机械强度大，且不溶于电解液的柔性复合胶。
与现有技术相比，以本发明所提供的柔性多功能的交联粘接剂作为锂硫二次电池水性正极粘合剂，与采用有机溶剂基粘结剂所制备的正极相比，具有环保无毒害、成本低、粘结性强、分散性好、柔韧性好、比容量较高、循环稳定性高等优点。采用AFB粘结剂制作的高载量正极(8mg/cm 2)和金属锂负极组成锂硫二次电池，首次放电比容量为1962.4mAh/g，以0.1C充放电循环测试，100圈后比容量为1447.2mAh/g，循环十分稳定，且面容量达4.45mAh/cm 2。其中，电池性能下降后拆开电池，正极结构完整，无裂缝和结构坍塌；更换新的锂片和电解液后，电池性能恢复，说明该交联粘结剂可以保证硫正极在循环过程的结构稳定性，电池的性能衰减源于锂负极的副反应和电解液不可逆消耗。在更大充放电倍率下，在0.2C充放电循环测试，170圈后面容量稳定在4.29mAh/cm 2；在0.5C充放电循环测试，250圈后面容量稳定在4.00mAh/cm 2。
上述锂硫二次电池所使用的电解液为1M的LiPF 6/EC:DMC:FEC(1:1:0.1体积比，EC:碳酸乙烯酯，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)，充放电测试中截止电压为1-3V(vs.Li/Li +)。
使用对锂负极兼容性更好的1M的LiPF 6/FEC:DMC(1:1体积比)，电池性能和循环寿命进一步提升，以0.2C充放电循环测试，200圈后比容量为1422.9mAh/g，面容量达4.37mAh/cm 2。
使用该柔性多功能的交联粘接剂进行更高载量的硫正极制备及电化学性能表征，正极载量高达15mg/cm 2时，硫利用率仍接近90％，且面容量实现8.31mAh/cm 2。
使用该柔性多功能的交联粘接剂进行更高载量的硫正极制备，使用羧基化的碳纳米管部分取代常用导电剂乙炔黑，羧基化的碳纳米管和乙炔黑比例为2:1-1:4。羧基化碳纳米管的引入可以在构建多维电极结构的同时，利用羧基和瓜尔豆胶富含的羟基进行分子间作用力，从而进一步提高正极结构稳定性。采用该方法制作的高载量正极(9.5mg/cm 2)和金属锂负极组成锂硫二次电池，以0.1C充放电循环测试，200圈后比容量为1420.9mAh/g，循环十分稳定，且面容量达5.19mAh/cm 2。
总之，本发明的水性粘接剂为柔性多功能交联粘结剂，粘结力强，机械强度大，且拉伸形变不开裂，不溶于电池电解液，可以有效容纳硫正极的体积效应，并保持循环操作正极结构完整，同时具有环境友好，成本低廉等显著优势，压实硫正极制 备过程简单，具有较大的应用前景。
附图说明
图1为实施例1得到的二次锂硫电池柔性多功能的交联粘接剂AFB和其他粘结剂做成的锂硫二次电池的倍率曲线图。
图2为实施例1得到的二次锂硫电池正极粘合剂做成的不同载量锂硫二次电池的循环曲线图。
图3为实施例1得到的二次锂硫电池正极粘合剂和其他粘结剂做成的高载量正极循环性能图。
图4为GG循环105圈及实施例1制备得到的二次锂硫电池正极粘合剂循环181圈后不同硫正极表面SEM图。
图5为实施例1得到的二次锂硫电池正极粘合剂做成的高载量正极大倍率循环性能图。
图6为实施例1得到的二次锂硫电池正极粘合剂做成的锂硫二次电池在0.2C倍率下循环176圈和0.5C倍率下循环275圈硫正极表面SEM图。
图7为实施例1得到的二次锂硫电池正极粘合剂做成的正极对折不同次数后锂硫二次电池的容量发挥图。
图8为实施例2得到的高载量正极锂硫二次电池大倍率循环性能图。
图9为实施例3得到的二次锂硫电池正极做成的锂硫二次电池的循环曲线图。
图10为实施例4得到的二次锂硫电池正极密度与外加压力的关系图。
图11为未经压力处理和实施例4得到的高压实硫正极表面和截面SEM图。
图12为实施例4得到的二次锂硫电池正极体积比容量和质量比容量与电极密度的关系图。
图13为实施例4得到的二次锂硫电池正极孔隙率与电极密度的关系图。
图14为实施例5得到的二次锂硫电池正极做成的锂硫二次电池的循环曲线图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将硫基复合材料、柔性多功能的交联粘接剂、乙炔黑按质量比为8:1:1均匀缓 和并分散于去离子水中，然后均匀涂布在覆碳铝箔上，干燥后压片得到锂硫二次电池正极，载量在1.6-15mg/cm 2之间；其中硫基复合材料为单质硫与聚丙烯腈按质量比10:1混合后氮气保护下加热至300℃并保温10h得到的；
电池组装和测试为：采用金属锂作为负极组装成锂硫二次电池，电解液为1M的LiPF 6/EC:DMC:FEC(1:1:0.1体积比，EC:碳酸乙烯酯，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)；充放电截止电压为1-3V(vs.Li/Li +)。
柔性多功能的交联粘接剂(AFB)由水系的GG和羧基丁苯橡胶SCR(1:1质量比)共溶液法交联制得。其中，羧基化程度3-20％的羧基丁苯橡胶，其50％的水溶液为乳白色液体，PH为6-8，粘度为20-350mPa·s，可选牌号包括AD5009、AD5010、0125115、165、021252或FSDB50等。具体制备方法如下：分别制备瓜尔豆胶水溶液和羧基丁苯橡胶水溶液，将两者按溶质质量比1:1搅拌1-3小时得到均匀乳白色溶液。将得到粘稠溶液直接应用于正极制备，在极片高温烘干过程中发生原位分子间交联。使用AFB粘结剂的载量为2.4mg/cm 2的普通载量正极在5C大倍率条件下，放电比容量仍为1239.0mAh/g，高于使用GG的1053.3mAh/g，如图1所示。
对于使用AFB粘结剂的不同载量硫正极，循环稳定性好，硫利用率接近或高于90％。当总载量更高，高达15mg/cm 2时，硫利用率仍接近90％，且面容量实现8.31mAh/cm 2，如图2所示。
同时，分别制备了载量为8mg/cm 2的GG、AFB粘结剂正极，进行循环性能测试。结果表明，在0.1C倍率下，AFB粘结剂正极2圈可逆比容量高，达1561.6mAh/g，且循环性能优于GG，100圈后容量仍为1447.2mAh/g，容量保持率达92.7％，且面容量可以保持在4.45mAh cm -2，如图3所示。
对循环后不同硫正极表面进行SEM表征，可以看出，循环后GG粘结剂正极从集流体上大块脱落散架，散落的电极碎片内部也表现出细微裂缝；相比之下，AFB粘结剂正极表面结构完整、无颗粒沉积，表明AFB粘结剂可以有效缓冲硫正极的体积效应，如图4所示(GG：循环前(a)，105圈后(b)(c)；AFB：循环前(d)，105圈后(e)(f)；(a)(b)(d)(e)：放大200倍；(c)(f)：放大2000倍)。
对载量为8mg/cm 2的AFB粘结剂正极，进行更大倍率下的循环性能测试。在0.2C充放电循环测试，170圈后面容量稳定在4.29mAh/cm 2；在0.5C充放电循环测试，250圈后面容量稳定在4.00mAh/cm 2，如图5所示。
同样地，对循环后硫正极表面进行SEM表征，大倍率长循环后AFB粘结剂正极表面平整无裂纹，表明AFB粘结剂可以有效保持正极结构稳定性，如图6所示(0.2C：176圈后(a)(b)；0.5C：275圈后(c)(d)；(a)(c)：放大200倍；(b)(d)：放大2000倍)。
对于使用AFB粘结剂的载量为9mg/cm 2的硫正极进行柔韧性测试，相比不做对折处理的硫正极，对折400次后的硫正极比容量仍可以发挥近90％，如图7所示。
实施例2
将硫基复合材料、粘结剂(AFB)、乙炔黑按质量比为8:1:1均匀缓和并分散于去离子水中，然后均匀涂布在覆碳铝箔上，干燥后压片得到锂硫二次电池正极，载量为8mg/cm 2；其中硫基复合材料为单质硫与聚丙烯腈按质量比10:1混合后氮气保护下加热至300℃并保温10h得到的；粘结剂AFB与实施例1中所述组成和制备方法相同；
电池组装和测试为：采用金属锂作为负极组装成锂硫二次电池，电解液为1M的LiPF 6/FEC:DMC(1:1体积比，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)；充放电截止电压为1-3V(vs.Li/Li +)。
基于AFB粘结剂的高载量正极性能和循环寿命进一步提升，以0.2C充放电循环测试，200圈后比容量为1422.9mAh/g，面容量达4.37mAh/cm 2，如图8所示。
实施例3
使用羧基化碳纳米管部分代替乙炔黑，将硫基复合材料、粘结剂(AFB)、乙炔黑、羧基化碳纳米管按质量比为8:1:0.75:0.25均匀缓和并分散于去离子水中，然后均匀涂布在覆碳铝箔上，干燥后压片得到锂硫二次电池正极，载量为9.5mg/cm 2；其中硫基复合材料为单质硫与聚丙烯腈按质量比10:1混合后氮气保护下加热至300℃并保温10h得到的；粘结剂AFB与实施例1中所述组成和制备方法相同；
电池组装和测试为：采用金属锂作为负极组装成锂硫二次电池，电解液为1M的LiPF 6/EC:DMC:FEC(1:1:0.1体积比，EC:碳酸乙烯酯，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)；充放电截止电压为1-3V(vs.Li/Li +)。
羧基化碳纳米管的引入可以在构建多维电极结构的同时，利用羧基和瓜尔豆胶富含的羟基进行分子间作用力，从而进一步提高正极结构稳定性。采用该方法制作的高载量正极(9.5mg/cm 2)和金属锂负极组成锂硫二次电池，以0.1C充放电循环 测试，200圈后比容量为1420.9mAh/g，循环十分稳定，且面容量达5.19mAh/cm 2，如图9所示。
实施例4
将硫基复合材料、粘结剂(AFB)、乙炔黑按质量比为8:1:1均匀缓和并分散于去离子水中，然后均匀涂布在覆碳铝箔上，干燥后压片得到锂硫二次电池正极；载量在8-10mg/cm 2之间；其中硫基复合材料为单质硫与聚丙烯腈按质量比10:1混合后氮气保护下加热至300℃并保温10h得到的；粘结剂AFB与实施例1中所述组成和制备方法相同；
正极压力处理和电池组装为：对搅浆、涂膜、干燥压片制得二次锂硫电池正极后，对单个极片进行0-25MPa的压力处理，制备高压实密度电极。采用金属锂作为负极组装成锂硫二次电池，电解液为LiPF 6/EC:DMC:FEC(1:1:0.1体积比，EC:碳酸乙烯酯，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)；充放电截止电压为1-3V(vs.Li/Li +)。
通过探究外加压力对电极厚度以及密度的影响，结果显示，对电极进行压力处理，可以有效地降低电极厚度并增大电极密度，有利于电池体积能量密度的提升，如图10所示。
选取未经压力处理和25MPa压力处理的硫正极分别进行表面和截面SEM表征，电极厚度从109.3μm有效降低至59.5μm，如图11所示。
比较不同压力处理后不同密度下电极循环性能，当密度为1.54g/cm 3时，体积比容量达到1060.3mAh/cm 3，如图12所示。
通过计算得出不同电极密度对应的电极孔隙率，相比未经压力处理的电极(52.7％)，25MPa压力处理的硫正极孔隙率仅为13.3％，，如图13所示，有利于降低润湿电极所需的电解液用量，从而提高电池质量能量密度。
实施例5
将硫基复合材料、粘结剂(AFB)、乙炔黑按质量比为8:1:1均匀缓和并分散于去离子水中，然后均匀涂布在覆碳铝箔上，干燥后压片得到锂硫二次电池正极，载量为8mg/cm 2；其中硫基复合材料为单质硫与聚丙烯腈按质量比10:1混合后氮气保护下加热至300℃并保温10h得到的；粘结剂AFB与实施例1中所述组成和制备方法相同；
电池组装和测试为：采用金属锂作为负极组装成锂硫二次电池，电解液为 LiPF 6/EC:DMC:FEC(1:1:0.1体积比，EC:碳酸乙烯酯，DMC:二甲基碳酸酯，FEC:氟代碳酸乙烯酯)；充放电截止电压为1-3V(vs.Li/Li +)。
控制电解液用量在极低的范围内(电解液体积/S@pPAN复合物质量:2.5-1.0mL/g)，探究贫液条件下锂硫电池性能。即使在1.0mL/g的低电解液用量下，使用AFB粘结剂的硫正极仍可以有效发挥容量，第二圈硫利用率为84％，如图12所示。
实施例6
本实施与实施例1基本相同，不同之处在于，本实施例中选择柔性多功能的交联粘接剂AFB与硫基复合材料、导电剂按照质量比90:5:5混合；其中粘结剂AFB与实例1中所述组成和制备方法相同。
实施例7
本实施与实施例1基本相同，不同之处在于，本实施例中选择柔性多功能的交联粘接剂AFB与硫基复合材料、导电剂按照质量比70:15:15混合粘结剂AFB与实例1中所述组成和制备方法相同。
实施例8
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为1万。
实施例9
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为10万。
实施例10
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为15万。
实施例11
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为30万。
实施例12
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为50万。
实施例13
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为70万。
实施例14
本实施与实施例1基本相同，不同之处在于，本实施例中选择用于合成硫化聚丙烯腈正极的聚丙烯腈分子量为100万。
实施例15
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为30％。
实施例16
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为40％。
实施例17
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为45％。
实施例18
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为50％。
实施例19
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为55％。
实施例20
本实施与实施例1基本相同，不同之处在于，本实施例中选择硫化聚丙烯腈正极的硫的质量含量为60％。
实施例21
本实施例与实施例1基本相同，不同之处在于，本实施例中的集流体为铝箔。
实施例22
本实施例与实施例1基本相同，不同之处在于，本实施例中的集流体为铝网。
实施例23
本实施例与实施例1基本相同，不同之处在于，本实施例中的集流体为包覆碳的铝网。
实施例24
本实施例与实施例1基本相同，不同之处在于，本实施例中的集流体为包覆碳的镍网。
实施例25
本实施例与实施例1基本相同，不同之处在于，本实施例中的集流体为泡沫镍。
实施例26
本实施与实施例3基本相同，不同之处在于，本实施例中选择羧基化碳纳米管和乙炔黑比例为2:1。
实施例27
本实施与实施例3基本相同，不同之处在于，本实施例中选择羧基化碳纳米管和乙炔黑比例为1:1。
实施例28
本实施与实施例3基本相同，不同之处在于，本实施例中选择羧基化碳纳米管和乙炔黑比例为1:2。
实施例29
本实施与实施例3基本相同，不同之处在于，本实施例中选择羧基化碳纳米管和乙炔黑比例为1:4。
实施例30
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米管和乙炔黑比例为2:1。
实施例31
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米管和乙炔黑比例为1:1。
实施例32
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米管和乙炔黑比例为1:2。
实施例33
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米管和乙炔黑比例为1:3。
实施例34
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米管和乙炔黑比例为1:4。
实施例35
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米纤维和乙炔黑比例为2:1。
实施例36
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米纤维和乙炔黑比例为1:1。
实施例37
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米纤维和乙炔黑比例为1:2。
实施例38
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米纤维和乙炔黑比例为1:3。
实施例39
本实施与实施例3基本相同，不同之处在于，本实施例中选择碳纳米纤维和乙炔黑比例为1:4。
实施例40
本实施与实施例3基本相同，不同之处在于，本实施例中选择石墨烯和乙炔黑比例为2:1。
实施例41
本实施与实施例3基本相同，不同之处在于，本实施例中选择石墨烯和乙炔黑比例为1:1。
实施例42
本实施与实施例3基本相同，不同之处在于，本实施例中选择石墨烯和乙炔黑比例为1:2。
实施例43
本实施与实施例3基本相同，不同之处在于，本实施例中选择石墨烯和乙炔黑比例为1:3。
实施例44
本实施与实施例3基本相同，不同之处在于，本实施例中选择石墨烯和乙炔黑比例为1:4。
实施例45
本实施与实施例3基本相同，不同之处在于，本实施例中选择氧化石墨烯和乙炔黑比例为2:1。
实施例46
本实施与实施例3基本相同，不同之处在于，本实施例中选择氧化石墨烯和乙炔黑比例为1:1。
实施例47
本实施与实施例3基本相同，不同之处在于，本实施例中选择氧化石墨烯和乙炔黑比例为1:2。
实施例48
本实施与实施例3基本相同，不同之处在于，本实施例中选择氧化石墨烯和乙炔黑比例为1:3。
实施例49
本实施与实施例3基本相同，不同之处在于，本实施例中选择氧化石墨烯和乙炔黑比例为1:4。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种柔性多功能的交联粘接剂，其特征在于，该交联粘接剂以瓜尔豆胶和羧基丁苯橡胶为原料，利用瓜尔豆胶含有的羟基与羧基丁苯橡胶带有的羧基分子进行分子间交联而成。
  2. 根据权利要求1所述的一种柔性多功能的交联粘接剂，其特征在于，所述的瓜尔豆胶与羧基丁苯橡胶的质量之比为9:1-1:9。
  3. 根据权利要求2所述的一种柔性多功能的交联粘接剂，其特征在于，所述的瓜尔豆胶与羧基丁苯橡胶的质量之比为3:1-1:3。
  4. 如权利要求1～3任一所述的柔性多功能的交联粘接剂的制备方法，其特征在于，该交联粘接剂由瓜尔豆胶和羧基丁苯橡胶通过采用共溶液法交联制得。
  5. 如权利要求1～3任一所述的柔性多功能的交联粘接剂的应用，其特征在于，将柔性多功能的交联粘接剂与含硫材料、导电剂按照质量比7-9:0.5-1.5:0.5-1.5分散于水中，然后涂覆于集流体上，干燥后压片，制备二次锂硫电池正极。
  6. 根据权利要求5所述的柔性多功能的交联粘接剂的应用，其特征在于，在二次锂硫电池正极制备过程中，分别配制瓜尔豆胶水溶液和羧基丁苯橡胶水溶液，按配比混合并搅拌得到均匀乳白色溶液，采用原位交联法，将得到的乳白色溶液直接用于正极制备并形成所述的柔性多功能的交联粘接剂，分子间交联在极片干燥过程中原位发生。
  7. 根据权利要求5所述的柔性多功能的交联粘接剂的应用，其特征在于，
    所述的导电剂由乙炔黑和替代碳材料组成，所述的替代碳材料包括碳纳米管、碳纳米纤维、石墨烯或氧化石墨烯；
    优选所述的导电剂由替代碳材料和乙炔黑按照质量比2:1-1:4混合组成；
    进一步优选所述的导电剂由羧基化的碳纳米管和乙炔黑按照质量比2:1-1:4混合组成。
  8. 根据权利要求5所述的柔性多功能的交联粘接剂的应用，其特征在于，所述的含硫材料为硫基复合材料，由单质硫与聚丙烯腈按质量比4-16:1混合后在氮气或氩气保护下加热至250-400℃并保温1-16h得到。
  9. 根据权利要求8所述的柔性多功能的交联粘接剂的应用，其特征在于，所述的含硫材料制备过程中，包括以下条件中的任一项或多项：
    (i)所述的聚丙烯腈的分子量为1万-100万；
    (ii)所述的含硫材料中硫的质量含量为30-70％。
  10. 根据权利要求5所述的柔性多功能的交联粘接剂的应用，其特征在于，对单个二次锂硫电池正极进行0-20MPa的压力处理，以制备高压实密度电极；不同压力处理后的二次锂硫电池正极压实密度为0.8-1.6g/cm 3，孔隙率50-10％。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114665094A (zh) * 2022-03-15 2022-06-24 南京航空航天大学 一种水系粘结剂和锂离子电池硅基负极及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111293312B (zh) * 2020-02-21 2024-02-20 上海交通大学 一种柔性多功能的交联粘接剂及其制备方法和应用
CN113161549B (zh) * 2021-03-25 2022-08-02 万向一二三股份公司 一种光交联的粘结剂体系、含有其的浆料组合物及浆料组合物的应用
CN114512671B (zh) * 2022-01-24 2023-04-21 江苏中兴派能电池有限公司 一种交联型粘结剂及其制备方法和用途
CN115677274A (zh) * 2022-09-09 2023-02-03 广州铁路职业技术学院（广州铁路机械学校） 一种基于高粘结性柔性电极的介电弹性体材料发电系统
CN116515392B (zh) * 2023-04-27 2024-02-06 北京首华建设经营有限公司 一种油满及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1641916A (zh) * 2004-01-17 2005-07-20 三星Sdi株式会社 用于锂二次电池的阳极和使用该阳极的锂二次电池
CN101981727A (zh) * 2008-03-31 2011-02-23 日本瑞翁株式会社 多孔膜以及二次电池电极
CN106531964A (zh) * 2016-10-21 2017-03-22 上海交通大学 硫正极用水性粘结剂及其应用
WO2018195897A1 (zh) * 2017-04-28 2018-11-01 罗伯特·博世有限公司 用于锂离子电池的复合粘结剂及其制备方法
CN109768282A (zh) * 2018-12-24 2019-05-17 上海交通大学 一种水性复合粘接剂及其应用
CN110770950A (zh) * 2017-06-13 2020-02-07 罗伯特·博世有限公司 用于锂离子电池的复合粘合剂及其制备方法
CN111293312A (zh) * 2020-02-21 2020-06-16 上海交通大学 一种柔性多功能的交联粘接剂及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104327762A (zh) * 2014-09-30 2015-02-04 河南师范大学 一种锂离子电池增强型复合粘合剂、制备方法和应用
CN104766945A (zh) * 2015-03-30 2015-07-08 深圳市斯盛能源股份有限公司 一种锂离子二次电池正极片及其制作方法
CN104934609A (zh) * 2015-05-04 2015-09-23 厦门大学 一种锂离子电池硅基负极材料粘结剂
KR20170122378A (ko) * 2016-04-27 2017-11-06 한국전기연구원 구아검을 포함하는 실리콘 전극 및 그 제조방법
CN108574103B (zh) * 2018-04-28 2020-08-28 浙江天晨胶业股份有限公司 一种锂离子电池用粘结剂及制法、电极材料、电极
CN109755579B (zh) * 2018-12-29 2020-12-01 山东华夏神舟新材料有限公司 锂离子电池用正极复合导电粘结剂的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1641916A (zh) * 2004-01-17 2005-07-20 三星Sdi株式会社 用于锂二次电池的阳极和使用该阳极的锂二次电池
CN101981727A (zh) * 2008-03-31 2011-02-23 日本瑞翁株式会社 多孔膜以及二次电池电极
CN106531964A (zh) * 2016-10-21 2017-03-22 上海交通大学 硫正极用水性粘结剂及其应用
WO2018195897A1 (zh) * 2017-04-28 2018-11-01 罗伯特·博世有限公司 用于锂离子电池的复合粘结剂及其制备方法
CN110770950A (zh) * 2017-06-13 2020-02-07 罗伯特·博世有限公司 用于锂离子电池的复合粘合剂及其制备方法
CN109768282A (zh) * 2018-12-24 2019-05-17 上海交通大学 一种水性复合粘接剂及其应用
CN111293312A (zh) * 2020-02-21 2020-06-16 上海交通大学 一种柔性多功能的交联粘接剂及其制备方法和应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114665094A (zh) * 2022-03-15 2022-06-24 南京航空航天大学 一种水系粘结剂和锂离子电池硅基负极及其制备方法

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