WO2021248766A1 - 一种复合聚合物固态电解质材料及其制备方法和应用 - Google Patents

一种复合聚合物固态电解质材料及其制备方法和应用 Download PDF

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WO2021248766A1
WO2021248766A1 PCT/CN2020/121426 CN2020121426W WO2021248766A1 WO 2021248766 A1 WO2021248766 A1 WO 2021248766A1 CN 2020121426 W CN2020121426 W CN 2020121426W WO 2021248766 A1 WO2021248766 A1 WO 2021248766A1
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lithium
composite polymer
solid electrolyte
electrolyte material
polymer electrolyte
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PCT/CN2020/121426
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French (fr)
Chinese (zh)
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朱敏
刘雨轩
胡仁宗
刘军
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华南理工大学
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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 solid electrolyte materials, and specifically relates to a composite polymer solid electrolyte material and a preparation method and application thereof.
  • the composite electrolyte In semi-crystalline polyethylene oxide, ion flow only occurs in the amorphous region of its matrix, which results in its room temperature ionic conductivity of only 10 -6 to 10 -8 S ⁇ cm -1 , which is far from satisfying practical applications. Therefore, the composite electrolyte is considered to be a compromise solution for realizing the application of solid electrolytes, which is used to realize the complementary advantages between the electrolyte components and improve the electrochemical performance of the composite electrolyte.
  • Studies have shown that in composite polymer electrolytes with inorganic fillers, the high-speed channel for lithium ion transmission at the interface between the inorganic filler and polymer is critical to the improvement of the ion conductivity of the composite polymer electrolyte. Therefore, the design has The interface of high-speed lithium ion transfer is an effective way to solve the low ion conductivity of the polymer matrix.
  • Existing fillers used for composite in composite polymer solid electrolytes mainly include nano-ceramic fillers, such as published patent applications CN 105655635A, patent CN 102709597A; ionic liquids, such as published patent CN 104538670A; organic micro-nano porous particles , Such as CN 106654363A, etc.
  • nano-ceramic fillers such as published patent applications CN 105655635A, patent CN 102709597A
  • ionic liquids such as published patent CN 104538670A
  • organic micro-nano porous particles Such as CN 106654363A, etc.
  • the interface interaction between the filler and the polymer electrolyte is weak, which makes the transfer rate of lithium ions in these interface transmission channels low. Therefore, these fillers have a lower ion conductivity of the polymer matrix. The lifting effect is limited.
  • the existing composite polymer electrolyte materials lack the control of the microstructure and the design of the ion rapid transfer channel for the compounding of the filler. These factors all lead to the unsatisfactory performance of the currently prepared composite polymer electrolyte materials in practical applications.
  • the present invention is to provide a composite polymer solid electrolyte material and a preparation method thereof.
  • the composite polymer solid electrolyte material of the present invention has better ionic conductivity in a larger temperature range.
  • Another object of the present invention is to provide the application of the composite polymer solid electrolyte material.
  • the composite polymer solid electrolyte material is applied in a lithium battery and used as a solid electrolyte of a lithium battery.
  • a composite polymer solid electrolyte material prepared from the following components:
  • the lithium salt is preferably at least one of lithium perchlorate, lithium hexafluorophosphate or lithium bistrifluoromethanesulfonimide;
  • the general formula of the lithium alloy is Li x M, where M is a metal or non-metal element, x ⁇ 1, and x is the atomic ratio of Li/M; the lithium alloy is one or more of Li x M.
  • M in the lithium alloy is preferably Si, Ge or Sn.
  • the lithium alloy is more preferably one or more of Li 21 Si 5 , Li 21 Ge 5 , and Li 21 Sn 5 .
  • the organic solvent includes at least one of 1,3-dioxolane or 2-methyl-1,3-dioxolane.
  • the organic solvent also includes an auxiliary solvent, and the auxiliary solvent is an ether or ester organic solvent, specifically ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate or dimethylformamide ( DMF) more than one kind.
  • auxiliary solvent is an ether or ester organic solvent, specifically ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate or dimethylformamide ( DMF) more than one kind.
  • the mass of the filler accounts for 1%-30% of the total mass of the polymer electrolyte, the lithium salt and the filler.
  • the mass ratio of the polymer electrolyte to the lithium salt is 1:0.1 to 1:0.8.
  • the polymer electrolyte is one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polycarbonate, polyvinylidene fluoride and copolymers thereof.
  • the volume-to-mass ratio of the organic solvent to the polymer electrolyte is (15-30) mL:1g.
  • the composite polymer solid electrolyte material is in the shape of a membrane, and the thickness of the membrane is 25-200 microns.
  • the preparation method of the composite polymer solid electrolyte material includes the following steps:
  • the organic solvent is a main solvent and an auxiliary solvent;
  • the main solvent is one or more of 1,3-dioxolane or 2-methyl-1,3-dioxolane;
  • the auxiliary solvent is an ether Or ester organic solvents, specifically one or more of ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate or dimethylformamide.
  • the auxiliary solvent adjusts the viscosity.
  • the volume-to-mass ratio of the organic solvent to the polymer electrolyte is (15-30) mL:1g.
  • the volume ratio of the auxiliary solvent to the main solvent is 0.1:1 to 5:1.
  • the film formation specifically refers to pouring the mixture on a substrate, drying at 60°C to 100°C for 6 hours to 24 hours in an anhydrous and oxygen-free environment, and peeling off to obtain a film material.
  • the solid electrolyte has an ionic conductivity greater than 3 ⁇ 10 -5 S/cm at 30°C.
  • the above-mentioned composite polymer solid electrolyte is applied to the field of ion conductor or lithium ion battery.
  • a lithium ion battery includes a positive electrode, a negative electrode, and a solid electrolyte placed between the positive and negative electrodes.
  • the solid electrolyte is the above-mentioned composite polymer solid electrolyte.
  • the principle of the present invention is: the present invention utilizes the reaction of a lithium alloy with an organic solvent to open the ring of the 1,3 dioxolane-based cyclic solvent, and form an organic layer on the surface of the lithium alloy that can realize the rapid transfer of lithium ions. Floor.
  • the organic layer is uniformly dispersed in the lithium salt-containing polymer electrolyte along with the lithium alloy, and interacts with the lithium salt-containing polymer matrix, so that a large number of ion rapid transmission channels are formed in the polymer matrix.
  • the promotion of has a key role.
  • the nano-scale lithium alloy filler interacts with the polymer matrix, the regular crystalline segments around it are broken, which increases the proportion of amorphous regions in the polymer matrix. Since the migration of lithium ions in the polymer electrolyte is mainly contributed by the amorphous region in the polymer, the improvement of the amorphous region can further enhance the ability of the composite polymer electrolyte to transfer lithium ions.
  • the present invention constructs a lithium-rich solid electrolyte interface similar to the liquid battery system between the polymer solid electrolyte and the filler. These interfaces constructed in the polymer electrolyte provide a fast channel for the migration of the lithium ion battery, so that the polymer The ionic conductivity of the electrolyte has been greatly improved.
  • the composite polymer solid electrolyte of the present invention can replace the diaphragm and electrolyte in a traditional battery to realize the circulation of an all-solid lithium battery at room temperature. At the same time, because the traditional liquid electrolyte is replaced, the lithium battery using the solid electrolyte does not need to be equipped with an additional temperature control system.
  • the preparation method of the present invention has universal applicability.
  • the main material polymer electrolyte and lithium salt have a wide range of choices and are cheap and easy to obtain.
  • This method can be used to prepare composite polymer solid electrolytes under different combinations of polymer electrolytes and lithium salts, and the prepared solid electrolytes have relatively high advantages. Good cycle stability.
  • Figure 1 is a high-resolution scanning electron micrograph of a cross-section of the composite polymer electrolyte material prepared in Example 1;
  • Example 4 is a charge-discharge cycle performance diagram of a lithium symmetric battery using the composite polymer electrolyte prepared in Example 6;
  • FIG. 5 is a graph showing the cycle performance of an all-solid-state lithium metal battery assembled using composite polymer electrolytes, lithium iron phosphate positive electrodes and lithium metal negative electrodes prepared in Examples 1 and 7.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy lithium silicon alloy Li 21 Si 5 , self-made by thermal reaction method, self-made method will be explained in the specific process.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • the lithium particles and silicon powder Under the protection of argon atmosphere, mix the lithium particles and silicon powder in a ratio of 21:5 (about 0.52g of lithium particles and about 0.48g of silicon powder) on a heating table and heat them to 200°C to melt the lithium particles. After the liquid lithium is stirred, the lithium-silicon alloy powder can be formed.
  • the powder is put into a ball milling tank, and the lithium-silicon alloy powder is refined by vibrating ball milling, in which the grinding ball is mixed with The powder ratio is 50:1, the ball milling time is 20h, the rotation speed is 1000rpm, and the Li 21 Si 5 lithium-silicon alloy powder (particle size 200-300nm) is prepared.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • the composite polymer electrolyte prepared in Example 1 was sandwiched between two stainless steel substrates with polished surfaces to form a blocking electrode. Using electrochemical work to perform AC impedance analysis on the composite material in the blocking electrode at different temperatures in a thermostat, the ionic conductivity corresponding to different temperatures can be obtained. The relationship between the electrical conductivity and temperature of the composite polymer electrolyte prepared in Example 1 in a wide temperature range is shown in Fig. 2 and Fig. 3.
  • the composite polymer electrolyte prepared in Example 1 was assembled with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode to form an all-solid-state lithium metal battery.
  • the cycle performance at 45° C. and 0.2 C is shown in FIG. 5. Its capacity is 140.5 mAh g-1 after 100 cycles at 30°C and 0.2C, and its capacity is 110.8 mAh g-1 after 200 cycles at 45°C and 0.5C.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy lithium germanium alloy Li 21 Ge 5 , self-made by the thermal reaction method, the self-made method is similar to the Li 21 Si 5 method in Example 1, and the silicon powder is replaced with Ge.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 2 The method for testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the relationship between the conductivity and temperature of the composite polymer electrolyte prepared in Example 2 in a wide temperature range is shown in FIG. 2.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy lithium tin alloy Li 21 Sn 5 , self-made by thermal reaction method, self-made method is the same as the above Li 21 Si 5 method, silicon powder is replaced with Sn.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 2 The method for testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the relationship between the conductivity and temperature of the composite polymer electrolyte prepared in Example 3 in a wide temperature range is shown in FIG. 2.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy lithium-silicon alloy Li 21 Si 5 , self-made by thermal reaction method, self-made method is the same as in Example 1.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 3 The method of testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the conductivity of the composite polymer electrolyte prepared in Example 4 in a wide temperature range is shown in FIG. 3.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy Li-silicon alloy Li 21 Si 5 , self-made by the thermal reaction method, and the self-made method is the same as in Example 1.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 3 The method of testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the conductivity of the composite polymer electrolyte prepared in Example 5 in a wide temperature range is shown in FIG. 3.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy a mixed lithium alloy of lithium silicon alloy Li 21 Si 5 and lithium germanium alloy Li 21 Ge 5 , self-made by the thermal reaction method, and the self-made method is the same as in Example 1.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • the composite polymer electrolyte prepared in Example 6 and lithium metal were assembled to form a lithium symmetric battery, and its cycle performance under the conditions of 30° C. and 0.1 mAcm -2 is shown in FIG. 4.
  • the composite polymer electrolyte prepared in Example 6 was assembled with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode to form an all-solid-state lithium metal battery.
  • the first discharge capacity was 143.2mAh g -1 at 45°C and 0.2C. After 50 cycles Its capacity is 131.6 mAh g -1 , and the capacity retention rate is 92%.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium perchlorate (LiClO 4 ), purchased from Aladdin Company.
  • Lithium alloy Li-silicon alloy Li 21 Si 5 , self-made by the thermal reaction method, and the self-made method is the same as in Example 1.
  • Organic solvents 2-methyl-1,3-dioxolane and ethylene carbonate, purchased from Macklin Company.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Li 21 Si 5 powder Weigh 74 mg of Li 21 Si 5 powder; add PEO, LiClO 4 and Li 21 Si 5 powder to the above 2-methyl-1,3-dioxolane and In the mixed organic solvent of ethylene carbonate, the mixture was continuously stirred for 12 hours and then poured on a clean polytetrafluoroethylene board, and then dried at a temperature of 60°C for 12 hours to obtain PEO with lithium-silicon alloy Li 21 Si 5 added. Based composite polymer electrolyte.
  • Example 7 The composite polymer electrolyte prepared in Example 7 was assembled with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode to form an all-solid-state lithium metal battery.
  • the cycle performance at 45° C. and 0.2 C is shown in FIG. 5.
  • Polymer electrolyte Polypropylene carbonate (PPC) powder, purchased from Macklin Company, with an average molecular weight of 50,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy Li-silicon alloy Li 21 Si 5 , self-made by the thermal reaction method, and the self-made method is the same as in Example 1.
  • Organic solvents 1,3-dioxolane and dimethylformamide, purchased from Macklin Company.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • the composite polymer electrolyte prepared in Example 8 was assembled with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode to form an all-solid-state lithium metal battery.
  • the first discharge capacity was 132.5mAh g -1 at 30°C and 0.2C. After 50 cycles Its capacity is 110 mAh g -1 , and the capacity retention rate is 83%.
  • PVDF-HFP polyvinylidene fluoride-co-hexafluoropropylene
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Lithium alloy Li-silicon alloy Li 21 Si 5 , self-made by the thermal reaction method, and the self-made method is the same as in Example 1.
  • Organic solvents 1,3-dioxolane 5mL, dimethylformamide 5mL, purchased from Macklin Company.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • the composite polymer electrolyte prepared in Example 9 was assembled with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode to form an all-solid-state lithium metal battery.
  • the first discharge capacity was 140.3mAh g -1 at 30°C and 0.2C. After 50 cycles Its capacity is 124.3 mAh g -1 , and the capacity retention rate is 88.5%.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a polymer electrolyte material includes the following steps:
  • Example 1 The method for testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the relationship between the conductivity and temperature of the composite polymer electrolyte prepared in Comparative Example 1 in a wide temperature range is shown in Figs. 2 and 3.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Filler pure silicon powder, powder particle size 1 ⁇ m, purchased from Aladdin Company. The powder was processed using the same ball milling process as in Example 1.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 2 The method of testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the relationship between the conductivity and temperature of the composite polymer electrolyte prepared in Comparative Example 2 in a wide temperature range is shown in FIG. 2.
  • Polymer electrolyte Polyethylene oxide (PEO) powder, purchased from Aladdin Company, with an average molecular weight of 600,000.
  • Lithium salt Lithium bistrifluoromethanesulfonimide (LiTFSI), purchased from Aladdin Company.
  • Silica powder powder particle size 1 ⁇ m, purchased from Aladdin Company. The powder was processed using the same ball milling process as in Example 1.
  • Organic solvents 1,3 dioxolane (DOL) and ethylene glycol dimethyl ether (DME), purchased from Macklin.
  • a method for preparing a composite polymer electrolyte material includes the following steps:
  • Example 2 The method of testing the ionic conductivity versus temperature curve in Example 1 is the same.
  • the relationship between the conductivity and temperature of the composite polymer electrolyte prepared in Comparative Example 3 in a wide temperature range is shown in FIG. 2.
  • Figure 1 is a cross-sectional high-resolution scanning electron micrograph of the composite polymer electrolyte material prepared in Example 1;
  • Figure 2 is a different lithium alloy and other inorganic materials prepared in Examples 1, 2, 3 and Comparative Examples 1, 2, and 3 The electrical conductivity of the filler composite polymer electrolyte versus temperature;
  • Figure 3 shows the electrical conductivity of the composite polymer electrolyte prepared in Examples 1, 4, 5 and Comparative Example 1 as a function of the Li 21 Si 5 filler content Graph;
  • Figure 4 is a graph showing the charge-discharge cycle performance of a lithium symmetrical battery prepared using the composite polymer electrolyte prepared in Example 6; Cycle performance graph of all solid-state lithium metal battery assembled with metal anode.
  • the above embodiments show the effect of the lithium alloy composite technology route used in the present invention on polymer-based solid electrolytes from four aspects: different polymer solid electrolyte substrates, different lithium salts, different lithium alloy fillers, and different organic solvent components.
  • the improvement of electrochemical performance has a wide range of universality and effectiveness.
  • the method of using lithium alloys to construct a lithium-rich artificial solid electrolyte interface is important for realizing the rapid transfer of lithium ions in the polymer electrolyte, and finally realizing the polymer
  • the improvement of electrolyte ionic conductivity is unique.
  • Figure 2 compares the variation curves of the ionic conductivity of polymer solid electrolytes with different lithium alloy fillers as a function of temperature. It can be seen from the figure that, compared to Comparative Example 1, the ion conductivity of the polymer solid electrolyte composited with a variety of lithium alloy fillers is significantly improved at different temperatures. For example, at 30°C, the ionic conductivity of the composite polymer electrolytes of Examples 1, 2, and 3 are 3.92 ⁇ 10 -5 S cm -1 , 2.72 ⁇ 10 -5 S cm -1 , and 1.80 ⁇ 10 -5 S, respectively cm -1 , which are several times higher than the ionic conductivity of Comparative Example 1 at 6.89 ⁇ 10 -6 S cm -1.
  • Example 1 Comparing Example 1 with Comparative Examples 2, 3, it can be seen that the ionic conductivity of Example 1 is higher than that of Comparative Examples 2 and 3 (7.55 ⁇ 10 -6 S cm -1 and 9.42 ⁇ 10 respectively). -6 S cm -1 ) is several times higher, which indicates that the polymer solid electrolyte composited with lithium alloy fillers has a significant advantage in improving ionic conductivity compared with other fillers. This difference and particularity comes from the lithium-rich artificial solid electrolyte interface formed by the interaction between the lithium alloy and the polymer electrolyte.
  • Example 1 the test results of the full battery assembled in Example 1 show that the composite polymer electrolyte has high ionic conductivity and can achieve long-cycle stability with a higher capacity under the test conditions given in Example 1. sex.
  • Examples 1, 4, and 5 compare the ionic conductivity of polymer electrolytes composited with different lithium alloy contents at different temperatures with Comparative Example 1, as shown in FIG. 3. It can be seen that the lithium alloy composite polymer electrolyte has a significant effect on improving its ionic conductivity within a wide range of lithium alloy content filling.
  • Example 6 uses two lithium alloy composite polymer electrolytes. After being assembled with lithium metal to form a symmetric battery, the symmetric battery remains stable within 500 cycles under set conditions, as shown in Figure 4, which proves that one or The polymer electrolyte compounded by a variety of lithium alloy fillers can realize the cycle of the battery and remain stable during the cycle. At the same time, the all-solid-state lithium metal battery of this embodiment can also maintain good cycle stability.
  • Example 7 Comparing the test results of Example 7 and the results of Example 1, it can be seen that the combination of different lithium salts and different solvents mentioned in the content of the invention can assemble an all-solid-state lithium metal battery with excellent cycle performance, indicating that the lithium alloy
  • the composite polymer electrolyte solution has universal applicability to different lithium salts and different solvents in the preparation process, as shown in Figure 5.

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PCT/CN2020/121426 2020-06-10 2020-10-16 一种复合聚合物固态电解质材料及其制备方法和应用 WO2021248766A1 (zh)

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