CN114759254A - Solid electrolyte membrane and preparation method thereof - Google Patents

Solid electrolyte membrane and preparation method thereof Download PDF

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Publication number
CN114759254A
CN114759254A CN202210457909.4A CN202210457909A CN114759254A CN 114759254 A CN114759254 A CN 114759254A CN 202210457909 A CN202210457909 A CN 202210457909A CN 114759254 A CN114759254 A CN 114759254A
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solid electrolyte
electrolyte membrane
lithium
fiber non
woven fabric
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谭龙
樊凯博
汤昊
赖俊宝
刘玉娟
孙润光
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Nanchang University
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Dispersion Chemistry (AREA)
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  • Secondary Cells (AREA)

Abstract

The invention discloses a solid electrolyte membrane and a preparation method thereof, and specifically relates to a solid electrolyte membrane which is prepared by adding a polymer matrix material, lithium salt and fast ion conductor particles into a specific solvent to obtain a sol mixed solution, then titrating solid electrolyte slurry on fiber non-woven fabric according to a preset amount to ensure that the fiber non-woven fabric is fully soaked with the solid electrolyte slurry, then carrying out drying treatment to remove residual organic solvent, and finally carrying out rolling treatment to obtain the solid electrolyte membrane taking the fiber non-woven fabric as a substrate. Compared with a solid electrolyte membrane independently formed on a polytetrafluoroethylene mold or a glass plate, the method is simpler in process and has excellent mechanical properties and thermal stability. On the other hand, the growth of lithium dendrites is effectively inhibited, the high mobility of lithium ions is ensured, the solid lithium ion battery is endowed with excellent cycle performance and higher holding capacity, and the application prospect is excellent.

Description

Solid electrolyte membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a solid electrolyte membrane and a preparation method thereof.
Background
With the development of new energy technology, lithium ion batteries stand out in numerous secondary batteries due to the advantages of low self-discharge rate, long service life, no memory effect and the like, but the current commercial lithium ion batteries face many problems due to the adoption of a non-aqueous electrolyte solution with high chemical activity, flammability and volatility, for example, when the conditions of overcharge, overdischarge, internal short circuit and the like occur, the electrolyte can be caused to generate heat and spontaneously combust, so that potential safety hazards such as explosion and the like are caused. The solid lithium ion battery adopts a layer of electrolyte membrane to replace a diaphragm and electrolyte, so that various safety problems caused by liquid electrolyte can be effectively avoided, and the energy density and the electrochemical performance are greatly improved.
Most of solid electrolyte membranes prepared in the current research are directly molded on a polytetrafluoroethylene mold or a glass plate so as to obtain independently molded electrolyte membranes, but the defects are obvious, the preparation method has long required period and strict control on drying time and drying temperature, and the prepared electrolyte membranes are generally adhered to the polytetrafluoroethylene template to cause electrolyte membrane damage and serious powdering. Further, in the subsequent battery assembly process, the lithium dendrites penetrate through the electrolyte membrane, which causes the problems of short circuit between the anode and cathode contacts or collapse of the anode structure. In contrast, a few of the electrode plates/electrolyte membranes prepared by the slurry coating technology have a slightly short molding cycle of composite membrane preparation, but are easily separated from the current collector substrate under the condition of improper control of process conditions, so that the electrochemical performance is affected. This makes it important to prepare a solid electrolyte membrane that is rapidly formed, has a simple process, and has high mechanical and electrochemical properties.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a solid electrolyte membrane and a preparation method thereof, and the prepared solid electrolyte membrane has excellent mechanical property and high ionic conductivity.
The invention is realized by the following technical scheme:
a solid electrolyte membrane is formed by cross-linking solid electrolyte slurry and fiber non-woven fabrics, wherein polymers in the solid electrolyte slurry are divided into rigid chain segment polymers and flexible chain segment polymers, the cross-linking of the rigid chain segment polymers and the fibers constructs a main body part of a three-dimensional conduction network, the flexible chain segment polymers make up overlarge pores in the fiber non-woven fabrics and serve as an auxiliary part of the conduction network, and finally fast ion conductor particles and lithium salt are uniformly dispersed on the conduction network and are mixed with the fibers for cross-linking to construct a new lithium ion transmission channel.
The preparation method of the solid electrolyte membrane comprises the following steps:
(1) preparation of solid electrolyte slurry: drying the selected polymer, lithium salt and fast ion conductor particles in a vacuum drying oven for more than 24 hours, weighing one or more rigid chain segment polymers according to a preset proportion, dissolving the rigid chain segment polymers in a preset amount of solvent in a physical blending mode, and stirring the rigid chain segment polymers in a constant-temperature water bath kettle for a first preset time to obtain a first type of sol mixed solution. And then, weighing one or more flexible chain segment polymers according to a preset proportion, directly adding the one or more flexible chain segment polymers into the first sol-like mixed solution, stirring at a constant temperature, and stirring for a second preset time to obtain a second sol-like mixed solution. And weighing one or more lithium salts according to a preset proportion, directly adding the one or more lithium salts into the second sol-like mixed solution, stirring at a constant temperature, and stirring for a third preset time to obtain a third sol-like mixed solution. And finally, weighing one or more fast ion conductor particles according to a preset proportion, directly adding the fast ion conductor particles into the third sol mixed solution, stirring at a constant temperature for fourth preset time to obtain a fourth sol mixed solution. I.e., a solid electrolyte slurry.
(2) And (3) infiltration treatment: soaking the fiber non-woven fabric in the solid electrolyte slurry obtained in the step (1) to preset the dropping amount of 10 mu L/cm2-200μL/cm2After the electrolyte slurry is fully soaked for 15min-30min, the electrolyte slurry is placed into an air-blast drying oven to remove residual organic solvent, then the electrolyte slurry is transferred into a vacuum drying oven, and is dried for 1h-2h at the temperature of 60 ℃ to 150 ℃ to prepare the electrolyte slurryA composite solid electrolyte membrane using a fiber non-woven fabric as a substrate.
(3) And (3) rolling treatment: rolling the solid electrolyte membrane with the fiber non-woven fabric as the substrate in a press machine under the pressure of 6MPa-45MPa to obtain the solid electrolyte membrane with the thickness of 10-70 μm and the compacted density of 5g/cm3-30g/cm3And a tensile strength of more than 10 MPa. After the rolling treatment, the high compaction density can obviously make the pore diameter and pore distribution of the composite solid electrolyte membrane more uniform, the polymer, lithium salt and fast ion conductor particles are distributed more uniformly on the fiber, the contact resistance and the charge exchange impedance between the electrolyte membrane and the pole piece are reduced, the area capable of participating in lithium ion transmission is increased, and thus the electrochemical performance of the material is obviously improved.
Further, the solvent in step (1) is one or more of acetone, N-Dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone (NMP), Tetrahydrofuran (THF), Dimethylacetamide (DMAC), Tetramethylurea (TMU), and Dimethylsulfoxide (DMSO).
Further, in the step (1), the ratio of the hard segment polymer substance is in a range of 50 wt.% to 65 wt.%, the ratio of the soft segment polymer substance is in a range of 10 wt.% to 30 wt.%, and the hard segment polymer is one or more of Succinonitrile (SN), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), Polymethacrylate (PMMA), polymethylethylene carbonate (PPC), Hexamethylene Diisocyanate (HDI). Wherein the soft segment polymer is one or more of polyvinyl acetate (PVAC), polyethylene glycol (PEG), tetraethylene glycol dimethyl ether (TEGDME), ethylene carbonate (VEC) and trimethoxymethyl silane (MTM);
further, in the step (1), the mass ratio of the fast ion conductor particles ranges from 2 wt.% to 30 wt.% in terms of mass percentage (wt.%). In particular fast ion conductor particles such as Perovskit type Li1/2La1/2TiO3Or NASICON type AM2(PO4)3Where A is Li, Na, M is Ge, Ti, Zr or Garnet type A3B2(XO4)3Where A ═ Ca, Mg, Y, La, B ═ Al, Fe, Ga, Ge, Mn, Ni, V, X ═ Si, Ge, Al or Li of the LISICON type14ZnGe4O16Or Li of the LISICON type4-xGe1-xPxS4One or more of (a). According to the preset proportion, on one hand, the crystallinity of the polymer is reduced and the glass transition temperature T of the polymer is reducedgMore amorphous regions capable of rapidly conducting lithium ions are provided, and on the other hand, the addition of a small amount of fast ion conductor particles does not cause large-area agglomeration.
Further, in the step (1), the mass ratio of the lithium salt ranges from 2 wt.% to 38 wt.%, in terms of mass percent (wt.%). Specifically, the lithium salt is lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF)6) One or more of lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium trifluoromethanesulfonate (LiTF), lithium bistrifluorosulfonylimide (LiFSI), lithium dioxalate borate (LiBOB), and lithium difluorooxalate borate (lidob).
Further, the first preset time in the step (1) is 1h-2h, specifically, the heating temperature of stirring in the constant-temperature water bath kettle is 40 ℃ to 60 ℃, and the rotating speed range of the stirring rotor is 2000r/min to 2500 r/min. By adopting the rotating speed, the first type of sol mixed solution can be more uniform, and the generation of bubbles can be reduced.
Further, the second preset time in the step (1) is 1h-2h, specifically, the heating temperature of stirring in the constant-temperature water bath kettle is 40 ℃ to 60 ℃, and the rotating speed range of the stirring rotor is 2000r/min to 2500 r/min. The second type of sol mixed solution can be more uniform by adopting the rotating speed, and the generation of bubbles is reduced.
Further, the third preset time in the step (1) is 2h-3h, specifically, the heating temperature of stirring in the constant-temperature water bath kettle is 40 ℃ to 60 ℃, and the rotating speed range of the stirring rotor is 2000r/min to 2500 r/min. The third type of sol mixed solution can be more uniform by adopting the rotating speed, and the generation of bubbles is reduced.
Further, after the fast ion conductor particles are added in the step (1), the fourth preset time is set to be 2h-3h, specifically, the heating temperature of stirring in the constant-temperature water bath kettle is 40-60 ℃, and the rotating speed range of the stirring rotor is 2000r/min-2500 r/min. Wherein the fourth type of sol-like mixed solution has an internal PH variation and an external color variation, depending on the polymer material selected.
All of the steps described above can be accomplished in an inert atmosphere or room temperature air environment.
The solid electrolyte membrane is prepared by directly soaking fiber non-woven fabrics in solid electrolyte slurry. The method utilizes the advantages that the non-woven fabric has high-efficiency liquid absorption characteristic and is not easy to cause chemical reaction, and the like, and constructs a new lithium ion rapid migration channel by crosslinking the rigid chain segment, the fast ion conductor particles, the lithium salt and the fibers in the non-woven fabric under the condition that the flexible chain segment in the polymer fills up the large pores in the non-woven fabric. The process flow is simple and the period is short, and the obtained solid electrolyte membrane has high Young modulus and bending resistance, and can adapt to various battery assembly forms such as soft packages, buckles, cylinders, blades and the like. The method has low cost and low requirement on preparation environment, and is more suitable for large-scale continuous production of solid electrolyte membranes in industry.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the preparation method has short process period and simple preparation flow, and is easy for large-scale continuous production.
Secondly, the solid electrolyte membrane is formed on the fiber non-woven fabric in a cross-linking mode, the polymer, the fast ion conductor particles and the lithium salt are uniformly dispersed on the three-dimensional conduction network, the conduction of lithium ions in the electrolyte is not hindered, the ionic conductivity of the prepared solid electrolyte membrane is even slightly higher than that of a pure solid electrolyte membrane, and the mechanical property, the thermal stability and the electrochemical property of the solid electrolyte membrane are obviously enhanced by the preparation method.
Thirdly, the preparation method of the solid electrolyte membrane is applicable to all solid electrolyte systems, including polymer electrolyte systems, inorganic electrolyte systems and organic-inorganic composite electrolyte systems.
Detailed Description
The present invention provides a solid electrolyte membrane and a method for preparing the same, and specific examples are provided to clearly describe the process route and the core technical idea of the present invention, but the examples are only a part of the complete system and should not be construed as limiting the present invention. Based on the embodiments, those skilled in the art can obtain specific embodiments without inventive breakthrough in the technical scheme and scheme of the invention, and the specific embodiments are within the scope of the invention.
The experimental starting materials selected were all commercially available, except where otherwise noted.
Example 1
(1) Preparation of solid electrolyte slurry: PVDF in mass percent (wt.%): 50%, PVAC: 20%, and Litf: 20%, LLZTO: the raw materials are weighed according to the proportion of 10 percent. Dissolving PVDF rigid chain segment polymer in 9mL DMF solvent by adopting a physical blending mode, and stirring for 1h at a rotating speed of 2500r/min in a constant-temperature water bath kettle at 60 ℃ to obtain a first type of sol mixed solution; and then directly adding the PVAC flexible chain segment polymer into the first type of sol mixed solution, and stirring for 1h in a constant-temperature water bath kettle at the temperature of 60 ℃ at the rotating speed of 2500r/min to obtain a second type of sol mixed solution. Then directly adding the LiTF particles into the second type of sol-like mixed solution, and stirring for 3 hours in a constant-temperature water bath kettle at 50 ℃ at a rotating speed of 2000r/min to obtain a third type of sol-like mixed solution; and finally, directly adding the LLZTO fast ion conductor particles into the third sol mixed solution, and stirring for 3 hours in a constant temperature water bath kettle at 50 ℃ at a rotating speed of 2000r/min to obtain a fourth sol mixed solution, namely solid electrolyte slurry.
(2) Infiltrating: cutting laboratory dust-free paper into 19mm round pieces on a slicer, titrating the solid electrolyte slurry obtained in the step (1) on the dust-free paper by using a pipette, and presetting the preset infiltration amount to be 150 mu L/cm2After the fiber non-woven fabric is fully soaked for 25min, the fiber non-woven fabric is placed into a forced air drying oven at the temperature of 80 ℃ for drying for 1h, the residual organic solvent is removed, then the fiber non-woven fabric is transferred into a vacuum drying oven for drying for 1h at the temperature of 60 ℃, and the fiber non-woven fabric is preparedA composite solid electrolyte membrane of a substrate.
(3) And (3) rolling treatment: rolling the prepared solid electrolyte membrane on a press machine, wherein the rolling pressure is set to be 45MPa, and the thickness of the solid electrolyte membrane is 26 mu m, and the compaction density of the solid electrolyte membrane is 13.8g/cm3The electrolyte membrane of (1).
Example 2
(1) Preparation of solid electrolyte slurry: PVDF as a mass percent (wt.%): 50%, PVAC: 20%, and Litf: 20%, LLZTO: the raw materials are weighed according to the proportion of 10 percent. A solid electrolyte slurry was prepared in the same manner as in step (1) in example 1.
(2) Infiltrating: cutting laboratory dust-free paper into 19mm round pieces on a slicing machine, and titrating the solid electrolyte slurry obtained in the step (1) on the dust-free paper by using a pipette gun, wherein the preset titration amount is 100 mu L/cm2And after the mixture is fully soaked for 20min, drying the mixture in an air drying oven at the temperature of 80 ℃ for 1h, removing residual organic solvent, transferring the dried mixture to a vacuum drying oven, and drying the dried mixture at the temperature of 60 ℃ for 1h to prepare the composite solid electrolyte membrane taking the fiber non-woven fabric as the substrate.
(3) And (3) rolling treatment: rolling the prepared solid electrolyte membrane on a press with the preset pressure of 34MPa to obtain the solid electrolyte membrane with the thickness of 43 mu m and the compaction density of 11.9g/cm3The electrolyte membrane of (1).
Example 3
(1) Preparation of solid electrolyte slurry: PVDF in mass percent (wt.%): 50%, PVAC: 20%, and LiTF: 20%, LLZTO: the raw materials are weighed according to the proportion of 10 percent. A solid electrolyte slurry was prepared in the same manner as in step (1) in example 1.
(2) Infiltrating: cutting laboratory dust-free paper into 19mm round pieces on a slicer, and titrating the solid electrolyte slurry obtained in the step (1) on the dust-free paper by using a pipette gun, wherein the preset titration amount is 70 mu L/cm2And after the membrane is fully soaked for 15min, drying the membrane in an air drying oven at 80 ℃ for 1h, removing residual organic solvent, transferring the membrane to a vacuum drying oven, and drying the membrane at 60 ℃ for 1h to prepare the composite solid electrolyte membrane taking the fiber non-woven fabric as the substrate.
(3) And (3) rolling treatment: the prepared solid electrolyte membrane is rolled on a press with the preset pressure of 23MPa to obtain the solid electrolyte membrane with the thickness of 57 mu m and the compaction density of 8.8g/cm3The electrolyte membrane of (1).
Example 4
(1) Preparation of solid electrolyte slurry: PEO in mass percent (wt.%): 56%, PEG: 14% LiClO4: 15%, LLZTO: weighing the raw materials according to the proportion of 15 percent. Dissolving a PEO rigid chain segment polymer in 10mL of THF solvent by adopting a physical blending mode, and stirring for 1h at a rotating speed of 2500r/min in a constant-temperature water bath kettle at 60 ℃ to obtain a first type of sol mixed solution; adding the PEG flexible chain segment polymer into the first sol-like mixed solution, stirring at the constant temperature of 60 ℃ in a water bath at the rotating speed of 2500r/min for 1h to obtain a second sol-like mixed solution, and adding LiClO4Directly adding the particles into the second type of sol mixed solution, and stirring for 3 hours in a constant-temperature water bath kettle at 50 ℃ at a rotating speed of 2000r/min to obtain a third type of sol mixed solution; and finally, directly adding the LLZTO fast ionic conductor particles into the third type of sol mixed solution, and stirring for 3 hours in a constant-temperature water bath kettle at the temperature of 50 ℃ at the rotating speed of 2000r/min to obtain a fourth type of sol mixed solution, namely solid electrolyte slurry.
(2) Infiltrating: cutting laboratory dust-free paper into 19mm round pieces on a slicer, titrating the third gel-like mixed solution obtained in the step (1) on the dust-free paper by using a pipette gun, and presetting the titration amount to 150 mu L/cm2And after the membrane is fully soaked for 25min, drying the membrane in an air drying oven at 80 ℃ for 3h, removing residual organic solvent, transferring the membrane to a vacuum drying oven, and drying the membrane for 1h at 60 ℃ to prepare the composite solid electrolyte membrane taking the fiber non-woven fabric as the substrate.
(3) And (3) rolling treatment: rolling the prepared solid electrolyte membrane on a press with the preset pressure of 45MPa to obtain the solid electrolyte membrane with the thickness of 31 mu m and the compaction density of 14.4g/cm3The electrolyte membrane of (1).
Example 5
(1) Preparation of solid electrolyte slurry: PEO in mass percent (wt.%):56％、PEG：14％、LiClO4: 15%, LLZTO: weighing the raw materials according to the proportion of 15 percent. A solid electrolyte slurry was prepared in accordance with the procedure of step (1) in example 4.
(2) Infiltrating: and (2) cutting the laboratory non-dust paper into 19mm round pieces on a slicer, titrating the third gel-like mixed solution obtained in the step (1) on the non-dust paper by using a liquid transfer gun, presetting the titration amount to be 100 mu L, after fully soaking for 20min, putting the non-dust paper into an air-blast drying oven at 80 ℃ for drying for 1h, removing residual organic solvent, transferring the non-dust paper to a vacuum drying oven, and drying for 1h at 60 ℃ to prepare the composite solid electrolyte membrane taking the fiber non-woven fabric as the substrate.
(3) And (3) rolling treatment: rolling the prepared solid electrolyte membrane on a press with the preset pressure of 34MPa to obtain the solid electrolyte membrane with the thickness of 44 mu m and the compaction density of 11.6g/cm3The electrolyte membrane of (1).
Example 6
(1) Preparation of solid electrolyte slurry: PEO in mass percent (wt.%): 56%, PEG: 14% LiClO4: 15%, LLZTO: weighing the raw materials according to the proportion of 15 percent. A solid electrolyte slurry was prepared in accordance with the procedure in step (1) of example 4.
(2) Infiltrating: cutting laboratory dust-free paper into 19mm round pieces on a slicer, and titrating the third gel-like mixed solution obtained in the step (1) on the dust-free paper by using a pipette gun, wherein the preset titration amount is 70 muL/cm2And after the membrane is fully soaked for 15min, drying the membrane in an air drying oven at 80 ℃ for 1h, removing residual organic solvent, transferring the membrane to a vacuum drying oven, and drying the membrane for 1h at 60 ℃ to prepare the composite solid electrolyte membrane taking the fiber non-woven fabric as the substrate.
(3) And (3) rolling treatment: rolling the prepared solid electrolyte membrane on a press with the preset pressure of 23MPa to obtain the solid electrolyte membrane with the thickness of 60 mu m and the compaction density of 8.7g/cm3The electrolyte membrane of (1).
In embodiments 1 to 6, a solid lithium ion battery is further provided, where the solid lithium ion battery is assembled by using the prepared solid electrolyte membrane with the fiber non-woven fabric as the substrate as the electrolyte layer, using lithium iron phosphate as the positive electrode, and using lithium metal as the negative electrode, and during the assembly of the battery, a small amount of wetting agent is selectively dropped to wet the surface of the solid electrolyte membrane according to the characteristics of the selected polymer material. The electrochemical performance of the solid lithium battery prepared in the embodiment is tested under the condition of normal temperature/0.2C, and a comparative example is provided, wherein the comparative example adopts a corresponding lithium iron phosphate positive pole piece, a liquid electrolyte and a diaphragm are added to assemble a lithium | lithium iron phosphate structure liquid lithium ion battery with metal lithium as a negative pole to perform charge and discharge tests, the charge and discharge voltage is set to be 2.5V-4.1V, and the electrochemical performance results are shown in table 1.
TABLE 1 test results of the charging and discharging performance of the solid-state Li-ion batteries of the samples of examples and comparative examples
Figure BDA0003621078420000061
Figure BDA0003621078420000071
The above-mentioned embodiments and comparative examples are only for illustrative purposes and are not intended to limit the overall content of the invention, and the technical features of the claims are similar to those of the examples, and the combination of the new systems can be constructed, so that the description is clear, and not all the combinations are described one by one, however, the combination of the technical systems should be considered as the scope of the description in the present specification as long as there is no contradiction.
In particular, variations or modifications which would occur to those skilled in the art without departing from the spirit and scope of the claims at the time of filing this specification are to be embraced within their scope.

Claims (10)

1. A solid electrolyte membrane, characterized in that: the solid electrolyte membrane is formed by cross-linking solid electrolyte slurry and fiber non-woven fabrics, wherein polymers in the solid electrolyte slurry are divided into a rigid chain segment polymer and a flexible chain segment polymer, the rigid chain segment polymer and the fibers are cross-linked to form a main part of a three-dimensional conduction network, the flexible chain segment polymer makes up overlarge pores in the fiber non-woven fabrics and serves as an auxiliary part of the conduction network, and finally fast ion conductor particles and lithium salt are uniformly dispersed on the conduction network and are mixed with the fibers to form a new lithium ion transmission channel after cross-linking.
2. The method for producing a solid electrolyte membrane according to claim 1, wherein: the method comprises the following steps:
s1 preparation of solid electrolyte slurry
(1-1) weighing one or more rigid chain segment polymers according to a preset proportion, dissolving the rigid chain segment polymers in a preset amount of solvent in a physical blending mode, and stirring in a constant-temperature water bath kettle for a first preset time to obtain a first sol-like mixed solution;
(1-2) weighing one or more flexible chain segment polymers according to a preset proportion, adding the flexible chain segment polymers into the first type of sol mixed solution, and stirring at a constant temperature for a second preset time to obtain a second type of sol mixed solution;
(1-3) weighing one or more lithium salts according to a preset ratio, directly adding the one or more lithium salts into the second sol-like mixed solution, stirring at a constant temperature, and stirring for a third preset time to obtain a third sol-like mixed solution;
(1-4) weighing one or more fast ion conductor particles according to a preset proportion, directly adding the fast ion conductor particles into a third sol mixed solution, stirring at a constant temperature for a fourth preset time to obtain a fourth sol mixed solution, namely solid electrolyte slurry;
s2 immersion treatment
Soaking the fiber non-woven fabric with the solid electrolyte slurry prepared in the step S1 according to a preset amount, and drying to remove residual solvent after the fiber non-woven fabric is fully soaked, thereby finally preparing the solid electrolyte composite membrane taking the fiber non-woven fabric as the substrate;
s3 rolling treatment
The solid electrolyte membrane based on the fibrous nonwoven fabric prepared in step S2 is subjected to rolling treatment in a press machine to obtain a solid electrolyte membrane having a smaller thickness and a higher compacted density.
3. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: in the step S1, the mass percentages (wt.%) of the hard segment polymer, the soft segment polymer, the lithium salt, and the fast ion conductor particles respectively account for 50% -65%, 10% -30%, 2% -38%, and 2% -30% of the total mass of the raw materials.
4. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: in the step (1-1), the rigid chain segment polymer is one or more of Succinonitrile (SN), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), Polymethacrylate (PMMA), polymethyl ethylene carbonate (PPC) and Hexamethylene Diisocyanate (HDI).
5. The method for producing a solid electrolyte membrane according to claim 2, characterized in that: the soft segment polymer in the step (1-2) is one or more of polyvinyl acetate (PVAC), polyethylene glycol (PEG), tetraethylene glycol dimethyl ether (TEGDME), ethylene carbonate (VEC) and trimethoxymethyl silane (MTM).
6. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: the lithium salt in the step (1-3) is lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) One or more of lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium trifluoromethanesulfonate (LiTF), lithium bistrifluorosulfonylimide (LiFSI), lithium dioxalate borate (LiBOB), and lithium difluorooxalate borate (lidob).
7. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: the fast ion conductor particles in the step (1-4) are of Perovskit typeLi of (2)1/2La1/2TiO3Or NASICON type AM2(PO4)3Where A is Li, Na, M is Ge, Ti, Zr or Garnet type A3B2(XO4)3Where A ═ Ca, Mg, Y, La, B ═ Al, Fe, Ga, Ge, Mn, Ni, V, X ═ Si, Ge, Al or Li of the LISICON type14ZnGe4O16Or Li of the LISICON type4-xGe1-xPxS4One or more of (a).
8. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: the solvent in the step (1-1) is one or more of acetone, N-Dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone (NMP), Tetrahydrofuran (THF), Dimethylacetamide (DMAC), Tetramethylurea (TMU) and dimethyl sulfoxide (DMSO).
9. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: the first preset time in the step (1-1) is 1h-2h, the second preset time in the step (1-2) is 1h-2h, the third preset time in the step (1-3) is 2h-3h, and the fourth preset time in the step (1-4) is 2h-3 h; the constant-temperature stirring in the steps (1-1), (1-2), (1-3) and (1-4) is: the heating temperature of stirring in the constant temperature water bath kettle is 40-60 ℃, and the rotating speed range of the stirring rotor is 2000r/min-2500 r/min.
10. The method of producing a solid electrolyte membrane according to claim 2, characterized in that: in the step S2, the preset infiltration amount is 10 mu L/cm2-200μL/cm2Soaking for 15-30 min; the fiber non-woven fabric in the step S2 is at least one of laboratory dust-free paper, aramid fiber non-woven fabric, polypropylene fiber non-woven fabric, polyester fiber non-woven fabric, nylon fiber non-woven fabric, acrylic fiber non-woven fabric and polyethylene fiber non-woven fabric; the pressure range of the rolling treatment in the step S3 is 6MPa-45MPa, the pressure stability is less than or equal to 1MPa/10min, and the solid state electrolysis obtained by the rolling treatmentThe thickness of the plasma membrane is 10-70 μm, and the tensile strength is more than 10 MPa.
CN202210457909.4A 2022-04-28 2022-04-28 Solid electrolyte membrane and preparation method thereof Pending CN114759254A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117855582A (en) * 2024-03-08 2024-04-09 河南师范大学 Flexible composite solid electrolyte and preparation and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117855582A (en) * 2024-03-08 2024-04-09 河南师范大学 Flexible composite solid electrolyte and preparation and application thereof
CN117855582B (en) * 2024-03-08 2024-05-24 河南师范大学 Flexible composite solid electrolyte and preparation and application thereof

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