A polymer electrolyte for inducing molecular orientation by electric field, and its preparation method and application

Abstract

The present invention discloses a polymer electrolyte with electric field-induced molecular orientation alignment, its preparation method and application. The raw materials for preparing the polymer electrolyte include: filler, monomer, crosslinking agent, electrolyte salt and photoinitiator. The molar ratio of the crosslinking agent to the monomer is 0.05% - 10%; the molar ratio of the photoinitiator to the monomer is 0.1% - 10%; the molar ratio of the electrolyte salt to the monomer is 1:12 - 2:1; the mass ratio of the filler in the mixed solution of all raw materials is 0.1% - 30%. The polymer electrolyte with electric field-induced molecular orientation alignment of the present invention has high conductivity, a wide temperature tolerance range, and high structural stability. It is used for the preparation of lithium-ion batteries, and the batteries can work well.

Description

Technical Field

[0001] The present invention relates to the field of polymer electrolytes, and particularly to a polymer electrolyte with a molecular orientation structure and a preparation method thereof, specifically to a polymer electrolyte with an electric-field-induced molecular orientation arrangement, a preparation method thereof, and an application thereof. Background Art

[0002] Nowadays, the rapid development of portable electrochemical devices has put forward higher and higher requirements for energy batteries. Lithium-ion batteries are widely used as power sources for various electronic devices because of their high energy density, working voltage, low cost, long cycle life, and basically no pollution to the environment. At present, liquid electrolytes have become the choice of most commercial lithium-ion batteries due to their high ionic conductivity, but there are also many problems, such as insufficient safety, poor sealing, limited operating temperature range, easy to be corroded, insufficient mechanical stability, etc. Therefore, it is necessary to study a new type of electrolyte to replace liquid electrolytes. The emerging solid electrolytes are considered to be ideal materials for electrochemical applications because of their high safety, non-flammability, chemical and electrochemical stability, and easy adjustment of shape and structure, and have received extensive attention and rapid development all over the world in recent years.

[0003] Solid polymer electrolytes have many advantages, but there are also problems such as low ionic conductivity and poor mechanical properties. The most effective method to improve the ionic conductivity of solid polymer electrolytes is to construct an ordered structure, align the conductive particles in the polymer matrix, form continuous ion channels, and achieve ion transport better and faster, thereby effectively improving the ionic conductivity of the polymer electrolyte. Therefore, it is of great significance to construct an ordered structure of polymer composites. There are many methods to construct an ordered structure of polymer composites, such as electric field, magnetic field, temperature field, etc., and a large number of studies have also proved the feasibility of these methods. Among them, the method of constructing an ordered structure of polymer composites by electric field has the advantages of less filler addition and simple process, and the material can show good anisotropy in optics, mechanics, electricity, etc.

[0004] To sum up, the structure of polymer composites has an important influence on their performance. For solid polymer electrolytes, only when the conductive particles form a continuous chain structure to constitute a conductive ion channel can the conductivity of the polymer electrolyte be significantly improved. In a homogeneous polymer composite electrolyte, usually, the mass fraction of conductive particles needs to reach more than 50% to form a continuous chain structure, but this will greatly reduce the stability of the film. Therefore, it is urgent to find an efficient and universal method to construct an ordered three-dimensional structure ion channel by external force, improve conductivity and environmental stability, and obtain a polymer composite solid electrolyte with high ionic conductivity and environmental stability.

[0005] When existing solid electrolytes are used in lithium-ion batteries, due to their low conductivity, they can only operate at relatively high temperatures. There are interface contact problems with the positive and negative electrodes, resulting in generally short cycle lives and being unable to meet the requirements of large-scale production applications. Summary of the Invention

[0006] The present invention provides a polymer electrolyte with electric-field-induced molecular orientation alignment, its preparation method and application, to overcome the defects existing in the prior art. The present invention induces the self-assembly orientation alignment of small molecules under the action of an electric field and in-situ fixes such alignment through photocuring to form a polymer electrolyte, achieving innovation in technology and improving the comprehensive performance of the polymer electrolyte. The polymer electrolyte with electric-field-induced molecular orientation alignment of the present invention has high conductivity, a wide temperature tolerance range, and high structural stability, and has broad application prospects in the field of polymer composite electrolytes. When used in the preparation of lithium-ion batteries, the batteries can work well.

[0007] The present invention is achieved through the following technical solutions:

[0008] A polymer electrolyte with electric-field-induced molecular orientation alignment, the preparation raw materials of the polymer electrolyte include: filler, monomer, cross-linking agent, electrolyte salt, and photoinitiator. The molar ratio of the cross-linking agent to the monomer is 0.05% - 10%; the molar ratio of the photoinitiator to the monomer is 0.1% - 10%; the molar ratio of the electrolyte salt to the monomer is 1:12 - 2:1; the mass percentage of the filler in the mixed solution formed by all raw materials is 0.1% - 30%;

[0009] The filler is an organic filler or an inorganic filler;

[0010] The monomer is one or a mixture of more than one of methoxypolyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol methacrylate, and 2-hydroxyethyl methacrylate;

[0011] The cross-linking agent is polyethylene glycol diacrylate or hexanediol diacrylate;

[0012] The electrolyte salt is a lithium salt, a sodium salt, or a potassium salt.

[0013] Furthermore, the lithium salt is lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropanesulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, or lithium chloride;

[0014] The sodium salt is sodium bis(trifluoromethanesulfonyl)imide, sodium perchlorate, sodium bis(fluorosulfonyl)imide, sodium chloride, or sodium nitrate;

[0015] The potassium salt is potassium bis(fluorosulfonyl)imide, potassium chloride or potassium nitrate.

[0016] Furthermore, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4-dihydroxybenzophenone, and diaryliodonium salt.

[0017] Further, the organic filler is 12-crown-4, 15-crown-5 or 18-crown-6;

[0018] The inorganic filler is lithium aluminum germanium phosphate LAGP, lithium aluminum titanium phosphate LATP, and lithium lanthanum zirconium tantalum oxide LLZTO.

[0019] A method for preparing a polymer electrolyte with electric field induced molecular orientation arrangement comprises the following steps:

[0020] Step 1: After the monomer and electrolyte salt are evenly mixed, the cross-linking agent, filler and photoinitiator are added respectively to make them fully dissolved;

[0021] Step 2: Place the transparent release film tightly on the two transparent conductive substrates, and then fix the silicone mold between the transparent release films;

[0022] Step 3: Use the transparent conductive substrate as the upper and lower electrodes, stick conductive tape on each of the upper and lower electrodes, drip the solution prepared in the first step into the silicone mold in the insulating area between the two electrodes, and apply a DC or AC voltage;

[0023] Step 4: After applying an electric field of preset time and voltage, use ultraviolet light to photocure it. The resulting cured product is a polymer electrolyte with electric field-induced molecular orientation.

[0024] Furthermore, the transparent release film is polyethylene terephthalate, o-phenylphenol, polyethylene or polytetrafluoroethylene;

[0025] The transparent conductive substrate is ITO conductive glass.

[0026] Furthermore, when a DC voltage is applied, the voltage range is 100-2000V, and the time is 5-20min; when an AC voltage is applied, the voltage range is 100-1000V, the frequency is 100-5000Hz, and the time is 5-20min.

[0027] Furthermore, when ultraviolet light is used for photocuring, the wavelength of the ultraviolet light used is 320-400nm, the irradiation power is 30-400W, and the irradiation time is 1-30min.

[0028] Application of a polymer electrolyte with electric-field-induced molecular orientation alignment in a battery, where the battery is a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery;

[0029] When the battery is a lithium-ion battery, assemble it in the order of the positive electrode case, the positive electrode, the polymer electrolyte with electric-field-induced molecular orientation alignment, the negative electrode, the steel sheet, the elastic sheet, and the negative electrode case to obtain a lithium-ion button battery;

[0030] When the battery is a sodium-ion battery, assemble it in the order of the positive electrode case, the positive electrode, the polymer electrolyte with electric-field-induced molecular orientation alignment, the negative electrode, the steel sheet, the elastic sheet, and the negative electrode case to obtain a sodium-ion button battery;

[0031] When the battery is a potassium-ion battery, assemble it in the order of the positive electrode case, the positive electrode, the polymer electrolyte with electric-field-induced molecular orientation alignment, the negative electrode, the steel sheet, the elastic sheet, and the negative electrode case to obtain a potassium-ion button battery.

[0032] Furthermore, when the battery is a lithium-ion battery, the positive electrode is an aluminum foil or a lithium sheet coated with lithium cobaltate, ternary material, or lithium iron phosphate, and the negative electrode is a lithium sheet;

[0033] When the battery is a sodium-ion battery, both the positive electrode and the negative electrode are sodium sheets

[0034] When the battery is a potassium-ion battery, both the positive electrode and the negative electrode are potassium sheets.

[0035] Compared with the prior art, the present invention has the following beneficial technical effects:

[0036] First, the filler, monomer, and electrolyte salt have good compatibility, and the prepared polymer solid electrolyte will not undergo phase separation, and a soft and highly transparent electrolyte membrane can be obtained. Additionally, these asymmetric structure monomers, crown ethers, and inorganic fillers have an inherent dipole moment and are easily polarized in an electric field, so they are arranged along the electric field direction under the drive of the electric field force. Crown ethers or inorganic fillers are more easily polarized in the electric field due to their relatively small molecular weight and are more likely to be arranged and oriented along the electric field direction. Further, they can drive the conductive polymer monomers to be arranged, causing the polymer chains to become unentangled to a certain extent. The dual-ion-channel composite solid electrolyte with an oriented arrangement has a stronger ability to transport ions, with more excellent ionic conductivity and lithium-ion transference number. Moreover, the selected monomers all have ethylene oxide (-CH2-CH2-O-) units and unsaturated acrylic acid units, and they are all good precursors for in-situ polymerized polymer electrolytes. After in-situ photocuring, this oriented structure is fixed, and this arrangement will be more stable due to the presence of the filler. The conductive salt has a high solubility in the system, and ions can migrate smoothly in the oriented structure, making the polymer solid electrolyte have good conductivity. Moreover, the materials used have no corrosiveness to metals and are difficult to undergo chemical reactions, resulting in a high decomposition voltage and a long service life for the prepared devices.

[0037] The polymer electrolyte with an electric-field-induced molecular orientation arrangement obtained in the present invention has the following remarkable characteristics: (1) High conductivity, with a room-temperature ionic conductivity reaching 5×10 -4 S / cm; (2) High lithium-ion transference, with a room-temperature lithium-ion transference number reaching 0.46; (3) High working voltage window, with a decomposition voltage ≥4.5 V, supporting its normal operation in the field of solid electrolytes; (4) High transparency, with a visible light transmittance exceeding 90%; (5) Good compressive performance, with no obvious deformation and performance degradation when the pressure exceeds 500 kg; (6) Good chemical and electrochemical stability, without corroding metals, and can be compounded with metals such as copper and aluminum to prepare complex devices.

[0038] The present invention constructs an ordered three-dimensional structure ion channel through the action of an electric field, which will greatly improve the comprehensive performance of the polymer electrolyte membrane with a molecular orientation arrangement, making it an ideal material for engineering ion devices, greatly expanding their application scope (such as polymer solid electrolytes, flexible batteries, micro-batteries, transparent batteries, etc.), providing a new idea for efficiently constructing an oriented structure electrolyte membrane, laying a foundation for the industrial application of solid electrolytes, and especially providing new opportunities for the fields of flexible electronics and soft machines.

[0039] When the method of the present invention is used to prepare a polymer electrolyte with electric-field-induced molecular orientation alignment, only one power supply is required. Multiple molds are connected in parallel, and an electric field can be applied simultaneously for orientation, which is very efficient and convenient. When forming the film, it only needs to be photocured under ultraviolet light to obtain it. The operation is simple. When preparing by ultraviolet light irradiation, the time used is very short, and it can be prepared in as fast as three minutes, greatly improving the preparation efficiency. The requirements for equipment are low, and the operation is also very simple, which is very conducive to large-scale production. Description of the Drawings

[0040] Figure 1 Schematic diagram of the preparation mold for the polymer electrolyte membrane with electric-field-induced molecular orientation alignment in Example 1.

[0041] Figure 2 Physical diagram of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment in Example 1.

[0042] Figure 3 Structural diagram of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment in Example 1 under a polarized light microscope.

[0043] Figure 4 Curve of the conductivity change with temperature of the polymer electrolyte with electric-field-induced molecular orientation alignment in Example 1 and the comparative sample from 20°C to 90°C.

[0044] Figure 5 Curve of the capacity and charge-discharge efficiency of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment in Example 1 for a lithium-ion full battery during long cycling at a 1C rate.

[0045] Figure 6 The polymer electrolyte with electric-field-induced molecular orientation alignment in Example 1 for a lithium-ion symmetric battery at a current density of 0.1 mAh / cm -2 Overpotential curve during long cycling. Detailed Embodiments

[0046] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0047] It should be noted that the description and claims of the present invention are used to distinguish similar objects, and do not necessarily describe a specific order or sequence. It should be understood that the data used in this way can be interchanged under appropriate circumstances, so that the embodiments of the present invention described here can be implemented in an order other than those described here. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0048] A polymer electrolyte with electric field-induced molecular orientation alignment, and the raw materials for preparing the polymer electrolyte include: fillers, monomers, crosslinking agents, electrolyte salts, and photoinitiators. The molar ratio of the crosslinking agent to the monomer is 0.05% to 10%; the molar ratio of the photoinitiator to the monomer is 0.1% to 10%; the molar ratio of the electrolyte salt to the monomer is 1:12 to 2:1; the mass percentage of the filler in the mixed solution of all raw materials is 0.1% to 30%.

[0049] The monomer is one or a mixture of more than one of methoxypolyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol methacrylate, and 2-hydroxyethyl methacrylate; the crosslinking agent is polyethylene glycol diacrylate or hexanediol diacrylate; the electrolyte salt is a lithium salt, a sodium salt, or a potassium salt. The lithium salt is lithium bis(trifluoromethanesulfonyl)imide LiTFSI, lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropanesulfonylimide, lithium bis(fluorosulfonyl)imide LiFSI, lithium hexafluorophosphate LiPF 6 、lithium tetrafluoroborate LiBF 4 、lithium perchlorate LiClO 4 or lithium chloride LiCl. The sodium salt is sodium bis(trifluoromethanesulfonyl)imide NaTFSI, sodium perchlorate NaClO 4 、sodium bis(fluorosulfonyl)imide NaFSI, sodium chloride NaCl, or sodium nitrate NaNO. The potassium salt is potassium bis(fluorosulfonyl)imide KFSI, potassium chloride KCl, or potassium nitrate KNO. The photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4-dihydroxybenzophenone, diaryliodonium salt. The filler is an organic filler or an inorganic filler, and the organic filler is 12-crown-4, 15-crown-5, 18-crown-6. The inorganic filler is lithium aluminum germanium phosphate LAGP, lithium titanium aluminum phosphate LATP, lithium lanthanum zirconium tantalum oxide LLZTO.

[0050] A preparation method of a polymer electrolyte membrane with electric field-induced molecular orientation alignment, comprising the following steps:

[0051] First step: After uniformly mixing the monomers and electrolyte salts, crosslinking agents, fillers, and photoinitiators are respectively added and fully dissolved.

[0052] Second step: A transparent release film is closely attached to two transparent conductive glass plates, and a silica gel mold with a specific shape is fixed between the release films; the release film is polyethylene terephthalate, o-phenylphenol, polyethylene, or polytetrafluoroethylene, and the transparent conductive glass plate is ITO conductive glass.

[0053] Third step: Using the ITO conductive glass as the upper and lower electrodes, conductive tapes are adhered to each of the upper and lower electrodes, and the solution prepared in the first step is dropped into the silica gel mold in the insulating area between the two electrodes, and a DC or AC voltage is applied.

[0054] Fourth step: After applying an electric field for a certain time and voltage, ultraviolet light is turned on for irradiation to cause photocuring, and the obtained cured product is a polymer electrolyte membrane with electric field-induced molecular orientation alignment. When applying a DC voltage, the voltage range is 100 - 2000V, and the time is 5 - 20min; when applying an AC voltage, the voltage range is 100 - 1000V, the frequency is 100 - 5000Hz, and the time is 5 - 20min. When using ultraviolet light irradiation for photocuring, the wavelength of the ultraviolet light used is 320 - 400nm, the irradiation power is 30 - 400W, and the irradiation time is 1 - 30min.

[0055] An application of a polymer electrolyte with electric field-induced molecular orientation alignment in a lithium-ion battery. Assembled in the order of the positive electrode case, positive electrode, polymer electrolyte with electric field-induced molecular orientation alignment, negative electrode, steel sheet, elastic sheet, and negative electrode case, a lithium-ion button battery is obtained; the positive electrode is an aluminum foil or lithium sheet coated with lithium cobaltate, ternary material, or lithium iron phosphate.

[0056] An application of a polymer electrolyte with electric field-induced molecular orientation alignment in a sodium-ion battery. Assembled in the order of the positive electrode case, positive electrode, polymer electrolyte with electric field-induced molecular orientation alignment, negative electrode, steel sheet, elastic sheet, and negative electrode case, a sodium-ion button battery is obtained, where the positive electrode is a sodium sheet and the negative electrode is a sodium sheet.

[0057] An application of a polymer electrolyte with electric field-induced molecular orientation alignment in a potassium-ion battery. Assembled in the order of the positive electrode case, positive electrode, polymer electrolyte with electric field-induced molecular orientation alignment, negative electrode, steel sheet, elastic sheet, and negative electrode case, a potassium-ion button battery is obtained; the positive electrode is a potassium sheet and the negative electrode is a potassium sheet.

[0058] The present invention will be further described in detail below with reference to specific embodiments:

[0059] Example 1

[0060] The raw materials of the polymer electrolyte membrane with electric field-induced molecular orientation alignment in this example include: 2 ml of methoxypolyethylene glycol acrylate, 0.04 g of polyethylene glycol diacrylate, 0.46 g of 15-crown-5, 0.08 g of 1-hydroxycyclohexyl phenyl ketone, and 0.6 g of lithium bis(trifluoromethanesulfonyl)imide. The electric field used is a direct current electric field.

[0061] This example includes the following steps:

[0062] The first step: Measure 2 ml of methoxypolyethylene glycol acrylate and 0.04 g of polyethylene glycol diacrylate and add them to a 5-ml glass bottle. Then weigh 0.6 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and stir magnetically. After the solid is completely dissolved, add 0.46 g of 15-crown-5 and continue stirring until evenly mixed. Finally, weigh 0.08 g of 1-hydroxycyclohexyl phenyl ketone into the glass bottle and stir in the dark until there are no solid particles.

[0063] The second step: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive side respectively, and then place a 0.1-mm-thick silicone rubber circular groove between the two layers of PET films.

[0064] The third step: Drop 60 μl of the solution prepared in the first step into the silicone mold in the second step, and then cover the other conductive glass plate with a PET film on the liquid drop, so that the liquid drop fills the entire circular groove of the silicone mold, and clamp it tightly around with clips.

[0065] The fourth step: Connect the two conductive tapes protruding from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply a direct current voltage of 300 V, and irradiate it with ultraviolet light with a wavelength of 365 nm and a power of 400 W for 3 minutes to cure it after 10 minutes. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is the polymer electrolyte with electric field-induced molecular orientation alignment.

[0066] The fifth step: Assemble a lithium-ion coin cell in the order of positive electrode shell - positive electrode - polymer electrolyte with electric field-induced molecular orientation alignment - negative electrode - steel sheet - elastic sheet - negative electrode shell. Among them, the positive electrode of the lithium iron phosphate|lithium full cell is an aluminum foil coated with lithium iron phosphate, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric cell is a lithium sheet, and the negative electrode is a lithium sheet.

[0067] The polymer electrolyte membrane with molecular orientation alignment obtained in this example and its performance test are shown in the figure: Figure 1Schematic diagram of a mold for preparing a polymer electrolyte membrane with electric-field-induced molecular orientation alignment. The mold can be made into different shapes according to different device requirements, so as to prepare a polymer electrolyte membrane with adjustable shape. Figure 2 Is a physical picture of a polymer electrolyte membrane with molecular orientation. Figure 2 It can be seen that the polymer electrolyte has excellent transparency and stretchability. Figure 3 Is the conductivity-temperature change curve of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment and the comparative sample in the embodiment at 20°C to 90°C. Figure 3 It can be seen that the molecularly oriented solid electrolyte membrane has a high ionic conductivity in a large temperature range and conforms to the Arrhenius formula, indicating that the molecular orientation alignment structure of the polymer solid electrolyte can be well maintained at various temperatures and can withstand extreme temperatures. Figure 4 Is the structural diagram of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment under a polarized light microscope. Figure 4 It can be intuitively seen the internal alignment structure of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment, proving the authenticity and reliability of the molecular orientation alignment of this membrane. In summary, the polymer electrolyte membrane with molecular orientation alignment obtained by electric-field induction in this example has high transparency and good conductivity, and can withstand extreme temperatures, and is a solid electrolyte that can be used in flexible conductive devices and lithium-ion batteries.

[0068] The molecularly oriented polymer electrolyte membrane obtained in this example and its performance tests are shown as follows: Figure 5 Is the capacity and charge-discharge efficiency curve of the polymer electrolyte membrane with electric-field-induced molecular orientation alignment in the embodiment for a lithium-ion full battery during long cycling at a 1C rate. At a high rate of 1C, the specific capacity of the full battery can reach 120 mAh / g, and after 100 cycles, there is still a capacity of 100 mAh / g. Figure 6 Is the overpotential curve of the polymer electrolyte with electric-field-induced molecular orientation alignment in the embodiment for a lithium-ion symmetric battery during long cycling at a current density of 0.1 mAh / cm -2 Under. The lithium symmetric battery stably cycles for more than 500 h with a minimum overpotential of 40 mV at a current density of 0.1 mAh / cm -2 The test results show that both the full battery and the symmetric battery exhibit very good performance.

[0069] Example 2

[0070] The raw materials of the polymer electrolyte membrane with electric field-induced molecular orientation alignment in this embodiment include: 2 ml of 2-hydroxyethyl methacrylate, 0.005 g of polyethylene glycol diacrylate, 0.38 g of 12-crown-4, 0.08 g of 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 0.6 g of lithium tetrafluoroborate. The electric field used is a direct current electric field.

[0071] This embodiment includes the following steps:

[0072] First step: Measure 2 ml of 2-hydroxyethyl methacrylate and 0.005 g of polyethylene glycol diacrylate and add them to a 5-ml glass bottle. Then weigh 0.6 g of lithium tetrafluoroborate and perform magnetic stirring. After the solid is completely dissolved, add 0.38 g of 12-crown-4 and continue stirring until evenly mixed. Finally, weigh 0.08 g of 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone into the glass bottle and stir in the dark until there are no solid particles.

[0073] Second step: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and place a 0.1-mm-thick silicone rubber circular groove between the two layers of PET films.

[0074] Third step: Drop 60 μl of the solution prepared in the first step into the silicone rubber mold in the second step, and then cover the conductive glass with another piece of PET film on the liquid drop, so that the liquid drop fills the entire circular groove of the silicone rubber mold, and clamp it tightly around with clips.

[0075] Fourth step: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply a direct current voltage of 100 V, and irradiate it with ultraviolet light with a wavelength of 365 nm and a power of 300 W for 5 minutes to cure it after 20 minutes. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is the polymer electrolyte with electric field-induced molecular orientation alignment.

[0076] Fifth step: Assemble a lithium-ion coin cell in the order of positive electrode case - positive electrode - polymer electrolyte with electric field-induced molecular orientation alignment - negative electrode - steel sheet - elastic sheet - negative electrode case.

[0077] Among them, the positive electrode of the lithium iron phosphate|lithium full cell is an aluminum foil coated with lithium iron phosphate, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric cell is a lithium sheet, and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0078] Effect: The ionic conductivity of the product obtained in this embodiment reaches 3.4×10 -4 S / cm at room temperature, and the decomposition voltage is 4.7 V.

[0079] Example 3

[0080] The raw materials of the polymer electrolyte membrane with electric field-induced molecular orientation alignment in this example include: 2 ml of methoxypolyethylene glycol acrylate, 0.35 g of polyethylene glycol diacrylate, 0.24 g of 15-crown-5, 0.08 g of lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, and 0.6 g of lithium perchlorate. The electric field used is a direct current electric field.

[0081] This example includes the following steps:

[0082] First step: Measure 2 ml of methoxypolyethylene glycol acrylate and 0.35 g of polyethylene glycol diacrylate and add them to a 5-ml glass bottle. Then weigh 0.6 g of lithium perchlorate (LiClO 4 ) and perform magnetic stirring. After the solid is completely dissolved, add 0.24 g of 15-crown-5 and continue stirring until evenly mixed. Finally, weigh 0.08 g of lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide into the glass bottle and stir in the dark until there are no solid particles.

[0083] Second step: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and then place a 0.2-mm-thick silicone rubber circular groove between the two layers of PET films.

[0084] Third step: Drop 60 μl of the solution prepared in the first step into the silicone mold in the second step, and then cover the conductive glass with another PET film on the liquid drop so that the liquid drop fills the entire circular groove of the silicone mold, and clamp it tightly around with clips.

[0085] Fourth step: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply a direct current voltage of 2000 V, and irradiate it with an ultraviolet lamp with a wavelength of 365 nm and a power of 30 W for 30 minutes to cure it after 5 minutes. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is the polymer electrolyte membrane with electric field-induced molecular orientation alignment.

[0086] Fifth step: Assemble a lithium-ion coin cell in the order of positive electrode shell - positive electrode - polymer electrolyte with electric field-induced molecular orientation alignment - negative electrode - steel sheet - elastic sheet - negative electrode shell.

[0087] Among them, the positive electrode of the lithium iron phosphate|lithium full cell is an aluminum foil coated with lithium iron phosphate, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric cell is a lithium sheet, and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0088] Effect: The ionic conductivity of the product obtained in this example reaches 2.5×10 -4 S / cm at room temperature, and the decomposition voltage is 4.5 V.

[0089] Example 4

[0090] The raw materials of the molecularly oriented polymer electrolyte in this example include: 2 ml of polyethylene glycol methyl ether methacrylate, 0.18 g of polyethylene glycol diacrylate, 0.46 g of 15-crown-5, 0.003 g of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, and 0.6 g of lithium bis(trifluoromethanesulfonyl)imide. The electric field used is an alternating current electric field.

[0091] This example includes the following steps:

[0092] First step: Measure 2 ml of polyethylene glycol methyl ether methacrylate and 0.18 g of polyethylene glycol diacrylate and add them to a 5 ml glass bottle. Then weigh 0.6 g of lithium bis(trifluoromethanesulfonyl)imide and perform magnetic stirring. After the solid is completely dissolved, add 0.46 g of 15-crown-5 and continue stirring until evenly mixed. Finally, weigh 0.003 g of 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone into the glass bottle and stir in the dark until there are no solid particles.

[0093] Second step: Take two clean and transparent conductive glass plates of 5 cm×5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and then place a 0.1 mm thick silicone rubber circular groove between the two PET films.

[0094] Third step: Drop 60 μl of the solution prepared in the first step into the silicone rubber mold in the second step, and then cover the conductive glass with another PET film on the liquid drop, so that the liquid drop fills the entire circular groove of the silicone rubber mold and clamp it tightly around with clips.

[0095] Fourth step: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply an alternating voltage of 500 V and a frequency of 600 Hz, keep it for 10 minutes, and then irradiate it under an ultraviolet lamp with a wavelength of 365 nm and a power of 400 W for 5 minutes to cure it. After the curing is completed, turn off the high-voltage power supply, open the glass plate, remove the groove, and gently peel off the cured product from the PET film. The obtained product is a polymer electrolyte membrane with molecular orientation arranged by electric field induction.

[0096] Fifth step: Assemble a lithium-ion button battery in the order of positive electrode case - positive electrode - polymer electrolyte with molecular orientation arranged by electric field induction - negative electrode - steel sheet - elastic sheet - negative electrode case.

[0097] Among them, the positive electrode of the lithium iron phosphate|lithium full battery is an aluminum foil coated with lithium iron phosphate, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric battery is a lithium sheet, and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0098] Effect: The ionic conductivity of the product obtained in this example reaches 5.2×10 -4 S / cm at room temperature, and the decomposition voltage is 4.7V.

[0099] Example 5

[0100] The raw materials of the polymer electrolyte membrane with electric field-induced molecular orientation arrangement in this example include: 6.4 g of ethoxyethoxyethyl acrylate, 0.2 g of hexanediol diacrylate, 1.15 g of 18-crown-6, 0.66 g of 2-hydroxy-2-methyl-1-phenylpropanone, and 1.87 g of lithium bis(fluorosulfonyl)imide. The electric field used is a direct current electric field.

[0101] This example includes the following steps:

[0102] First step: Weigh 6.4 g of ethoxyethoxyethyl acrylate and 0.2 g of hexanediol diacrylate and add them to a 15 ml glass bottle. Then weigh 1.87 g of lithium bis(fluorosulfonyl)imide and add it to the bottle for magnetic stirring. After the solid is completely dissolved, add 1.15 g of 18-crown-6 and continue stirring until evenly mixed. Finally, weigh 0.66 g of 2-hydroxy-2-methyl-1-phenylpropanone into the glass bottle and stir in the dark until there are no solid particles.

[0103] Second step: Take two clean and transparent conductive glass plates of 5 cm×5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and place a 0.5 mm thick silicone rubber "U" groove between the two layers of PET films.

[0104] Third step: Drop 2 ml of the solution prepared in the first step into the groove of the silicone mold between the glass plates, so that the liquid drop fills the entire "U" groove of the silicone mold, and clamp it tightly around with clips.

[0105] Fourth step: Connect the two conductive tapes protruding from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply a direct current voltage of 1000 V, and irradiate it under an ultraviolet lamp with a wavelength of 365 nm and a power of 400 W for 10 minutes to cure it. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is the polymer electrolyte membrane with electric field-induced molecular orientation arrangement.

[0106] Step 5: Assemble a lithium-ion button battery in the order of positive electrode case - positive electrode - polymer electrolyte with molecular orientation arranged by electric field - negative electrode - steel sheet - elastic sheet - negative electrode case. For the lithium cobaltate|lithium full battery, the positive electrode is an aluminum foil coated with cobalt acid, and the negative electrode is a lithium sheet; for the nickel cobalt manganese ternary|lithium full battery, the positive electrode is an aluminum foil coated with the ternary material, and the negative electrode is a lithium sheet; for the lithium symmetric battery, the positive electrode is a lithium sheet and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0107] Effect: The ionic conductivity of the product obtained in this example reaches 1.1×10 -4 S / cm at room temperature, and the decomposition voltage is 4.5V.

[0108] Example 6

[0109] The raw materials of the polymer electrolyte membrane with molecular orientation arranged by electric field in this example include 9.4 g of ethoxyethoxy acrylate, 0.3 of polyethylene glycol diacrylate, 0.009 g of 15-crown-5, 0.28 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 1.52 g of lithium hexafluorophosphate. The electric field used is an alternating current electric field.

[0110] This example includes the following steps:

[0111] First step: Weigh 9.4 g of ethoxyethoxy acrylate and 0.3 g of polyethylene glycol diacrylate and add them to a 30 ml glass bottle. Then weigh 1.52 g of lithium hexafluorophosphate and add it for magnetic stirring. After the solid is completely dissolved, add 0.009 g of 15-crown-5 and continue stirring until evenly mixed. Finally, weigh 0.28 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide into the glass bottle and stir in the dark until there are no solid particles.

[0112] Second step: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive side respectively, and then place a 0.5 mm thick silicone rubber "U" - shaped groove between the two layers of PET films.

[0113] Third step: Drop 2 ml of the solution prepared in the first step into the groove of the silicone mold between the glass plates, so that the liquid drop fills the entire "U" - shaped groove of the silicone mold, and clamp it tightly around with clips.

[0114] Step 4: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply an alternating voltage of 100 V with a frequency of 5000 Hz, keep it for 5 minutes, and then irradiate it under an ultraviolet lamp with a wavelength of 365 nm and a power of 400 W for 10 minutes to cure it. After curing, turn off the high-voltage power supply, open the glass plate to remove the groove, and gently peel off the cured product from the PET film. The obtained product is a polymer electrolyte with an electric-field-induced molecular orientation arrangement.

[0115] Step 5: Assemble a lithium-ion coin cell in the order of positive electrode case - positive electrode - polymer electrolyte with an electric-field-induced molecular orientation arrangement - negative electrode - steel sheet - elastic sheet - negative electrode case. Among them, the positive electrode of the lithium cobalt oxide|lithium full cell is an aluminum foil coated with cobalt acid, and the negative electrode is a lithium sheet; the positive electrode of the nickel cobalt manganese ternary|lithium full cell is an aluminum foil coated with the ternary, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric cell is a lithium sheet, and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0116] Effect: The ionic conductivity of the product obtained in this example reaches 1.5×10 -4 S / cm at room temperature, and the decomposition voltage is 4.5 V.

[0117] Example 7

[0118] The raw materials of the polymer electrolyte membrane with an electric-field-induced molecular orientation arrangement in this example include: 2 ml of polyethylene glycol monomethyl ether acrylate, 0.04 g of polyethylene glycol diacrylate, 0.06 g of LAGP, 0.14 g of diaryliodonium salt, and 0.018 g of lithium chloride. The electric field used is an alternating electric field.

[0119] This example includes the following steps:

[0120] Step 1: Measure 2 ml of polyethylene glycol monomethyl ether acrylate and 0.04 g of polyethylene glycol diacrylate and add them to a 5-ml glass bottle. Then weigh 0.018 g of lithium chloride and stir magnetically. After the solid is completely dissolved, add 0.06 g of LAGP and continue to stir until it is evenly mixed. Finally, weigh 0.14 g of diaryliodonium salt into the glass bottle and stir in the dark until there are no solid particles.

[0121] Step 2: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive side respectively, and then place a 0.5-mm-thick silicone rubber "U"-shaped groove between the two layers of PET films.

[0122] Step 3: Drop 2 ml of the solution prepared in the first step into the groove of the silicone mold between the glass plates, so that the liquid drop fills the entire "U"-shaped groove of the silicone mold, and clamp it tightly around with clips.

[0123] Step 4: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of a high-voltage power supply respectively, apply an alternating voltage of 1000 V with a frequency of 100 Hz, keep it for 20 minutes, and then irradiate it under an ultraviolet lamp with a wavelength of 365 nm and a power of 400 W for 30 minutes to cure it. After curing, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is a polymer electrolyte with an electric-field-induced molecular orientation arrangement.

[0124] Step 5: Assemble a lithium-ion coin cell in the order of positive electrode case - positive electrode - polymer electrolyte with an electric-field-induced molecular orientation arrangement - negative electrode - steel sheet - elastic sheet - negative electrode case. Among them, the positive electrode of the lithium cobalt oxide|lithium full cell is an aluminum foil coated with cobalt acid, and the negative electrode is a lithium sheet; the positive electrode of the nickel cobalt manganese ternary|lithium full cell is an aluminum foil coated with the ternary, and the negative electrode is a lithium sheet; the positive electrode of the lithium symmetric cell is a lithium sheet, and the negative electrode is a lithium sheet. That is, the assembly of the lithium-ion battery is completed.

[0125] Effect: The ionic conductivity of the product obtained in this example reaches 4.6×10 -4 S / cm at room temperature, the decomposition voltage is 4.7 V, and its various properties show no obvious changes in the temperature range of 20 °C to 100 °C.

[0126] Example 8

[0127] The raw materials of the polymer electrolyte membrane with an electric-field-induced molecular orientation arrangement in this example include: 5 ml of polyethylene glycol methacrylate, 0.2 g of hexanediol diacrylate, 1.5 g of LLZTO, 1.15 g of 18-crown-6, 0.24 g of 2-hydroxy-2-methyl-1-phenylpropanone, and 3.65 g of potassium bis(fluorosulfonyl)imide. The electric field used is an alternating electric field.

[0128] This example includes the following steps:

[0129] Step 1: Weigh 5 ml of polyethylene glycol methacrylate and 0.2 g of hexanediol diacrylate and add them to a 15-ml glass bottle. Then weigh 3.65 g of potassium bis(fluorosulfonyl)imide and add it to the bottle for magnetic stirring. After the solid is completely dissolved, add 1.15 g of 18-crown-6 and continue stirring until it is evenly mixed. Then add 1.5 g of LLZTO and continue stirring until it is evenly mixed. Finally, weigh 0.24 g of 2-hydroxy-2-methyl-1-phenylpropanone into the glass bottle and stir it in the dark until there are no solid particles.

[0130] Step 2: Take two clean and transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and place a 0.5-mm-thick silicone rubber "U"-shaped groove between the two layers of PET films.

[0131] Step 3: Drop 2 ml of the solution prepared in Step 1 into the groove of the silica gel mold between the glass plates, so that the liquid droplet fills the entire "U"-shaped groove of the silica gel mold, and clamp it tightly around with clips.

[0132] Step 4: Connect the two conductive tapes protruding from this glass plate to the positive and negative electrodes of the high-voltage power supply respectively, apply an alternating voltage of 800 V and a frequency of 3000 Hz, keep it for 10 minutes, and then irradiate it under an ultraviolet lamp with a wavelength of 320 nm and a power of 360 W for 20 minutes to cure it. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is a polymer electrolyte with an electric-field-induced molecular orientation arrangement.

[0133] Step 5: Assemble a lithium-ion coin cell in the order of positive electrode case - positive electrode - polymer electrolyte with an electric-field-induced molecular orientation arrangement - negative electrode - steel sheet - elastic sheet - negative electrode case. The positive electrode of the symmetric cell is a potassium sheet, and the negative electrode is a potassium sheet. That is, the assembly of the potassium-ion battery is completed.

[0134] Effect: The ionic conductivity of the product obtained in this example reaches 5.5×10 -4 S / cm at room temperature, the decomposition voltage is 4.8 V, and its various properties show no obvious changes in the temperature range of 20 °C to 100 °C.

[0135] The potassium salt in this example can also be potassium chloride or potassium nitrate.

[0136] Example 9

[0137] The raw materials of the polymer electrolyte membrane with an electric-field-induced molecular orientation arrangement in this example include: 5 ml of polyethylene glycol methacrylate, 0.5 g of polyethylene glycol diacrylate, 1.5 g of LATP, 1.15 g of 15-crown-5, 0.2 g of 2,4-dihydroxybenzophenone, and 1.8 g of sodium perchlorate. The electric field used is a direct current electric field.

[0138] This example includes the following steps:

[0139] Step 1: Measure 5 ml of polyethylene glycol methacrylate and 0.5 g of polyethylene glycol diacrylate and add them to a 10-ml glass bottle. Then weigh 1.8 g of sodium perchlorate (NaClO 4 ) and perform magnetic stirring. After the solid is completely dissolved, add 1.15 g of 15-crown-5 and continue stirring until it is evenly mixed. Finally, weigh 0.2 g of 2,4-dihydroxybenzophenone into the glass bottle and stir it in the dark until there are no solid particles.

[0140] Step 2: Take two clean transparent conductive glass plates of 5 cm × 5 cm, stick a layer of polyethylene terephthalate (PET) film and conductive tape on the conductive sides respectively, and then place a circular silicone rubber groove with a thickness of 0.1 mm between the two PET films.

[0141] Step 3: Drop 60 μl of the solution prepared in Step 1 into the silicone rubber mold in Step 2, and then cover the conductive glass with another PET film on the liquid drop, so that the liquid drop fills the entire circular groove of the silicone rubber mold, and clamp it tightly with clips around.

[0142] Step 4: Connect the two conductive tapes extending from this glass plate to the positive and negative electrodes of the high-voltage power supply respectively, apply a DC voltage of 2000 V, keep it for 5 minutes, and then irradiate it under an ultraviolet lamp with a wavelength of 400 nm and a power of 400 W for 1 minute to cure it. After the curing is completed, turn off the high-voltage power supply, open the glass plate and remove the groove, and gently peel off the cured product from the PET film. The obtained product is a polymer electrolyte membrane with electric-field-induced molecular orientation arrangement.

[0143] Step 5: Assemble a lithium-ion button battery in the order of positive electrode case - positive electrode - polymer electrolyte with electric-field-induced molecular orientation arrangement - negative electrode - steel sheet - elastic sheet - negative electrode case. The positive electrode of its symmetric battery is a sodium sheet, and the negative electrode is a sodium sheet. That is, the assembly of the sodium-ion battery is completed.

[0144] Effect: The product obtained in this example has a visible light transmittance of 90%; the ionic conductivity at room temperature reaches 2.1×10 -4 S / cm, and the decomposition voltage is 4.5 V.

[0145] The sodium salt in this example can also be sodium bis(trifluoromethanesulfonyl)imide NaTFSI, sodium difluoromethanesulfonimide NaFSI, sodium chloride NaCl or sodium nitrate NaNO 3 .

[0146] The above content is only to illustrate the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A preparation method of a polymer electrolyte with electric field-induced molecular orientation arrangement, characterized in that, the raw materials for preparing the polymer electrolyte with electric field-induced molecular orientation arrangement include: filler, monomer, cross-linking agent, electrolyte salt and photoinitiator, and the molar ratio of the cross-linking agent to the monomer is 0.05% - 10%; the molar ratio of the photoinitiator to the monomer is 0.1% - 10%; the molar ratio of the electrolyte salt to the monomer is 1:12 - 2:1; the mass percentage of the filler in the mixed solution formed by all raw materials is 0.1% - 30%; the filler is an organic filler or an inorganic filler; the monomer is one or a mixture of more than one of methoxypolyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol methacrylate and 2-hydroxyethyl methacrylate; the cross-linking agent is polyethylene glycol diacrylate or hexanediol diacrylate; the electrolyte salt is a lithium salt, a sodium salt or a potassium salt; the preparation method includes the following steps: The first step: After uniformly mixing the monomer and the electrolyte salt, then add the cross-linking agent, filler and photoinitiator respectively to make them fully dissolve; The second step: Stick the transparent release film closely on two transparent conductive substrates, and then fix the silicone mold between the transparent release films; The third step: Use the transparent conductive substrates as the upper and lower electrodes, stick conductive tapes on each of the upper and lower electrodes, drop the solution prepared in the first step into the silicone mold in the insulating area between the two electrodes, and apply a DC or AC voltage; The fourth step: After applying an electric field with a preset time and voltage, irradiate it with ultraviolet light to make it photocured, and the obtained cured product is the polymer electrolyte with electric field-induced molecular orientation arrangement.

2. The preparation method of a polymer electrolyte with electric field-induced molecular orientation arrangement according to claim 1, characterized in that, the transparent release film is polyethylene terephthalate, o-phenylphenol, polyethylene or polytetrafluoroethylene; the transparent conductive substrate is ITO conductive glass.

3. The preparation method of a polymer electrolyte with electric field-induced molecular orientation arrangement according to claim 1, characterized in that, when applying a DC voltage, the voltage range is 100 - 2000V and the time is 5 - 20min; when applying an AC voltage, the voltage range is 100 - 1000V, the frequency is 100 - 5000Hz, and the time is 5 - 20min.

4. The preparation method of a polymer electrolyte with electric field-induced molecular orientation arrangement according to claim 1, characterized in that, when using ultraviolet light irradiation for photocuring, the wavelength of the ultraviolet light used is 320 - 400nm, the irradiation power is 30 - 400W, and the irradiation time is 1 - 30min.

5. The preparation method of a polymer electrolyte with electric field-induced molecular orientation arrangement according to claim 1, characterized in that, the lithium salt is lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropanesulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate or lithium chloride; The sodium salt is sodium bis(trifluoromethanesulfonyl)imide, sodium perchlorate, sodium bis(fluorosulfonyl)imide, sodium chloride or sodium nitrate; The potassium salt is potassium bis(fluorosulfonyl)imide, potassium chloride or potassium nitrate.

6. The preparation method of a polymer electrolyte with electric-field-induced molecular orientation arrangement according to claim 1, characterized in that the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4-dihydroxybenzophenone, diaryliodonium salt.

7. The preparation method of a polymer electrolyte with electric-field-induced molecular orientation arrangement according to claim 1, characterized in that the organic filler is 12-crown-4, 15-crown-5 or 18-crown-6; the inorganic filler is lithium aluminum germanium phosphate LAGP, lithium aluminum titanium phosphate LATP, lithium lanthanum zirconium tantalum oxide LLZTO.

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