In-situ polymerized solid polymer electrolyte and preparation method thereof

Abstract

The present invention provides an in-situ polymerized solid polymer electrolyte and a preparation method thereof, belonging to the field of polymer electrolyte technology. The electrolyte comprises a cross-linked polymer matrix, a lithium salt or sodium salt, and an additive. The structure of the cross-linked polymer matrix is ​​shown in Formula (I). The solid polymer electrolyte provided by the present invention is prepared through a curing reaction between amino and epoxy groups, resulting in solid polymer electrolytes with varying ether chain lengths and cross-linking degrees. The solid polymer electrolyte also contains a large number of hydrogen bonds, which can reduce the crystallinity of the PEO chain segments and further adjust the lithium or sodium ion transport performance and mechanical properties of the solid polymer electrolyte.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer electrolytes, and in particular relates to an in-situ polymerized solid polymer electrolyte and a preparation method thereof. Background Art

[0002] Among solid electrolyte materials, solid polymer electrolytes stand out for their light weight, flexibility, excellent film forming properties, processability, and good interface wettability, which are in line with the current trend of lightweight, flexible, bendable, and designable appearance of electronic devices. Polyethylene oxide (PEO) is the most promising solid-state battery product. Although it has the advantages of flexibility, light weight, excellent viscoelasticity, good film forming properties, and excellent processability, the room temperature lithium ion conductivity of polyethylene oxide-based solid electrolytes is relatively low (10 -7 -10 -6 S cm -1 ), its modulus drops significantly at high temperatures, making it unable to inhibit the growth of sodium dendrites and other damage caused by them.

[0003] In recent years, researchers have developed a variety of polymer matrices, such as polyether, polyacrylonitrile, polyvinylidene fluoride, polymethacrylate, polycarbonate, polyurethane, polysiloxane and polyphosphazene. Polyethylene oxide (PEO) is the earliest and most studied polymer matrix, but PEO-based solid polymer electrolytes still have low room temperature ionic conductivity (about 10 -6 ~10 - 7 S cm -1 ), narrow electrochemical stability window (<4V), and poor contact with the electrode interface. To improve the room temperature ionic conductivity of PEO-based solid polymer electrolytes, researchers usually use modification methods such as blending, copolymerization, grafting, and cross-linking to reduce the crystallinity of the PEO chain segments, increase the area of ​​the amorphous region in the chain segments, and thus promote the rapid transport of lithium ions in the solid polymer electrolyte. However, the preparation process involved in common modification methods is relatively complicated and environmentally unfriendly. To improve the problem of poor contact between solid polymer electrolytes and electrodes, researchers usually prepare solid polymer electrolytes through in situ polymerization to reduce interfacial impedance, thereby further improving the ionic conductivity and energy density of solid-state batteries. In situ polymerization to prepare solid polymer electrolytes is usually obtained by adding an initiator to initiate the ring-opening reaction of oxygen-containing cyclic compounds or by initiating a free radical polymerization reaction of carbon-carbon double bonds or carbon-oxygen double bonds through an initiator or ultraviolet light. However, the introduction of the initiator will have a negative impact on the battery, and the closed conditions of the battery will also limit the use of ultraviolet light. Summary of the Invention

[0004] The purpose of the present invention is to provide an in-situ polymerized solid polymer electrolyte and a preparation method thereof. The method can improve the electrical conductivity and electrochemical stability window of the solid polymer electrolyte, while improving the technical problem of poor contact between the solid polymer electrolyte and the electrode material. The preparation process of the solid polymer electrolyte provided by the present invention is simple, does not require the addition of initiators or the use of ultraviolet light, has no complicated post-processing process, is environmentally friendly, and is suitable for industrial production.

[0005] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides an in-situ polymerized solid polymer electrolyte comprising a cross-linked polymer matrix, a lithium salt or a sodium salt, and an additive. The structure of the cross-linked polymer matrix is ​​shown in formula (I):

[0007]

[0008] wherein R comprises aliphatic chains or aromatic rings in different diamine monomers;

[0009] n is an integer from 4 to 113.

[0010] Preferably, the cross-linked polymer matrix is ​​prepared by in situ polymerization of polyethylene glycol diglycidyl ether and diamine monomers through nucleophilic addition reaction, wherein the diamine monomers include aliphatic diamine monomers and aromatic diamine monomers, and the aliphatic diamine monomers include NH2-(CH2) m -NH2 (m is an integer of 2 to 30) and aliphatic diamine monomers containing branches of different carbon chain lengths at different positions; aromatic diamine monomers include benzyl diamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-phenyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2-propyl-1,4-phenylenediamine, 2-isopropyl-1,4-phenylenediamine , 2-butyl-1,4-phenylenediamine, 2-isobutyl-1,4-phenylenediamine, 2-pentyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2-bromo-1,4-phenylenediamine, 4,4-diphenylenediamine, 2,2'-dimethyl-4,4'-diphenylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2-phenyl-p-phenylenediamine, 2-phenoxy-p-phenylenediamine;

[0011] The structure of polyethylene glycol diglycidyl ether (PEGDE) is shown in (II):

[0012]

[0013] Wherein, n is an integer of 4 to 113, and the relative molecular mass of polyethylene glycol in polyethylene glycol diglycidyl ether (PEGDE) is 200 to 5000.

[0014] Preferably, the lithium salt is one or more of lithium bis(trifluoromethanesulfonyl imide), lithium bis(fluorosulfonyl imide), lithium perchlorate, lithium difluorooxalatoborate, lithium hexafluorophosphate, and lithium tetrafluoroborate.

[0015] Preferably, the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide.

[0016] Preferably, the additives are inorganic additives and organic additives, the inorganic additives are one or more of lithium lanthanum zirconium oxide, lithium lanthanum titanate, lithium titanium phosphate, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, zinc oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, zeolite, montmorillonite or kaolin; the organic additives are one or more of plastic crystal succinonitrile, ethylene carbonate, propylene carbonate, N,N-dimethylformamide and PEG.

[0017] The present invention also provides a method for preparing an in-situ polymerized solid polymer electrolyte, comprising the following steps:

[0018] The polyethylene glycol diglycidyl ether is melted, and then lithium salt or sodium salt and additives are added in sequence. After stirring and dissolving, the diamine monomer is added. After dissolving, the monomer is allowed to stand and degas to perform in-situ polymerization reaction to obtain an in-situ polymerized solid polymer electrolyte.

[0019] Preferably, the molar ratio of the diamine monomer to polyethylene glycol diglycidyl ether is 1:(1-8); the molar ratio of the lithium ions or sodium ions in the lithium salt or sodium salt to the ether oxygen atoms in the polymer (I) is 1:(2-128); and the content of the additive is 0.2-300wt% of the polymer electrolyte.

[0020] Preferably, the melting temperature of the polyethylene glycol diglycidyl ether is 25-80°C, the stirring and dissolving time is 5 min-24 h, the dissolving temperature of the added diamine monomer is 10-80°C, the dissolving time is 3 min-48 h, the standing and degassing temperature is 5-40°C, and the standing and degassing time is 0.05-4 h.

[0021] Preferably, the in-situ polymerization temperature is 10-120° C. and the time is 2-72 hours.

[0022] The present invention also provides use of the polymer electrolyte in preparing lithium ion batteries or sodium ion batteries.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The solid polymer electrolyte provided by the present invention is prepared by the curing reaction of amino and epoxy groups, and a solid polymer electrolyte containing different ether chain lengths and cross-linking degrees can be obtained. At the same time, the solid polymer electrolyte contains a large number of hydrogen bonds, which can reduce the crystallinity of the PEO chain segment and further adjust the lithium ion transport performance and mechanical properties of the solid polymer electrolyte.

[0025] (2) Compared with traditional PEO-based solid electrolytes, the solid polymer electrolyte provided by the present invention has an adjustable cross-linking degree, which reduces the crystallinity and glass transition temperature of the solid polymer electrolyte, such as Figure 5 As shown, the solid polymer electrolyte of Example 1 has no obvious crystallization peak, and the peak is in a diffuse state. The crystallinity is less than 10% using the software JADE fitting. Figure 4 As shown in FIG1 , the glass transition temperature of the solid polymer electrolyte of Example 1 is -36.71°C. It has a more excellent segment mobility, improves the lithium ion transmission capacity, and further improves the conductivity of the solid polymer electrolyte. The room temperature ionic conductivity is as high as 1.71×10 -4 S cm -1 In addition, the addition of additives can inhibit the crystallization of PEO and improve the mobility of polymer chain segments. The interface area between the additives and the PEO matrix can be Na + It provides more migration paths and can improve the mechanical strength of the polymer electrolyte to a certain extent, thereby inhibiting the growth of sodium dendrites and improving the electrochemical performance of the solid polymer electrolyte. Figure 12 As shown, the solid polymer electrolyte of Example 11 has no obvious crystallization peak, and the peak is in a diffuse state. The crystallinity is less than 10% using the JADE software for fitting. Figure 11 As shown in FIG11 , the glass transition temperature of the solid polymer electrolyte of Example 11 is -32.56°C. It has a more excellent segment mobility, improves the lithium ion transmission capacity, and further improves the conductivity of the solid polymer electrolyte. The room temperature ionic conductivity is as high as 1.59×10 -4 S cm -1 .

[0026] (3) The cross-linked solid polymer electrolyte provided by the present invention is prepared by an in-situ polymerization method, which can effectively solve the problem of poor interface contact between the solid polymer electrolyte and the positive and negative electrodes, reduce the interface impedance, and further improve the lithium ion transmission performance.

[0027] (4) Compared with traditional liquid electrolytes, the cross-linked solid polymer electrolyte provided by the present invention does not contain flammable organic solvents, has higher thermal stability and safety, and its thermal decomposition temperature reaches above 250°C.

[0028] (5) The preparation method of the solid polymer electrolyte provided by the present invention is simple, the reaction conditions are mild, no catalyst is required, and no post-treatment is required. At the same time, the thickness of the solid polymer electrolyte can be controlled by the volume of the added precursor solution, and it can be prepared into different shapes, which is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a physical picture of the cross-linked solid polymer electrolyte described in Comparative Example 1.

[0030] Figure 2 This is a comparative infrared spectrum of the cross-linked solid polymer electrolyte described in Example 1 and PEGDE.

[0031] Figure 3 This is the thermogravimetric curve of the cross-linked solid polymer electrolyte described in Example 1.

[0032] Figure 4 This is the differential scanning calorimetry test curve of the cross-linked solid polymer electrolyte described in Example 1.

[0033] Figure 5 This is the X-ray diffraction pattern of the cross-linked solid polymer electrolyte described in Example 1.

[0034] Figure 6 3 is the impedance diagram of the cross-linked solid polymer electrolyte described in Example 1 at room temperature.

[0035] Figure 7 This is a curve showing the change in conductivity of the cross-linked solid polymer electrolyte described in Example 1 as a function of temperature.

[0036] Figure 8 This is the electrochemical window test curve of the cross-linked solid polymer electrolyte described in Example 1.

[0037] Figure 9 This is a schematic diagram of the in-situ polymerization of the solid polymer electrolyte and the electrode described in Example 9.

[0038] Figure 10 This is the thermogravimetric curve of the solid polymer electrolyte described in Example 11.

[0039] Figure 11 This is the differential scanning calorimetry test curve of the solid polymer electrolyte described in Example 11.

[0040] Figure 12 This is the X-ray diffraction pattern of the solid polymer electrolyte described in Example 11.

[0041] Figure 13 This is an impedance diagram of the solid polymer electrolyte described in Example 11 at room temperature.

[0042] Figure 14This is a curve showing the change in electrical conductivity of the solid polymer electrolyte described in Example 11 with temperature.

[0043] Figure 15 This is the electrochemical window test curve of the solid polymer electrolyte described in Example 11. DETAILED DESCRIPTION

[0044] The following will be combined with the embodiments of the present invention and the accompanying drawings to clearly and completely describe the purpose, technical solutions and advantages of the present invention. It should be understood that the embodiments described herein are only part of the embodiments of the present invention and are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without making creative efforts are all within the scope of protection of the present invention.

[0045] The present invention provides an in-situ polymerized solid polymer electrolyte comprising a cross-linked polymer matrix, a lithium salt or a sodium salt, and an additive. The structure of the cross-linked polymer matrix is ​​shown in formula (I):

[0046]

[0047] wherein R comprises aliphatic chains or aromatic rings in different diamine monomers;

[0048] n is an integer from 4 to 113.

[0049] According to the present invention, the cross-linked polymer matrix is ​​prepared by in situ polymerization of polyethylene glycol diglycidyl ether and diamine monomers through nucleophilic addition reaction, wherein the diamine monomers preferably include aliphatic diamine monomers and aromatic diamine monomers, and the aliphatic diamine monomers preferably include NH2-(CH2) m -NH2 (m is an integer of 2 to 30) and aliphatic diamine monomers containing branches of different carbon chain lengths at different positions thereof; aromatic diamine monomers preferably include benzyl diamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-phenyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2-propyl-1,4-phenylenediamine, 2-isopropyl-1,4-phenylenediamine amine, 2-butyl-1,4-phenylenediamine, 2-isobutyl-1,4-phenylenediamine, 2-pentyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2-bromo-1,4-phenylenediamine, 4,4-diphenylenediamine, 2,2'-dimethyl-4,4'-diphenylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2-phenyl-p-phenylenediamine, 2-phenoxy-p-phenylenediamine;

[0050] According to the present invention, the structure of polyethylene glycol diglycidyl ether (PEGDE) is shown in (II):

[0051]

[0052] Wherein, n is an integer of 4 to 113, and the relative molecular mass of polyethylene glycol in polyethylene glycol diglycidyl ether (PEGDE) is 200 to 5000.

[0053] According to the present invention, the lithium salt is preferably one or more of lithium bis(trifluoromethanesulfonyl imide), lithium bis(fluorosulfonyl imide), lithium perchlorate, lithium difluorooxalatoborate, lithium hexafluorophosphate, and lithium tetrafluoroborate; the sodium salt is preferably one or more of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(fluorosulfonyl imide), and sodium bis(trifluoromethanesulfonyl imide.

[0054] According to the present invention, the additives are preferably inorganic and organic. The inorganic additives are preferably one or more of lithium lanthanum zirconium oxide, lithium lanthanum titanate, lithium titanium phosphate, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, zinc oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, zeolite, montmorillonite, or kaolin. The organic additives are preferably one or more of plastic crystal succinonitrile, ethylene carbonate, propylene carbonate, N,N-dimethylformamide, and low molecular weight PEG. The number average molecular weight of the PEG is preferably 100-800.

[0055] According to the present invention, for lithium salts, the addition of plastic crystals to the solid polymer electrolyte can act as a plasticizer, further increasing the transmission capacity of lithium ions in the solid polymer electrolyte and increasing the lithium ion conductivity of the solid polymer electrolyte. For sodium salts, the addition of fillers can inhibit the crystallization of PEO and improve the mobility of polymer chain segments. The interface area between the filler and the PEO matrix can be Na + Provide more migration paths; at the same time, it can improve the mechanical strength of the polymer electrolyte to a certain extent; the addition of plasticizers can further increase the transmission capacity of sodium ions in the solid polymer electrolyte and improve the electrochemical properties of the solid polymer electrolyte.

[0056] The present invention also provides a method for preparing an in-situ polymerized solid polymer electrolyte, comprising the following steps:

[0057] Polyethylene glycol diglycidyl ether is melted, preferably at a melting temperature of 25-80°C, and then lithium salt or sodium salt and additives are added in sequence, stirred and dissolved, preferably for 5 minutes to 24 hours, and then diamine monomer is added. After the dissolution reaction is completed, the solution is allowed to stand for degassing, preferably at a temperature of 5-40°C and for 0.05-4 hours, and then an in-situ polymerization reaction is carried out to obtain an in-situ polymerized solid polymer electrolyte. The dissolution temperature of the added diamine monomer is preferably 10-80°C, and the dissolution time is preferably 3 minutes to 48 hours.

[0058] In actual application, a polymer electrolyte precursor solution is obtained after standing and degassing, and then the polymer electrolyte precursor solution is assembled with the positive electrode sheet and the negative electrode sheet to form a solid-state battery. The solution is then allowed to stand at 10-120°C for in-situ polymerization for 0.5-48 hours, and an in-situ polymerized solid polymer electrolyte is obtained in this process.

[0059] According to the present invention, the molar ratio of the diamine monomer to polyethylene glycol diglycidyl ether is preferably 1:(1-8); the molar ratio of the lithium ions or sodium ions in the salt to the ether oxygen atoms in the polymer of formula (I) is preferably 1:(2-128); and the content of the additive is preferably 0.2-300 wt% of the polymer electrolyte.

[0060] The present invention also provides application of the polymer electrolyte in lithium ion batteries or sodium ion batteries.

[0061] The present invention is further described in detail below with reference to specific examples, in which the raw materials involved are all commercially available.

[0062] Example 1

[0063] 1,4-Butanediamine-polyethylene glycol diglycidyl ether PEGDE 500 solid polymer electrolyte

[0064] The preparation method of the solid polymer electrolyte is as follows: 1.702g polyethylene glycol diglycidyl ether PEGDE 500 , which is liquid at room temperature. Add 0.611g of lithium bis(trifluoromethanesulfonyl)imide and stir to dissolve completely. Add 0.36g of succinonitrile and stir to dissolve completely. Add 0.1g of 1,4-butanediamine monomer and stir for 5 minutes (diamine monomer is completely dissolved). Then, let the mixture stand at 30°C for degassing for 7 minutes. Take 0.2ml of viscous precursor solution and assemble it with stainless steel sheet and lithium sheet into 'stainless steel sheet / SPE / stainless steel sheet' R2032 button battery and 'lithium sheet / SPE / stainless steel sheet' R2032 button battery respectively. Let it stand in situ for 8 hours at room temperature. The conductivity and electrochemical stability window are tested respectively. The film thickness of the obtained solid polymer electrolyte is 123μm, and the room temperature conductivity is 1.71×10-4 S cm -1 , the electrochemical stability window is 4.6V.

[0065] Figure 2 This is a comparative infrared spectrum of the cross-linked solid polymer electrolyte described in Example 1 and PEGDE. Figure 2 This indicates that the solid polymer electrolyte was successfully synthesized. Compared with the characteristic peak of PEGDE, the solid polymer electrolyte has a wave number of 1255 cm -1 and 910cm -1 The characteristic peak of the epoxy group at 1201cm -1 The stretching vibration of aliphatic CN bonds appears at 620 cm -1 The characteristic peak of Li-O bond appears at , indicating the successful synthesis of solid polymer electrolyte.

[0066] Figure 3 This is the thermogravimetric curve of the cross-linked solid polymer electrolyte described in Example 1. Figure 3 This shows that the solid polymer electrolyte has good thermal stability and the thermal decomposition temperature reaches above 250°C.

[0067] Figure 4 This is the differential scanning calorimetry test curve of the cross-linked solid polymer electrolyte described in Example 1. Figure 4 This shows that the solid polymer electrolyte has a low glass transition temperature of -36.71℃.

[0068] Figure 5 This is the X-ray diffraction pattern of the cross-linked solid polymer electrolyte described in Example 1. Figure 5 This shows that the solid polymer electrolyte has no obvious crystallization peak, and the peak is in a diffuse state. The crystallinity is less than 10% when fitted with the software JADE.

[0069] Figure 6 3 is the impedance diagram of the cross-linked solid polymer electrolyte described in Example 1 at room temperature. Figure 6 This shows that the solid polymer electrolyte has a low impedance value of only 36 ohms at room temperature.

[0070] Figure 7 This is a curve showing the change in conductivity of the cross-linked solid polymer electrolyte described in Example 1 as a function of temperature. Figure 7 This shows that the conductivity of the solid polymer electrolyte increases with increasing temperature and has a relatively high conductivity.

[0071] Figure 8 This is the electrochemical window test curve of the cross-linked solid polymer electrolyte described in Example 1. Figure 8 This shows that the solid polymer electrolyte has a wide electrochemical window, up to 4.6V.

[0072] Example 2

[0073] 1,6-Hexanediamine-polyethylene glycol diglycidyl ether PEGDE 1000 solid polymer electrolyte

[0074] The preparation method of the solid polymer electrolyte is as follows: 1.291g polyethylene glycol diglycidyl ether PEGDE 1000 After complete melting at 40°C, 0.318g of lithium tetrafluoroborate was added and stirred to dissolve completely. After adding 0.7g of inorganic solid electrolyte lithium lanthanum zirconium oxide and stirring evenly, 0.1g of 1,6-hexanediamine monomer was added and stirred for 7 minutes (the diamine monomer was completely dissolved). The mixture was then allowed to stand at room temperature for degassing for 6.5 minutes. 0.5ml of the viscous precursor solution was assembled with stainless steel sheets and lithium sheets to form 'stainless steel sheet / SPE / stainless steel sheet' R2032 button cells and 'lithium sheet / SPE / stainless steel sheet' R2032 button cells, and allowed to stand at room temperature for in-situ polymerization for 7 hours. The conductivity and electrochemical stability window were tested respectively. The obtained solid polymer electrolyte had a film thickness of 524μm and a room temperature conductivity of 6.4×10 -6 S cm -1 , the electrochemical stability window is 4.6V.

[0075] Example 3

[0076] 1,4-Butanediamine-polyethylene glycol diglycidyl ether PEGDE 2000 solid polymer electrolyte

[0077] The preparation method of the solid polymer electrolyte is as follows: take 4.538g polyethylene glycol diglycidyl ether PEGDE 2000 Heat to 54°C and melt completely, add 0.885g lithium perchlorate and stir to dissolve completely, add 0.16g succinonitrile and stir to dissolve completely, add 0.1g diamine monomer and stir for 8 minutes (diamine monomer is completely dissolved), and then let the mixture stand at 30°C for degassing for 8 minutes. Take 0.3ml of viscous precursor solution and assemble it with stainless steel sheet and lithium sheet into 'stainless steel sheet / SPE / stainless steel sheet' R2032 button battery and 'lithium sheet / SPE / stainless steel sheet' R2032 button battery respectively, and let it stand at 20°C for in-situ polymerization for 10 hours, and test its conductivity and electrochemical stability window respectively. The obtained solid polymer electrolyte has a film thickness of 312μm and a room temperature conductivity of 2.65×10 -5 S cm -1 , the electrochemical stability window is 4.5V.

[0078] Example 4

[0079] 1,6-Hexanediamine-polyethylene glycol diglycidyl ether PEGDE 500 solid polymer electrolyte

[0080] The preparation method of the solid polymer electrolyte is as follows: 1.291g polyethylene glycol diglycidyl ether PEGDE 500 , which is liquid at room temperature. Add 0.463g of lithium bis(trifluoromethanesulfonyl)imide and stir to dissolve completely. Add 1.04g of succinonitrile and stir to dissolve completely. Add 0.1g of 1,6-hexanediamine monomer and stir for 6 minutes (diamine monomer is completely dissolved). Then, let the mixture stand at room temperature for degassing for 6 minutes. Take 0.4ml of viscous precursor solution and assemble it with stainless steel sheet and lithium sheet into 'stainless steel sheet / SPE / stainless steel sheet' R2032 button battery and 'lithium sheet / SPE / stainless steel sheet' R2032 button battery respectively. Let it stand at room temperature for in-situ polymerization for 12 hours. The conductivity and electrochemical stability window are tested respectively. The film thickness of the obtained solid polymer electrolyte is 438μm, and the room temperature conductivity is 1.03×10 -4 S cm -1 , the electrochemical stability window is 4.2V.

[0081] Example 5

[0082] p-phenylenediamine-polyethylene glycol diglycidyl ether PEGDE 500 solid polymer electrolyte

[0083] The preparation method of the solid polymer electrolyte is as follows: take 0.555g polyethylene glycol diglycidyl ether PEGDE 500 , which is liquid at room temperature. Add 0.1g of lithium bis(difluorooxalato)borate and stir to dissolve completely. Add 0.033g of silica nanoparticles (30±10nm) and stir evenly. Add 0.1g of p-phenylenediamine monomer and stir for 6min (diamine monomer is completely dissolved). The mixture is then allowed to stand at room temperature for degassing for 6min. Take 0.4ml of the viscous precursor solution and assemble it with stainless steel sheet and lithium sheet into 'stainless steel sheet / SPE / stainless steel sheet' R2032 button battery and 'lithium sheet / SPE / stainless steel sheet' R2032 button battery respectively. The cells are then allowed to stand at 40°C for in-situ polymerization for 15h. The conductivity and electrochemical stability window are tested respectively. The film thickness of the obtained solid polymer electrolyte is 385μm, and the room temperature conductivity is 2.58×10 -5 S cm -1 , the electrochemical stability window is 4.4V.

[0084] Example 6

[0085] 1,10-Decanediamine-polyethylene glycol diglycidyl ether PEGDE 1000 solid polymer electrolyte

[0086] The preparation method of the solid polymer electrolyte is as follows: 1.272g polyethylene glycol diglycidyl ether PEGDE1000 After complete melting at 40°C, 0.34g of lithium hexafluorophosphate was added and stirred to dissolve completely. After adding 0.137g of polyethylene glycol (PEG) with a molecular weight of 200 and stirring to dissolve completely, 0.1g of 1,10-decanediamine monomer was added and stirred for 10 minutes (the diamine monomer was completely dissolved). The mixture was then allowed to stand at room temperature for degassing for 8 minutes. 0.2ml of the viscous precursor solution was assembled with a stainless steel sheet and a lithium sheet to form a 'stainless steel sheet / SPE / stainless steel sheet' R2032 button cell and a 'lithium sheet / SPE / stainless steel sheet' R2032 button cell, and the cells were allowed to stand at room temperature for in-situ polymerization for 15 hours. The conductivity and electrochemical stability window were tested respectively. The obtained solid polymer electrolyte had a film thickness of 128μm and a room temperature conductivity of 5.86×10 -5 S cm -1 , the electrochemical stability window is 4.6V.

[0087] Example 7

[0088] Ethylenediamine-polyethylene glycol diglycidyl ether PEGDE 200 solid polymer electrolyte

[0089] The preparation method of the solid polymer electrolyte is as follows: 0.1g of liquid polyethylene glycol diglycidyl ether PEGDE is taken at room temperature. 200 , add 0.161g of lithium bis(trifluoromethanesulfonyl)imide and stir to dissolve completely, then add 0.1g of ethylenediamine monomer and stir for 3min (diamine monomer is completely dissolved), then let the mixture stand at 20°C for degassing for 5min. Take 0.3ml of viscous precursor solution and assemble it with stainless steel sheet and lithium sheet into 'stainless steel sheet / SPE / stainless steel sheet' R2016 button cell and 'lithium sheet / SPE / stainless steel sheet' R2016 button cell respectively. Then let it stand at 20°C for in-situ polymerization for 5h, and test its conductivity and electrochemical stability window respectively. The obtained solid polymer electrolyte has a film thickness of 200μm and a room temperature conductivity of 1.03×10 -6 S cm -1 , the electrochemical stability window is 5.0V.

[0090] Example 8

[0091] 1,6-Hexanediamine-polyethylene glycol diglycidyl ether PEGDE 4000 solid polymer electrolyte

[0092] The preparation method of the solid polymer electrolyte is as follows: take 7.57g polyethylene glycol diglycidyl ether PEGDE 4000After complete melting at 60°C, 1.947g of lithium bis(fluorosulfonyl)imide was added and stirred to dissolve completely. After 3.835g of succinonitrile was added and stirred to dissolve completely, 0.1g of 1,6-hexanediamine monomer was added and stirred for 30min (diamine monomer was completely dissolved). The mixture was then allowed to stand at room temperature for degassing for 10min. 0.2ml of the viscous precursor solution was assembled with stainless steel sheet and lithium sheet to form a 'stainless steel sheet / SPE / stainless steel sheet' R2032 button cell and a 'lithium sheet / SPE / stainless steel sheet' R2032 button cell, respectively. The cells were allowed to stand at room temperature for in-situ polymerization for 24h, and their conductivity and electrochemical stability window were tested. The obtained solid polymer electrolyte had a film thickness of 128μm and a room temperature conductivity of 1.01×10 -4 S cm -1 , the electrochemical stability window is 4.9V.

[0093] Comparative Example 1

[0094] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold or a glass culture dish and allowed to stand for polymerization for the same time and temperature as in Example 1 after the battery was assembled. After solidification, a solid polymer electrolyte film was obtained. This film was then sliced ​​into 16 mm diameter discs for assembly into corresponding button cells. Other feed ratios, reaction conditions, and precursor solution preparation and testing conditions were similar to those in Example 1. The resulting solid polymer electrolyte film had a thickness of 159 μm and a room temperature conductivity of 5.99 × 10 -6 S cm -1 , the electrochemical stability window is 4.2V.

[0095] Comparative Example 2

[0096] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold or a glass culture dish and allowed to stand for polymerization for the same time and temperature as in Example 3 after the battery was assembled. After solidification, a solid polymer electrolyte film was obtained. This film was then cut into 16 mm diameter discs using a slicer to assemble the corresponding button cells. Other feed ratios, reaction conditions, and precursor solution preparation and testing conditions were similar to those in Example 3. The resulting solid polymer electrolyte film had a thickness of 125 μm and a room temperature conductivity of 4.28 × 10 -6 S cm -1 , the electrochemical stability window is 4.1V.

[0097] Figure 1 The following are the physical pictures of the cross-linked solid polymer electrolyte described in Comparative Example 1. Figure a is a physical picture of the electrolyte film in a flat state, and Figure b is a physical picture of the electrolyte film after being bent. Figure 1 This shows that the solid polymer electrolyte has excellent film-forming properties and good flexibility.

[0098] Comparative Example 3

[0099] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold or a glass culture dish and allowed to stand for polymerization for the same time and temperature as in-situ polymerization after battery assembly in Example 4. After solidification, a solid polymer electrolyte film was obtained. This film was then sliced ​​into 16 mm diameter discs for assembly into corresponding button cells. Other feed ratios, reaction conditions, and precursor solution preparation and testing conditions were similar to those in Example 4. The resulting solid polymer electrolyte film had a thickness of 350 μm and a room temperature conductivity of 1.84 × 10 -5 S cm -1 , the electrochemical stability window is 3.9V.

[0100] Comparative Example 4

[0101] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold or a glass culture dish and allowed to stand for polymerization for the same time and temperature as in Example 7 after the battery was assembled. After solidification, a solid polymer electrolyte film was obtained. This film was then cut into 16 mm diameter discs using a slicer to assemble the corresponding button cells. Other feed ratios, reaction conditions, and precursor solution preparation and testing conditions were similar to those in Example 7. The resulting solid polymer electrolyte film had a thickness of 222 μm and a room temperature conductivity of 2.85 × 10 -7 S cm -1 , the electrochemical stability window is 4.5V.

[0102] Comparative Example 5

[0103] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold or a glass culture dish and allowed to stand for polymerization for the same time and temperature as in Example 8 after the battery was assembled. After solidification, a solid polymer electrolyte film was obtained. This film was then cut into 16 mm diameter discs using a slicer to assemble the corresponding button cells. Other feed ratios, reaction conditions, and precursor solution preparation and testing conditions were similar to those in Example 8. The resulting solid polymer electrolyte film had a thickness of 265 μm and a room temperature conductivity of 3.58 × 10 -5 S cm -1 , the electrochemical stability window is 4.6V.

[0104] The preparation process of the solid polymer electrolyte provided by the present invention is carried out under low water and oxygen content conditions, with the water and oxygen content being less than 0.5 ppm. During the preparation process of the solid polymer electrolyte, the order of adding the lithium salt and additives can be reversed. The lithium ion conductivity of the solid polymer electrolyte is measured by electrochemical impedance spectroscopy using the formula: Where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R b is the measured impedance.

[0105] Table 1 Comparison of feed composition and electrochemical performance of solid polymer electrolytes in Examples and Comparative Examples

[0106]

[0107]

[0108] Example 9

[0109] Ethylenediamine-polyethylene glycol diglycidyl ether PEGDE 500 solid polymer electrolyte

[0110] The preparation method of the solid sodium ion solid polymer electrolyte is as follows: 1.664g of liquid polyethylene glycol diglycidyl ether PEGDE is taken at room temperature. 500 0.146g of sodium perchlorate was added and stirred at room temperature until completely dissolved. 0.265g of silica was added and stirred at room temperature until evenly mixed. 0.1g of ethylenediamine monomer was added and stirred for 10 minutes (until the diamine monomer was completely dissolved). The mixture was then allowed to stand at room temperature for 8 minutes to degas, yielding a viscous precursor solution. This solution was then in-situ polymerized with the corresponding positive and negative electrodes and allowed to stand at room temperature for 30 hours to yield a solid polymer electrolyte.

[0111] Testing the ionic conductivity of solid-state sodium-ion solid polymer electrolytes: 0.04 ml of the precursor solution was assembled with a stainless steel sheet to form a R2032 coin cell with a "stainless steel sheet / SPE / stainless steel sheet" pattern. Sodium ion conductivity was measured using electrochemical impedance spectroscopy (EIS) with a frequency range of 400 mHz to 1 MHz and a scan rate of 10 mV·s. -1 , using the formula: σ=L / AR b , where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R b The measured impedance is shown in Figure 2. The thickness of the solid sodium ion solid polymer electrolyte membrane is 287 μm, and the ionic conductivity is 3.85×10 -6 S cm -1 .

[0112] Testing the electrochemical window of a solid-state sodium-ion solid polymer electrolyte: A certain amount of viscous precursor solution was assembled with a stainless steel sheet and a sodium sheet to form a "stainless steel sheet / SPE / sodium sheet" R2032 button cell. The electrochemical window was measured using a linear voltammetric sweep using an electrochemical workstation, starting at the open circuit potential, with a maximum potential of 7 V and a scan rate of 1 mV·s. -1 After testing, the electrochemical window of the solid polymer electrolyte was found to be 4.3V.

[0113] Figure 9This is a schematic diagram of the in-situ polymerization of the solid polymer electrolyte and the electrode described in Example 9. Figure 9 This shows that the solid polymer electrolyte has good compatibility with the electrode.

[0114] Example 10

[0115] 1,10-Decanediamine-polyethylene glycol diglycidyl ether PEGDE 2000 solid polymer electrolyte

[0116] The preparation method of the solid sodium ion solid polymer electrolyte is as follows: take 2.089g polyethylene glycol diglycidyl ether PEGDE 2000 Melt the mixture at 56°C, add 0.871g of sodium bis(trifluoromethanesulfonyl)imide and stir at 56°C until completely dissolved. Then, add 0.657g of succinonitrile and stir at 56°C until evenly mixed. Add 0.1g of 1,10-decanediamine monomer and stir for 22 minutes (until the diamine monomer is completely dissolved). The mixture is then allowed to stand at room temperature for 10 minutes to degas, yielding a viscous precursor solution. This solution is then in-situ polymerized with the corresponding positive and negative electrodes and allowed to stand at room temperature for 55 hours to yield a solid polymer electrolyte.

[0117] Testing the ionic conductivity of solid-state sodium-ion solid polymer electrolytes: 0.1 ml of the precursor solution was assembled with a stainless steel sheet to form a R2032 coin cell with a "stainless steel sheet / SPE / stainless steel sheet" pattern. Sodium ion conductivity was measured using electrochemical impedance spectroscopy (EIS) with a frequency range of 400 mHz to 1 MHz and a scan rate of 10 mV·s. -1 , using the formula: σ=L / AR b , where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R b The measured impedance is shown in Figure 2. The solid sodium ion solid polymer electrolyte membrane has a thickness of 56 μm and an ionic conductivity of 2.04×10 -5 S cm -1 .

[0118] Testing the electrochemical window of a solid-state sodium-ion solid polymer electrolyte: A certain amount of viscous precursor solution was assembled with a stainless steel sheet and a sodium sheet to form a "stainless steel sheet / SPE / sodium sheet" R2032 button cell. The electrochemical window was measured using a linear voltammetric sweep using an electrochemical workstation, starting at the open circuit potential, with a maximum potential of 7 V and a scan rate of 1 mV·s. -1 . After testing, the electrochemical window of the solid polymer electrolyte is 4.5V.

[0119] Example 11

[0120] 1,4-Butanediamine-polyethylene glycol diglycidyl ether PEGDE 1000solid polymer electrolyte

[0121] The preparation method of the solid sodium ion solid polymer electrolyte is as follows: take 4.538g polyethylene glycol diglycidyl ether PEGDE 1000 Melt the mixture at 42°C, add 3.611g of sodium bis(trifluoromethanesulfonyl)imide and stir at 42°C until completely dissolved. Then, add 0.928g of succinonitrile and stir at 42°C until evenly mixed. Add 0.1g of 1,4-butanediamine monomer and stir for 18 minutes (until the diamine monomer is completely dissolved). The mixture is then allowed to stand at room temperature for 15 minutes to degas, yielding a viscous precursor solution. This solution is then in-situ polymerized with the corresponding positive and negative electrodes and allowed to stand at room temperature for 37 hours to yield a solid polymer electrolyte.

[0122] Testing the ionic conductivity of solid-state sodium-ion solid polymer electrolytes: 0.25 ml of the precursor solution was assembled with a stainless steel sheet to form a R2032 coin cell with a "stainless steel sheet / SPE / stainless steel sheet" pattern. Sodium ion conductivity was measured using electrochemical impedance spectroscopy (EIS) with a test frequency range of 400 mHz to 1 MHz and a scan rate of 10 mV·s. -1 , using the formula: σ=L / AR b , where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R b The measured impedance is shown in Figure 2. The thickness of the solid sodium ion solid polymer electrolyte membrane is 189 μm, and the ionic conductivity is 1.59×10 -4 S cm -1 .

[0123] Testing the electrochemical window of a solid-state sodium-ion solid polymer electrolyte: A certain amount of viscous precursor solution was assembled with a stainless steel sheet and a sodium sheet to form a "stainless steel sheet / SPE / sodium sheet" R2032 button cell. The electrochemical window was measured using a linear voltammetric sweep using an electrochemical workstation, starting at the open circuit potential, with a maximum potential of 7 V and a scan rate of 1 mV·s. -1 After testing, the electrochemical window of the solid polymer electrolyte was found to be 4.6V.

[0124] Figure 10 This is the thermogravimetric curve of the solid polymer electrolyte described in Example 9. Figure 10 This shows that the solid polymer electrolyte has good thermal stability and the thermal decomposition temperature reaches above 250°C.

[0125] Figure 11 This is the differential scanning calorimetry test curve of the solid polymer electrolyte described in Example 11. Figure 11 This shows that the solid polymer electrolyte has a low glass transition temperature of -32.56℃.

[0126] Figure 12 This is the X-ray diffraction pattern of the solid polymer electrolyte described in Example 11. Figure 12 This shows that the solid polymer electrolyte has no obvious crystallization peak, and the peak is in a diffuse state. The crystallinity is less than 10% when fitted with the software JADE.

[0127] Figure 13 This is an impedance diagram of the solid polymer electrolyte described in Example 11 at room temperature. Figure 13 This shows that the solid polymer electrolyte has a low impedance value of only 39 ohm at room temperature.

[0128] Figure 14 This is a curve showing the change in electrical conductivity of the solid polymer electrolyte described in Example 11 with temperature. Figure 14 This shows that the conductivity of the solid polymer electrolyte increases with increasing temperature and has a relatively high conductivity.

[0129] Figure 15 This is the electrochemical window test curve of the solid polymer electrolyte described in Example 11. Figure 15 This shows that the solid polymer electrolyte has a wide electrochemical window, up to 4.6V.

[0130] Example 12

[0131] 1,6-Hexanediamine-polyethylene glycol diglycidyl ether PEGDE 4000 solid polymer electrolyte

[0132] The preparation method of the solid sodium ion solid polymer electrolyte is as follows: take 5.164g polyethylene glycol diglycidyl ether PEGDE 4000 Melt the mixture at 62°C, add 0.305g of sodium trifluoromethanesulfonate and stir at 62°C until completely dissolved. Then, add 0.158g of titanium dioxide and stir at 62°C until evenly mixed. Add 0.1g of 1,6-hexanediamine monomer and stir for 30 minutes (until the diamine monomer is completely dissolved). The mixture is then allowed to stand at room temperature for 15 minutes to degas, yielding a viscous precursor solution. This solution is then in-situ polymerized with the corresponding positive and negative electrodes and allowed to stand at room temperature for 45 hours to yield a solid polymer electrolyte.

[0133] Testing the ionic conductivity of solid-state sodium-ion solid polymer electrolytes: 0.3 ml of the precursor solution was assembled with a stainless steel sheet to form a R2032 coin cell with a "stainless steel sheet / SPE / stainless steel sheet" pattern. Sodium ion conductivity was measured using electrochemical impedance spectroscopy (EIS) with a frequency range of 400 mHz to 1 MHz and a scan rate of 10 mV·s. -1 , using the formula: σ=L / AR b , where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R bThe measured impedance is shown in Figure 2. The thickness of the solid sodium ion solid polymer electrolyte membrane is 237 μm, and the ionic conductivity is 1.00×10 -4 S cm -1 .

[0134] Testing the electrochemical window of a solid-state sodium-ion solid polymer electrolyte: A certain amount of viscous precursor solution was assembled with a stainless steel sheet and a sodium sheet to form a "stainless steel sheet / SPE / sodium sheet" R2032 button cell. The electrochemical window was measured using a linear voltammetric sweep using an electrochemical workstation, starting at the open circuit potential, with a maximum potential of 7 V and a scan rate of 1 mV·s. -1 . After testing, the electrochemical window of the solid polymer electrolyte is 4.7V.

[0135] Example 13

[0136] p-phenylenediamine-polyethylene glycol diglycidyl ether PEGDE 500 solid polymer electrolyte

[0137] The preparation method of the solid sodium ion solid polymer electrolyte is as follows: 1.387g of liquid polyethylene glycol diglycidyl ether PEGDE is taken at room temperature. 500 0.146g of sodium bis(fluorosulfonyl)imide was added and stirred at room temperature until completely dissolved. 0.119g of polyethylene glycol (PEG) with a molecular weight of 500 was added and stirred at room temperature until evenly mixed. 0.1g of ethylenediamine monomer was added and stirred for 16 minutes (until the diamine monomer completely dissolved). The mixture was then allowed to stand at room temperature for 5 minutes to degas, yielding a viscous precursor solution. This solution was then in-situ polymerized with the corresponding positive and negative electrodes and allowed to stand at room temperature for 40 hours to yield a solid polymer electrolyte.

[0138] Testing the ionic conductivity of solid-state sodium-ion solid polymer electrolytes: 0.4 ml of the precursor solution was assembled with a stainless steel sheet to form a R2032 coin cell with a "stainless steel sheet / SPE / stainless steel sheet" pattern. Sodium ion conductivity was measured using electrochemical impedance spectroscopy (EIS) with a frequency range of 400 mHz to 1 MHz and a scan rate of 10 mV·s. -1 , using the formula: σ=L / AR b , where L is the thickness of the electrolyte, A is the area of ​​the stainless steel sheet at room temperature, and R b The measured impedance is shown in Figure 2. The solid sodium ion solid polymer electrolyte membrane has a thickness of 376 μm and an ionic conductivity of 8.97×10 -5 S cm -1 .

[0139] Testing the electrochemical window of a solid-state sodium-ion solid polymer electrolyte: A certain amount of viscous precursor solution was assembled with a stainless steel sheet and a sodium sheet to form a "stainless steel sheet / SPE / sodium sheet" R2032 button cell. The electrochemical window was measured using a linear voltammetric sweep using an electrochemical workstation, starting at the open circuit potential, with a maximum potential of 7 V and a scan rate of 1 mV·s. -1 . After testing, the electrochemical window of the solid polymer electrolyte is 4.5V.

[0140] Comparative Example 6

[0141] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold and allowed to stand for polymerization for the same time and temperature as in-situ polymerization after battery assembly in Example 11. After solidification, a solid polymer electrolyte film was obtained. This film was then sliced ​​into 16 mm diameter discs for assembly into corresponding button cells. Other feed ratios, reaction conditions, and testing conditions were similar to those in Example 11. The resulting solid sodium ion polymer electrolyte film had a thickness of 89 μm and a room temperature conductivity of 5.68 × 10 -5 S cm -1 , the electrochemical stability window is 4.2V.

[0142] Comparative Example 7

[0143] Instead of in-situ polymerization, the resulting viscous precursor solution was poured into a polytetrafluoroethylene mold and allowed to stand for polymerization for the same time and temperature as in-situ polymerization after battery assembly in Example 12. After solidification, a solid polymer electrolyte film was obtained. This film was then sliced ​​into 16 mm diameter discs for assembly into corresponding button cells. Other feed ratios, reaction conditions, and testing conditions were similar to those in Example 12. The resulting solid sodium ion polymer electrolyte film had a thickness of 146 μm and a room temperature conductivity of 3.28 × 10 -5 S cm -1 , the electrochemical stability window is 4.0V.

[0144] Table 2 Comparison of feed composition and electrochemical performance of solid polymer electrolytes in Examples and Comparative Examples

[0145]

[0146] It will be easily understood by those skilled in the art that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, improvements and embellishments made without departing from the spirit and principles of the present invention should be regarded as the scope of protection of the present invention.

Claims

1. An in-situ polymerized solid polymer electrolyte, characterized in that It includes a cross-linked polymer matrix, a lithium salt or a sodium salt and an additive. The structure of the cross-linked polymer matrix is ​​shown in formula (I): wherein R comprises aliphatic chains or aromatic rings in different diamine monomers; n is an integer from 4 to 113.

2. The in-situ polymerized solid polymer electrolyte according to claim 1, characterized in that: The cross-linked polymer matrix is ​​prepared by in-situ polymerization of polyethylene glycol diglycidyl ether and diamine monomers through nucleophilic addition reaction, wherein the diamine monomers include aliphatic diamine monomers and aromatic diamine monomers, and the aliphatic diamine monomers include NH2-(CH2) m -NH2, m is an integer of 2 to 30, and aliphatic diamine monomers containing branches of different carbon chain lengths at different positions; aromatic diamine monomers include benzyl diamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-phenyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2-propyl-1,4-phenylenediamine, 2-isopropyl-1,4-phenylenediamine , 2-butyl-1,4-phenylenediamine, 2-isobutyl-1,4-phenylenediamine, 2-pentyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2-bromo-1,4-phenylenediamine, 4,4-diphenylenediamine, 2,2'-dimethyl-4,4'-diphenylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2-phenyl-p-phenylenediamine, 2-phenoxy-p-phenylenediamine; The structure of polyethylene glycol diglycidyl ether is shown in (II): Wherein, n is an integer of 4 to 113, and the relative molecular mass of polyethylene glycol in polyethylene glycol diglycidyl ether is 200 to 5000.

3. The in-situ polymerized solid polymer electrolyte according to claim 1, characterized in that: The lithium salt is one or more of lithium bis(trifluoromethanesulfonyl imide), lithium bis(fluorosulfonyl imide), lithium perchlorate, lithium difluorooxalatoborate, lithium hexafluorophosphate, and lithium tetrafluoroborate.

4. The in-situ polymerized solid polymer electrolyte according to claim 1, characterized in that: The sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bis(fluorosulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide.

5. The in-situ polymerized solid polymer electrolyte according to claim 1, characterized in that: The additives are inorganic additives and organic additives. The inorganic additives are one or more of lithium lanthanum zirconium oxide, lithium lanthanum titanate, lithium titanium phosphate, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, zinc oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, zeolite, montmorillonite or kaolin; the organic additives are one or more of plastic crystal succinonitrile, ethylene carbonate, propylene carbonate, N,N-dimethylformamide and PEG.

6. The method for preparing an in-situ polymerized solid polymer electrolyte according to claim 1, characterized in that: The following steps are involved: The polyethylene glycol diglycidyl ether is melted, and then lithium salt or sodium salt and additives are added in sequence. After stirring and dissolving, the diamine monomer is added. After dissolving, the monomer is allowed to stand and degas to perform in-situ polymerization reaction to obtain an in-situ polymerized solid polymer electrolyte.

7. The method for preparing an in-situ polymerized solid polymer electrolyte according to claim 6, characterized in that: The molar ratio of the diamine monomer to polyethylene glycol diglycidyl ether is 1:(1-8); the molar ratio of the lithium ions or sodium ions in the lithium salt or sodium salt to the ether oxygen atoms in the polymer (I) is 1:(2-128); and the content of the additive is 0.2-300wt% of the polymer electrolyte.

8. The method for preparing an in-situ polymerized solid polymer electrolyte according to claim 6, characterized in that: The melting temperature of the polyethylene glycol diglycidyl ether is 25-80°C, the stirring and dissolving time is 5min-24h, the dissolving temperature of the added diamine monomer is 10-80°C, the dissolving time is 3min-48h, the standing and degassing temperature is 5-40°C, and the standing and degassing time is 0.05-4h.

9. The method for preparing an in-situ polymerized solid polymer electrolyte according to claim 6, characterized in that: The temperature of the in-situ polymerization is 10-120° C., and the time is 2-72 hours.

10. Use of the polymer electrolyte according to claim 1 in lithium ion batteries or sodium ion batteries.

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