Polyether type polyurethane solid polymer, preparation method thereof and application of polyether type polyurethane solid polymer in solid electrolyte

Abstract

The invention discloses a polyether polyurethane solid polymer, a preparation method thereof and application of the polyether polyurethane solid polymer in a solid electrolyte, and belongs to the technical field of polymer electrolytes and preparation of the polymer electrolytes. The problems that an existing solid polymer electrolyte is low in ionic conductivity and poor in interface stability are solved. According to the invention, polyether amine and cyclic carbonate are subjected to an in-situ polymerization reaction to synthesize a series of polyether polyurethane solid polymer electrolytes with different molecular weights and monomer proportions. The obtained polyether polyurethane solid polymer electrolyte contains rich carbamate groups, hydroxyl groups, fluorine ions and the like, and can form a strong reversible hydrogen bond network, so that the electrolyte has excellent mechanical properties, can be used as a self-supporting electrolyte membrane, and does not need an additional diaphragm. Meanwhile, a large number of dynamic reversible hydrogen bonds also enable the solid polymer electrolyte to have excellent self-healing ability, and can be self-repaired when the battery is damaged by external force in the operation process, so that the structural stability of the solid polymer electrolyte is remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a polyether polyurethane solid-state polymer, a preparation method thereof and an application thereof in solid-state electrolytes, and belongs to the technical field of polymer electrolytes and preparation thereof. BACKGROUND

[0002] The organic electrolyte used in traditional liquid lithium batteries has safety hazards such as flammability, leakage, combustion and explosion risk. Solid-state batteries use solid-state electrolytes to replace traditional organic liquid electrolytes, which generally perform better in terms of thermal stability and mechanical safety, thereby reducing the risk of thermal runaway and related safety accidents to some extent.

[0003] As the core component of all-solid-state batteries, solid-state electrolytes (SSEs) are mainly divided into inorganic ceramic / glass electrolytes and solid-state polymer electrolytes (SPEs). Among them, polyethylene oxide (PEO)-based solid-state polymer electrolytes have been widely studied due to their good interface compatibility with electrodes, excellent flexibility and mature processing technology. However, traditional PEO-based SPEs still have several key technical bottlenecks that need to be solved: first, their room temperature ionic conductivity is generally low (usually 10⁻ 8 ~10⁻ 6 S cm⁻ 1 ), which severely limits the performance of the battery; second, the crystallinity of PEO can cause uneven lithium ion transport during cycling, which may trigger the growth of lithium dendrites, posing a safety hazard; third, the volume change of electrode materials during cycling can cause physical separation of the solid-solid interface, leading to increased interface impedance and rapid capacity decay.

[0004] To overcome the above challenges, researchers have developed an "in-situ polymerization" technology. This technology directly injects a polymerizable precursor liquid solution into the battery and polymerizes it in-situ into a solid-state electrolyte. This method can perfectly fit the electrode surface and form an extremely tight and low-impedance interface contact, significantly improving ion transport efficiency and suppressing lithium dendrites. However, the current in-situ polymerization SPE systems (such as those based on acrylate, vinyl and other monomers) usually form highly cross-linked thermoset polymer networks. Although this network structure provides good mechanical strength and dimensional stability, its three-dimensional network structure is irreversible, which brings new problems: first, under long-term cycling stress and strain, micro-cracks and other damage may occur in the material, and these defects cannot be repaired, which will gradually expand, leading to electrolyte failure; second, the irreversible cross-linked structure makes it difficult to recycle and reprocess the material, which goes against the principles of green chemistry and sustainable development. Once the battery reaches the end of its life, these solid-state electrolytes will become electronic waste, causing resource waste and environmental burden.

[0005] And the existing in-situ method for preparing solid-state polymer electrolyte, the monomer used is mostly olefin compound, usually through free radical polymerization or ion polymerization. This process often needs to introduce initiator or catalyst, but these substances may induce side reactions at the electrode / electrolyte interface, forming unstable interface phase, thereby reducing the overall performance of the battery; in addition, the current electrolyte prepared by in-situ method is mostly linear structure, which has poor mechanical strength, and often needs to rely on the diaphragm to maintain the structural stability, which will lead to the decrease of the energy density of the battery. In order to realize the electrolyte material which has good mechanical properties and is easy to recycle, researchers usually design and build solid-state polymer electrolyte based on physical crosslinking mechanism. Physical crosslinking solid-state polymer electrolyte mainly relies on covalent interaction such as hydrogen bond and van der Waals force to build crosslinking network, rather than permanent linkage of chemical bond. This crosslinking method not only can realize self-healing and structural reversible reconstruction of the material while ensuring high ion transmission efficiency, but also greatly simplifies the processing and recycling process, which is conducive to improving the environmental friendliness. The material for building electrolyte through physical crosslinking is polyether urethane (PEUR). The molecular structure of polyurethane contains repeating unit urethane (-NH-COO-), which can form reversible hydrogen bond, giving the electrolyte self-healing performance and recycling performance. The traditional polyurethane is generally synthesized and prepared by step-by-step growth polycondensation reaction between polyol and isocyanate. The high reactivity of common isocyanate raw materials not only constitutes a certain health risk to the production environment and operating personnel, but also requires that the humidity and temperature of the reaction system must be strictly controlled, otherwise side reactions are easy to occur. In addition, the preparation of polyurethane solid-state electrolyte by traditional process usually needs to react at high temperature and requires catalyst, which may cause side effects of the battery system, and the obtained solid-state electrolyte is generally not prepared in-situ, which leads to poor interface contact performance between the electrolyte and the electrode. These problems limit the development of PEUR solid-state polymer electrolyte.

[0006] Therefore, the development of a PEO-based in-situ polymerization solid-state electrolyte with high ionic conductivity, excellent interface stability, self-healing ability to prolong service life, and recyclable characteristics to realize green and sustainable development has become a key technical breakthrough to promote the commercial application of all-solid-state lithium batteries, which has extremely important scientific research value and huge market application prospect. SUMMARY

[0007] The present application is aimed at the above-mentioned problems existing in the prior art solid-state polymer electrolyte, and provides a polyether urethane solid-state polymer, a preparation method thereof and application thereof in solid-state electrolyte.

[0008] The technical scheme of the present application is as follows: One of the purposes of the present application is to provide a preparation method of polyether urethane solid-state polymer, characterized in that the reaction of polyether amine and cyclic carbonate is carried out at room temperature; The cyclic carbonate is a five-membered ring carbonate or a six-membered ring carbonate.

[0009] Further limitation, when the cyclic carbonate is a five-membered ring carbonate, the reaction general formula of the polyether polyurethane solid polymer is as follows: ; In the formula, R is 、 or ; R3 is H, CH3 or C2H5.

[0010] Further limitation, when the cyclic carbonate is a six-membered ring carbonate, the reaction general formula of the polyether polyurethane solid polymer is as follows: .

[0011] Further limitation, the polyether amine is one or a mixture of several of the following structural formulae: 、 、 、 ; In the formula, x, y, z are integers from 1 to 536; R is H, CH3 or C2H5.

[0012] Further limitation, the polyether amine is one or a mixture of several of D-230, D-400, D-2000, D-4000.

[0013] Further limitation, the polyether amine is one or a mixture of several of ED-600, ED-900, ED-2003, ED-4000.

[0014] Further limitation, it is one or a mixture of several of EDR-148, EDR-400, EDR-600, EDR-800, EDR-1000.

[0015] Further limitation, the structural formula of the five-membered ring carbonate is as follows:

[0016] In the formula, R1 and R2 are selected from H, CH3, CH2OH, Cl, F.

[0017] Further limitation, the structural formula of the six-membered ring carbonate is as follows:

[0018] In the formula, R1 and R3 are selected from H, CH3, CH2OH, Cl, F; R2 is selected from H, CH3, CH2OH, C(CH2CH3)CH2OH, Cl, F.

[0019] The second object of the present application is to provide a polyether polyurethane solid polymer prepared by the above method, which has the structure shown in Formula I or Formula II.

[0020] Formula I In Formula I, R1 and R2 are selected from H, CH3, CH2OH, Cl, and F.

[0021] Formula II In Formula II, R1 and R3 are selected from H, CH3, CH2OH, Cl, and F; and R2 is selected from H, CH3, CH2OH, C(CH2CH3)CH2OH, Cl, and F.

[0022] Further, the polyether polyurethane solid polymer is used as a polymer matrix for preparing a solid electrolyte.

[0023] The third object of the present application is to provide a polyether polyurethane solid polymer electrolyte, which specifically comprises the above-mentioned polyether polyurethane solid polymer, a lithium salt or a sodium salt, and an additive.

[0024] Further, the lithium salt is one or a mixture of several of lithium bis(trifluorosulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluoro(oxalato)borate, lithium bis(oxalato)borate, and lithium trifluorosulfonate.

[0025] Further, the sodium salt is one or a mixture of several of sodium bis(trifluorosulfonyl)imide, sodium bis(fluorosulfonyl)imide, sodium hexafluorophosphate, sodium tetrafluoroborate, sodium perchlorate, sodium difluoro(oxalato)borate, and sodium trifluorosulfonate.

[0026] Further, the additive is an inorganic additive and an organic additive.

[0027] Further, the inorganic additive is one or a mixture of several of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, zinc oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomite, montmorillonite, kaolin, lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium germanium phosphorus sulfur, lithium phosphorus sulfur chloride, lithium phosphorus sulfur bromide, lithium borohydride, lithium nitride, lithium borate, lithium bismuth oxide, or lithium phosphorus oxynitride.

[0028] More specifically, the organic additive is one or a mixture of several of plastic crystal succinonitrile, low molecular weight polyethylene glycol, trifluoroethanol, difluoroethanol, hexafluoropropanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyltrifluoroacetamide, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, propyl phosphonate pentafluoride, ethyl phosphonate hexafluoride, N-methyl pyrrolidone, tris(pentafluorophenyl)borane, 3-(trimethylsilyl)phenylboronic acid, boronized polyethylene glycol, imidazolium ionic liquid, pyridinium ionic liquid, piperidinium ionic liquid, and pyrrolidinium ionic liquid.

[0029] The fourth object of the present application provides a preparation method of the above-mentioned polyether polyurethane solid-state polymer electrolyte, which comprises dissolving a lithium salt or a sodium salt, an additive, and a polyether amine in a cyclic carbonate, stirring until uniform, and then performing a standing defoaming treatment to obtain a precursor solution, and then performing a standing solidification treatment at a temperature of -30 to 100°C to obtain the polyether polyurethane solid-state polymer electrolyte.

[0030] More specifically, the molar ratio of the amine group in the polyether amine to the cyclic carbonate is 1:(0.5-4), the amount of the lithium salt or the sodium salt is 0.2-300% of the total mass of the polyether amine and the cyclic carbonate, and the amount of the additive is 0.2-300% of the total mass of the polyether amine and the cyclic carbonate.

[0031] More specifically, the standing defoaming treatment time is 0.05-4h.

[0032] More specifically, the standing solidification time at room temperature is 0.5-72h.

[0033] The fifth object of the present application provides a preparation method of a solid-state battery, which comprises dissolving a lithium salt or a sodium salt, an additive, and a polyether amine in a cyclic carbonate, stirring until uniform, and then performing a standing defoaming treatment to obtain a precursor solution, and then uniformly coating the precursor solution on the surface of a negative electrode, and then covering a positive electrode on the surface of the electrolyte precursor solution, and then performing a standing solidification treatment at a temperature of -30 to 100°C to obtain the solid-state battery.

[0034] More specifically, the standing defoaming treatment time is 0.05-4h.

[0035] More specifically, the standing solidification time at room temperature is 0.5-72h.

[0036] The sixth object of the present application provides a recycling method of the solid-state battery obtained by the above-mentioned preparation method, which comprises disassembling the waste solid-state battery to obtain an electrode adhered with an electrolyte, cutting the electrode into small pieces, placing the small pieces in a solvent, heating and stirring, filtering to remove the electrode particles to obtain a clear electrolyte solution, pouring the solution into a mold, air-drying, vacuum-drying, and obtaining the recycled solid-state electrolyte.

[0037] Further limited, the solvent is one or a mixture of several of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,4-dioxane, tetrahydrofuran, acetonitrile, ethyl acetate.

[0038] Further limited, the heating and stirring temperature is 30-90°C, and the time is 1-72h.

[0039] Further limited, the air drying is carried out in a blast oven, the air drying temperature is 40-90°C, and the time is 2-72h.

[0040] Further limited, the vacuum drying temperature is 40-90°C, the pressure is -0.01-0.1MPa, and the time is 1-48h.

[0041] Further limited, the recovered solid electrolyte can be used to continue assembling the solid-state battery.

[0042] Beneficial effects: The application utilizes in-situ polymerization of polyether amine and cyclic carbonate to synthesize a series of polyether-type polyurethane solid-state polymer electrolytes with different molecular weights and monomer ratios. Compared with the prior art, the application has the following advantages: (1) The application uses in-situ polymerization to prepare the solid-state polymer electrolyte. The reaction is spontaneous and does not require the introduction of catalysts and initiators which may have side effects on the battery system, effectively improving the compatibility and contact between the electrolyte and the electrode interface. The obtained polyether-type polyurethane solid-state polymer electrolyte contains abundant urethane groups, hydroxyl groups and fluoride ions, etc., and can form a strong reversible hydrogen bond network. This physical crosslinking network structure through non-covalent bonding endows the electrolyte with excellent mechanical properties, enabling it to be used as a self-supporting electrolyte membrane without additional separators. At the same time, the large number of dynamic reversible hydrogen bonds in this structure also endow the solid-state polymer electrolyte with excellent self-healing ability, which can spontaneously repair when damaged by external force during battery operation, thereby significantly improving its structural stability.

[0043] (2) The application uses cyclic carbonate as a polymerization monomer, which also acts as a common film-forming additive. It can form a stable interface layer at the interface, has the dual functions of reaction monomer and interface modifier, and synergistically enhances the electrochemical performance, providing an effective guarantee for the improvement of the comprehensive performance of the battery.

[0044] (3) The solid-state polymer electrolyte based on the physical crosslinking mechanism constructed by the application has recyclable performance, which not only helps to realize efficient use of resources and reduce environmental load, but also provides a new way for sustainable design and economic benefit improvement of the battery system. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 Impedance plot of solid state polymer electrolyte prepared for example 2 at room temperature; Figure 2 Impedance plot of solid state polymer electrolyte prepared for example 2 at room temperature; Figure 3 Self-healing performance characterization plot of solid state polymer electrolyte prepared for example 2 at room temperature; Figure 4 Full cell cycling performance of assembled battery with solid state polymer electrolyte prepared for example 2 at room temperature; Figure 5 Recycling process of solid state polymer electrolyte prepared for example 2. DETAILED DESCRIPTION

[0046] In order to make the above objectives, features and advantages of the present application more apparent, specific embodiments of the present application will be described in detail below with reference to the embodiments of the present application.

[0047] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application can be practiced without the specific details given herein, that the present application can be practiced with other than the described implementations, and that variations from the particular examples given can be made and practiced within the scope of the present application. Accordingly, the particular embodiments of the present application described are presented for purposes of illustration and description, and not limitation.

[0048] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an embodiment that is separate or alternative to other embodiments.

[0049] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained by commercial channels by those skilled in the art.

[0050] Example 1: Take 0.739 g of lithium bisfluorosulfonylimide and dissolve it in fluorinated ethylene carbonate (0.353 g, 3.33 mmol), stir for 30 min until completely dissolved, then add polyetheramine D-2000 (3.34 g, 1.67 mmol), stir for 20 min until uniform, then obtain a transparent precursor solution. After vacuum degassing the electrolyte precursor solution for 5 min, uniformly coat the surface of the negative electrode, then gently cover the positive electrode on the surface of the electrolyte precursor solution, and let stand at room temperature for 24 h, to obtain an in-situ polymerized solid state polymer electrolyte between the positive electrode and the negative electrode.

[0051] The ion conductivity of the above solid-state polymer electrolyte was tested. Specifically, 200 μL of the above precursor solution was uniformly coated on the surface of a circular stainless steel negative electrode with a diameter of 1.56 cm and a thickness of 0.05 cm, and then a circular stainless steel positive electrode with a diameter of 1.56 cm and a thickness of 0.05 cm was gently covered on the surface of the electrolyte precursor solution, which was then left to stand at room temperature for 24 h, and then assembled into a R2023 button block cell of stainless steel sheet / SPE / stainless steel sheet.

[0052] The impedance R of the polymerized solid-state polymer electrolyte was characterized by electrochemical impedance spectroscopy under the conditions of a test frequency range of 100 mHz-10 MHz and a scanning speed of 10 mV / s. Then the ion conductivity of the solid-state polymer electrolyte was calculated by the following formula: σ=L / AR In the formula, L is the thickness of the electrolyte, A is the area of the stainless steel sheet, and R is the impedance of the electrolyte obtained by testing.

[0053] The ion conductivity of the solid-state polymer electrolyte at room temperature was obtained by testing and calculation to be 6.8 x 10 -5 S / cm.

[0054] Example 2: 0.217 g of lithium bis-trifluorosulfonylimide and 0.325 g of succindinitrile were dissolved in fluorinated ethylene carbonate (0.353 g, 3.33 mmol), and after stirring for 60 min until complete dissolution, 1 g of polyetheramine ED-600 (1.67 mmol) was added, and after stirring for 10 min until uniform, a transparent precursor solution was obtained. The electrolyte precursor solution was vacuum degassed for 10 min, then uniformly coated and left to stand at room temperature for 12 h to obtain a solid-state polymer electrolyte polymerized in situ.

[0055] Figure 1 The solid-state polymer electrolyte prepared in this example had a uniform and dense structure and excellent flexibility, as shown by the actual pictures of the solid-state polymer electrolyte in the flat and bent states.

[0056] The ion conductivity of the above solid-state polymer electrolyte was tested (the test method and conditions were the same as in Example 1), and the impedance spectrum of the solid-state polymer electrolyte at room temperature is shown in Figure 2 As shown by the figure, the solid-state polymer electrolyte had a low impedance value at room temperature, specifically 146 ohm. Further calculation showed that the ion conductivity of the solid-state polymer electrolyte at room temperature was 2.16 x 10 -4 S / cm.

[0057] The self-healing performance of the solid-state polymer electrolyte obtained in this example was characterized, as shown in Figure 3As shown, the solid-state polymer electrolyte was first cut into two parts, and then spliced with each other. After lapping, the electrolyte was left to stand at room temperature for 10 min, and the cracks were basically closed and could bear its own weight. Even in the pulling test, no cracks appeared again, which fully proved the excellent self-healing ability of the electrolyte. When subjected to external mechanical stress or deformation damage, the electrolyte can automatically repair micro-cracks and broken parts, thereby prolonging the service life of the material and improving the stability of the long-term operation of the equipment.

[0058] A full battery was assembled using the above solid-state polymer electrolyte. Specifically, 200 μL of the above precursor solution was uniformly coated on the surface of a circular lithium metal negative electrode with a diameter of 1.4 cm and a thickness of 0.04 cm. Then, a circular lithium iron phosphate positive electrode with a diameter of 1.2 cm and a thickness of 0.002 cm was gently covered on the surface of the electrolyte precursor solution. The assembly was left to stand at room temperature for 24 h, and then a full battery was assembled. The cycle performance of the battery was characterized, and the test results are shown in Figure 4 The results show that after 150 cycles at a current density of 0.2 C, the capacity retention rate reaches 93.3%, and the coulombic efficiency is as high as 99.7%.

[0059] The assembled full battery was disassembled, crushed, dissolved in DMSO solvent, and heated and stirred at 60°C for 12 h. The electrode particles were removed by filtration to obtain a clear electrolyte solution. After casting the solution, it was placed in a blast oven at 80°C for air drying for 12 h, and then placed in a vacuum drying box with a pressure of -0.1 MPa and dried at 80°C for 12 h. The recovered solid-state electrolyte was obtained, which can be used to assemble a battery, as shown in Figure 5 .

[0060] The above recovered electrolyte has an ionic conductivity of 6.97 x 10 -5 S / cm at room temperature. The recovered electrolyte was used to assemble a battery (the assembly method was the same as above), and the performance of the battery was tested. The results show that the assembled battery can successfully run, and after 90 cycles at a current density of 0.2 C, the battery can still provide a discharge specific capacity of 105.1 mAh / g, with a capacity retention rate of 96.7%, showing excellent cycle stability.

[0061] Example 3: Take 0.217 g of lithium bis-trifluorosulfonimide and 0.15 g of lithium difluoro(oxalato)borate and dissolve in propylene carbonate (0.170 g, 1.67 mmol), stir for 60 min to dissolve completely, then add polyetheramine EDR-1000 (1.67 g, 1.67 mmol), stir for 10 min to get a transparent precursor solution. The electrolyte precursor solution is vacuum degassed for 2 min, then evenly coated on the surface of the positive electrode, and then the negative electrode is gently covered on the surface of the electrolyte precursor solution, and left to stand at room temperature for 6 h, to obtain an in-situ polymerized solid-state polymer electrolyte between the positive electrode and the negative electrode.

[0062] The solid-state polymer electrolyte was tested to have a room temperature ionic conductivity of 1.09 x 10 -4 S / cm.

[0063] Example 4: Take 0.486 g of lithium bis-trifluorosulfonimide and 0.3 g of lithium lanthanum zirconium oxide and dissolve in polyetheramine ED-900 (1.67 g, 1.67 mmol), stir to uniform, then add fluoroethylene carbonate (0.531 g, 5.01 mmol), stir for 60 min to get a precursor solution. The electrolyte precursor solution is vacuum degassed for 6 min, then evenly coated on the surface of the positive electrode, and then the negative electrode is gently covered on the surface of the electrolyte precursor solution, and left to stand at room temperature for 48 h, to obtain an in-situ polymerized solid-state polymer electrolyte between the positive electrode and the negative electrode.

[0064] The solid-state polymer electrolyte was tested to have a room temperature ionic conductivity of 3.28 x 10 -4 S / cm.

[0065] Example 5: After heating ED-2003 (3.34 g, 1.67 mmol) to complete melting at 46 °C, take 0.486 g of sodium bis-trifluorosulfonimide and dissolve it in ED-2003, and stir for 10 min at this temperature to dissolve completely, then add fluoroethylene carbonate (0.708 g, 6.68 mmol), stir for 25 min to get a precursor solution. The electrolyte precursor solution is vacuum degassed for 15 min, then evenly coated on the surface of the positive electrode, and then the negative electrode is gently covered on the surface of the electrolyte precursor solution, and left to stand at room temperature for 60 h, to obtain an in-situ polymerized solid-state polymer electrolyte between the positive electrode and the negative electrode.

[0066] The solid-state polymer electrolyte was tested to have a room temperature ionic conductivity of 5.98 x 10 -4 S / cm.

[0067] The above merely describes preferred embodiments of the present application, and the skilled in the art can make appropriate changes and modifications to the above embodiments, and the present application is not limited to the above specific embodiments. Some modifications and changes of the present application should fall within the protection scope of the claims of the present application.

Claims

1. A method for preparing a polyether-type polyurethane solid polymer, characterized in that, It is obtained by reacting polyetheramine and cyclic carbonate at room temperature; The cyclic carbonate is a five-membered or six-membered cyclic carbonate.

2. The preparation method according to claim 1, characterized in that, Polyetheramines are one or a mixture of the following structural formulas; 、 、 、 ； In the formula, x, y, and z are integers from 1 to 536; R is H, CH3, or C2H5.

3. The preparation method according to claim 1 or 2, characterized in that, The polyetheramine is one or a mixture of several of the following: D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, ED-4000, EDR-148, EDR-400, EDR-600, EDR-800, and EDR-1000.

4. The preparation method according to claim 1, characterized in that, The structural formula of the five-membered ring carbonate is as follows: In the formula, R1 and R2 are selected from H, CH3, CH2OH, Cl, and F; The structural formula of a six-membered ring carbonate is as follows: In the formula, R1 and R3 are selected from H, CH3, CH2OH, Cl, and F; R2 is selected from H, CH3, CH2OH, C(CH2CH3)CH2OH, Cl, and F.

5. A polyether-type polyurethane solid polymer obtained by the preparation method according to any one of claims 1 to 4, characterized in that, The structure of polyether-type polyurethane solid polymers is shown in Formula I or Formula II: Formula I In Formula I, R1 and R2 are selected from H, CH3, CH2OH, Cl, and F; Formula II In Formula II, R1 and R3 are selected from H, CH3, CH2OH, Cl, and F; R2 is selected from H, CH3, CH2OH, C(CH2CH3)CH2OH, Cl, and F. The polyether-type polyurethane solid polymer is used as the polymer matrix for preparing solid electrolytes.

6. A polyether-type polyurethane solid polymer electrolyte, characterized in that, It includes the polyether-type polyurethane solid polymer as described in claim 5, lithium salt or sodium salt, and additives.

7. A method for preparing the polyether-type polyurethane solid polymer electrolyte according to claim 6, characterized in that, Lithium or sodium salt, additives and polyetheramine are dissolved in cyclic carbonate, stirred evenly and then subjected to static degassing treatment to obtain a precursor solution. The precursor solution is then allowed to stand and solidify at a temperature of -30~100℃. After complete solidification, a polyether-type polyurethane solid polymer electrolyte is obtained.

8. The preparation method according to claim 7, characterized in that, The molar ratio of amino groups to cyclic carbonates in the polyetheramine is 1:(0.5~4), the amount of lithium salt or sodium salt is 0.2-300% of the total mass of polyetheramine and cyclic carbonates, and the amount of additives is 0.2-300% of the total mass of polyetheramine and cyclic carbonates.

9. A method for preparing a solid-state battery, characterized in that, The precursor solution described in claim 7 is uniformly coated onto the surface of the negative electrode, and then the positive electrode is covered onto the surface of the electrolyte precursor solution. The mixture is then allowed to stand and solidify at a temperature of -30 to 100°C, and then encapsulated to obtain a solid-state battery.

10. A method for recycling a solid-state battery obtained by the preparation method of claim 9, characterized in that, Discarded solid-state batteries are disassembled to obtain electrodes with adhered electrolyte. These electrodes are cut into pieces, placed in a solvent, heated and stirred, and filtered to remove electrode particles, resulting in a clear electrolyte solution. The solution is then cast into a mold, air-dried, and vacuum-dried to obtain the recycled solid electrolyte.

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