Polymer containing polymetallic-oxygen clusters and its preparation method and application

Abstract

The present invention discloses a polymer containing polymetallic oxygen clusters, a preparation method thereof, and an application thereof. The polymer is a polyurea-type high molecular polymer formed by reacting functional polymetallic oxygen clusters as crosslinking points with polyetheramine and polyisocyanate or diisothiocyanate in a certain ratio. The polymer has the advantages of simple synthesis, non-toxicity, easy processing and molding, good thermal stability, mechanical properties, and good flame retardancy. The polymer is applied as an all-solid-state electrolyte, which has high ionic conductivity, high ion migration number and wide electrochemical stability window at room temperature, and the lithium ion battery prepared with the polymer has excellent battery performance. The all-solid-state electrolyte prepared based on the polymer of the present invention can effectively suppress lithium dendrites, improve the cycle stability and lithium ion mobility of the battery, and at the same time has good flame retardancy, thereby improving the safety of the battery.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium batteries, and in particular to a polymer containing polyoxometallic acid clusters and a preparation method thereof, as well as applications of the polymer in all-solid-state electrolytes and all-solid-state lithium batteries. Background Art

[0002] Lithium batteries have attracted widespread attention due to their advantages such as light weight, low price, high energy density, low charge loss, long life, high number of charge and discharge cycles, and no memory effect, and have been widely used in portable electronic devices, electric vehicles and other fields. Currently, traditional lithium-ion batteries use organic liquid electrolytes such as carbonates, carboxylates and ethers. Although liquid electrolytes can provide high ionic conductivity and good interfacial contact, they cannot be safely used in metallic lithium systems. Lithium ions have problems such as low migration number, easy leakage, volatility, flammability, and poor safety. Such batteries require shells made of materials such as aluminum and steel, which to some extent reduces the energy density of the battery and restricts the development of high-performance lithium-ion batteries.

[0003] Gel polymer electrolytes are composed of polymer matrix, plasticizer and lithium salt. The polymer matrix serves as the skeleton of the entire electrolyte and supports the entire electrolyte membrane. Although gel polymer electrolytes have good mechanical properties, high electrochemical window and good chemical stability, their room temperature conductivity can usually reach 10 -4 Scm -1 However, the defects caused by the porous structure and liquid absorption destroy the mechanical strength of the polymer matrix, affecting the processing performance and the ability to inhibit lithium dendrites, and its safety performance cannot be guaranteed.

[0004] With the rapid advancement of electronic technology, more and more electronic devices are becoming bendable and wearable, leading to a rapidly increasing demand for flexible batteries and, consequently, higher safety requirements. To address the safety risks of liquid electrolyte lithium-ion batteries and gel polymer electrolytes, all-solid-state lithium batteries (ALLSLBs) using all-solid-state electrolytes are a key development direction for next-generation lithium batteries. Solid polymer electrolytes are a novel type of electrolyte composed of a polymer matrix and a metal salt. They contain no organic solvents and are immune to safety issues such as leakage. Furthermore, the polymer itself exhibits excellent flexibility, which mitigates the volume change of the active material during charge and discharge, significantly improving the battery's cycle life and safety. Polymer electrolytes also offer advantages such as light weight, ease of processing, and suitability for large-scale production. They are used in most flexible ALLSLBs and are therefore attracting increasing attention from research institutions worldwide. Solid electrolytes can be categorized into three main categories based on their composition: inorganic solid electrolytes, polymer solid electrolytes, and composite solid electrolytes. Inorganic solid electrolytes offer advantages such as high room-temperature ionic conductivity, mechanical strength, and electrochemical stability, but they present challenges related to the high impedance electrode / electrolyte interface.

[0005] Currently, the polymer solid electrolyte systems that are widely studied and used include polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polyvinylidene fluoride (PVDF). PEO has high crystallinity at room temperature, low ionic conductivity, and poor mechanical strength, making it unsuitable for direct use as an electrolyte. Although PAN offers advantages such as simple synthesis, good stability, strong heat resistance, and good flame retardancy, it can cause severe passivation reactions on lithium electrodes when in contact with PAN-based polymer electrolytes, thus affecting the battery's cycling performance and safety. The internal resistance of lithium-ion batteries gradually increases with increasing charge and discharge cycles. PMMA has the disadvantages of low crystallinity, resulting in brittle films, poor flexibility, and poor mechanical strength. PVDF offers excellent thermal and electrochemical stability and film-forming properties, but its homopolymer structure results in a high intramolecular crystallinity (65%-78%), which is detrimental to ionic conductivity. While new cross-linked network polymer electrolytes offer high ionic conductivity and mechanical strength, they suffer from limited mobility of cross-linked polymer chains, reduced ion conductivity, and difficulty processing cross-linked polymers, hindering large-scale device production. The complex production process of new dendrimer-based solid electrolytes also limits their application.

[0006] Although solid-state composite polymer electrolytes can improve certain properties of pure polymers, such as conductivity and flame retardancy, there are still problems such as poor compatibility between additives and polymers, poor interface stability, and difficulty in post-processing.

[0007] The ideal lithium battery polymer electrolyte matrix should have the following characteristics:

[0008] 1. The polymer matrix has a high dielectric constant, and the chain segments contain polar groups that can complex with metal ions, such as: -O-, =O, -S-, -N-, -P-, -C=O, etc. These groups can dissolve lithium salts and form a polymer / salt composite system;

[0009] 2. The polymer can provide a channel for the migration of ions. According to the conductive mechanism of polymer electrolytes, the polymer should have more amorphous regions and better flexibility;

[0010] 3. The polymer has a wide electrochemical stability window;

[0011] 4. The polymer itself has good mechanical properties, which can inhibit the growth of lithium dendrites and give the battery better processing performance, facilitating large-scale production;

[0012] 5. Excellent chemical and thermal stability. The polymer electrolyte should be inert to battery components. Excellent thermal stability ensures safe use of the battery even in situations such as short circuit and overcharge.

[0013] Currently reported polymer electrolytes still have problems such as low room temperature ionic conductivity and narrow electrochemical window. Therefore, the development of polymer solid electrolytes with new structures is of great significance to improving the overall performance of batteries. Summary of the Invention

[0014] To address the above issues, the present invention provides a polyurea polymer constructed using metal coordination and containing functional multimetal-oxygen clusters as crosslinking points, which is reacted with polyetheramine and polyisocyanate or diisothiocyanate in a specific ratio, as well as its preparation method and application. This polymer is simple to synthesize, easy to process and shape, non-toxic and harmless, and has excellent thermal stability, mechanical properties, and flame retardancy. When used as an all-solid-state electrolyte, this polymer exhibits high ionic conductivity, a high ion transference number, and a wide electrochemical stability window at room temperature. Lithium-ion batteries prepared using this polymer exhibit excellent battery performance.

[0015] To achieve the above object, the present invention adopts the following technical solutions:

[0016] A polymer containing a polymetallic-oxygen cluster, wherein the structure of the repeating unit of the polymer is: M as a center connects n L segments;

[0017] in,

[0018] n is an integer from 1 to 18;

[0019] M is selected from [X 1] n [Mo6O 19 ]、[X 1 ] n [W6O 19 ]、[X 1 ] n [Nd6O 19 ]、[X 1 ] n [Ta6O 19 ]、[X 1 ] n [Mo7O 24 ]、[X 1 ] n [V3O9]、[X 1 ] n [V4O 12 ] or [X 1 ] n [V 10 O 18 ];

[0020] L is

[0021] Among them, X 1 With X 2 Direct connection;

[0022] X 1 Selected from or -(CH2) m -, wherein R is independently selected from a hydrogen atom, a halogen or a C1-C3 alkyl group; m is an integer from 1 to 5;

[0023] X 2 、X 5 are independently selected from -NH-, an O atom or a S atom;

[0024] X 3 is an O atom or a S atom;

[0025] X 4 It is a spacer group between -NCO in polyisocyanate or a spacer group between -NCS in diisothiocyanate;

[0026] X 6 It is a spacer group between terminal amino groups, between terminal thiol groups or between terminal hydroxyl groups in a polymer with multiple terminals of amino groups, thiol groups or hydroxyl groups.

[0027] M represents a polymetallic-oxygen cluster compound, serving as a crosslinking point within the polymer to connect multiple polymer chains. The number of polymer chains that can be connected, i.e., n, corresponds to the number of active sites within the oxygen cluster structure. Polyisocyanate, diisothiocyanate, polyamino-terminated, thiol-terminated, or hydroxyl-terminated polymers must contain at least two active groups (-NCO, -NCS, -NH2, -SH, -OH). When the number of active groups exceeds two, crosslinks other than the M crosslinks can form between polymer chains.

[0028] Preferably, X 4 Selected from 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, toluene-2,4-diisocyanate, dimethyl biphenyl diisocyanate, o-phenylenediisocyanate, naphthalene diisocyanate, m-phenylenediisocyanate, polyhexamethylene diisocyanate, 3,3'-dichlorobiphenyl diisocyanate A spacer group between -NCO in benzene-4,4'-diisocyanate, L-lysine diisocyanate or hexamethylene triisocyanate, or 1,3,5-triisocyanate benzene; or a spacer group between -NCS in 1,4-cyclohexane diisocyanate, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, or p-phenylene diisocyanate.

[0029] Preferably, X 6 The spacer is selected from the spacer groups between amino groups in polyetheramine D230, polyetheramine D400, polyetheramine D600, polyetheramine D1000, polyetheramine D2000, and polyetheramine D4000, or the spacer groups between hydroxyl groups in PEG200-20000, or the spacer groups between sulfhydryl groups in thiol-terminated PEG200-20000, or the spacer groups between amino groups in amino-terminated PDMS800-25000, or the spacer groups between hydroxyl groups in hydroxyl-terminated PDMS800-25000, or the spacer groups between hydroxyl groups in thiol-terminated PDMS800-25000.

[0030] Preferably, the repeating units of the polymer containing polymetallic-oxo clusters are selected from:

[0031]

[0032]

[0033]

[0034]

[0035] Another object of the present invention is to provide a method for preparing the above-mentioned polymer containing polymetallic-oxo clusters, comprising the following steps:

[0036] In an organic solvent, M(Y) n , a polymer with multiple amino, thiol or hydroxyl ends and polyisocyanate or diisothiocyanate are mixed evenly and reacted at 0°C to 100°C for 0.5 to 24h to obtain the product.

[0037] Among them, M(Y) n wherein M and n are the same as defined above, and Y is one of -NH2, -OH or -SH.

[0038] Preferably, M(Y) n The present invention is selected from a fatty chain platinum complex containing -NH2, -OH or -SH active groups, substituted or unsubstituted benzene, biphenyl or anthracene coordinated molybdenum tetraamine, substituted or unsubstituted benzene, biphenyl or anthracene coordinated molybdenum tetraphenol, substituted or unsubstituted benzene, biphenyl or anthracene coordinated molybdenum tetrathiophenol, substituted or unsubstituted benzene, biphenyl or anthracene coordinated titanium hexamine, substituted or unsubstituted benzene, biphenyl or anthracene coordinated titanium hexiophenol, substituted or unsubstituted benzene, biphenyl or anthracene coordinated titanium hexiothiophenol or substituted or unsubstituted benzene, biphenyl or anthracene coordinated molybdenum hexamine, more preferably substituted or unsubstituted benzene, biphenyl or anthracene coordinated molybdenum tetraamine. More preferably, benzene coordinated molybdenum tetraamine.

[0039] Preferably, the polymer having multiple ends of amino, thiol or hydroxyl groups is selected from polyetheramine D230, polyetheramine D400, polyetheramine D600, polyetheramine D1000, polyetheramine D2000, polyetheramine D4000, PEG200-20000, thiol-terminated PEG200-20000, amino-terminated PDMS800-25000, hydroxyl-terminated PDMS800-25000, thiol-terminated PDMS800-25000, preferably polyetheramine D2000.

[0040] Preferably, the organic solvent is selected from one or more of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, dimethyl diethyl ether or diethyl ether, preferably N,N-dimethylformamide. The organic solvent does not contain water.

[0041] Preferably, the polyisocyanate is selected from 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, toluene-2,4-diisocyanate, dimethylbiphenyl diisocyanate, o-phenylenediisocyanate, naphthalene diisocyanate, m-phenylene diisocyanate, polyhexamethylene diisocyanate, 3,3'-dichlorobiphenyl-4,4'-diisocyanate, L-lysine diisocyanate or hexamethylene triisocyanate, 1,3,5-triisocyanate benzene, preferably isophorone diisocyanate.

[0042] Preferably, the diisocyanate is selected from 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate or p-phenylene diisocyanate, preferably isophorone diisocyanate.

[0043] Preferably, M(Y) n The molar ratio of the polymer having amino, thiol or hydroxyl groups at the ends to the polyisocyanate or diisothiocyanate is 1:(0.1-20):(0.1-50)

[0044] In one preferred embodiment, the molar ratio of substituted or unsubstituted benzene, biphenyl or anthracene molybdenum tetraamine, polyetheramine D2000 and isophorone diisocyanate is 1:1:3.

[0045] The present invention also provides the use of the above-mentioned polymer containing polymetallic-oxygen clusters in the preparation of an all-solid-state electrolyte.

[0046] The preparation method of the all-solid-state electrolyte comprises the following steps:

[0047] The polymer containing the polymetallic-oxygen clusters is dissolved in an organic solvent, lithium salt is added and mixed evenly, and then the solvent is removed under a protective gas atmosphere to obtain an all-solid-state polymer electrolyte.

[0048] Preferably, the organic solvent is one or more of acetone, tetrahydrofuran, dimethyl diethyl ether, N,N-dimethylformamide, acetonitrile, ethanol, methanol, N-methylpyrrolidone, dimethyl sulfoxide, ethyl acetate or dichloromethane, preferably tetrahydrofuran.

[0049] Preferably, the lithium salt is one or more of lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl imide), lithium bis(oxalatoborate), lithium oxalatodifluoroborate or lithium malonate oxalatoborate, preferably lithium bis(trifluoromethanesulfonyl imide).

[0050] Preferably, the method for uniform mixing is ultrasonic mixing. More preferably, the time for ultrasonic mixing is 5 minutes to 3 hours, preferably 30 minutes.

[0051] Preferably, the ratio of the polymetallic-oxygen cluster-containing polymer, lithium salt and solvent is 1 g:(0.1-100) g:(1-500 mL), more preferably 1 g:2 g:15 mL.

[0052] Preferably, the protective atmosphere is a nitrogen or argon atmosphere, preferably a nitrogen atmosphere.

[0053] Preferably, the method for removing the solvent is heating or vacuum drying, preferably heating. More preferably, the heating temperature is 30 to 120° C., more preferably 80° C., and the heating time is 1 to 24 hours, more preferably 8 hours.

[0054] The present invention also provides the use of the above-mentioned all-solid-state polymer electrolyte in the preparation of an all-solid-state lithium battery.

[0055] The preparation method of the all-solid-state lithium battery comprises the following steps:

[0056] The positive electrode, the all-solid polymer electrolyte and the negative electrode are stacked in sequence to obtain;

[0057] The all-solid-state polymer electrolyte is in the form of a membrane.

[0058] Preferably, the thickness of the film is 0.1 to 500 μm, more preferably 10 μm.

[0059] In order to solve the problem that the PEO system has high crystallinity and poor mechanical strength at room temperature, the polymer containing polymetallic-oxygen clusters of the present invention has low crystallinity and high mechanical strength.

[0060] To address the problem that cross-linked PEO systems have hindered polymer chain movement after cross-linking, making them difficult to process and apply on a large scale, the polymer containing polymetallic-oxygen clusters of the present invention uses polymetallic-oxygen clusters bound by coordination bonds as cross-linking points, exhibiting good mechanical properties and high ionic conductivity. The dynamic introduction of coordination bonds also facilitates the processing and large-scale application of the material.

[0061] In order to solve the problem that the PEO system is easily flammable, the present invention provides a polymetallic-oxygen cluster-containing polymer having amino groups formed by coordination bonds to form an intrinsic polymetallic-oxygen cluster flame retardant material, which has good flame retardancy.

[0062] In order to solve the problem of low ionic conductivity of PEO system at room temperature, the present invention adopts a polymetallic-oxygen cluster-containing polymer, which uses amino-containing molybdenum, titanium and other metal-oxygen clusters as crosslinking points formed by coordination bonds, and a coordination polyurea / polyurethane material formed by polyetheramine or polyethylene glycol and polyisocyanate or diisothiocyanate. The material has a low glass transition temperature (about -50°C). At the same time, the introduction of amino-containing molybdenum, titanium and other metal-oxygen cluster crosslinking points can selectively complex with anions, restrict the movement of anions, and improve the Li + migration number, reducing concentration polarization during battery charge and discharge, lowering electrode overpotential, and improving battery energy density.

[0063] In view of the interface compatibility problem between polymers and doping materials in composite polymer all-solid-state electrolytes, the intrinsic functional complex of the polymer containing multi-metal-oxygen clusters of the present invention, which is cross-linked by coordination bonds, can effectively improve the contact between the solid polymer electrolyte and the electrode, greatly reduce the contact impedance, and improve the cycle performance of the all-solid-state lithium battery.

[0064] With the widespread use of lithium batteries in portable electronic devices and electric vehicles, they face increasingly severe challenges in energy density and safety. All-solid-state lithium batteries using solid electrolytes made from polymers containing polymetallic-oxygen clusters of the present invention can well solve the above problems.

[0065] Compared with the existing technology, the polymer containing polymetallic-oxygen clusters of the present invention adopts the functional complex molybdenum tetraamine as a cross-linking point, providing the material with excellent mechanical properties and good repairability. At the same time, the introduction of molybdenum ions enhances the ionic conductivity and electrochemical stability of the material, and makes the material have good flame retardant properties. The polymer containing polymetallic-oxygen clusters of the present invention has good compatibility with lithium salts and excellent film-forming properties. The polymer containing polymetallic-oxygen clusters of the present invention contains polyetheramine blocks and has low crystallinity, which can make the all-solid-state polymer electrolyte have higher ionic conductivity, Li ion migration number and wide electrochemical window. At the same time, the all-solid-state polymer electrolyte prepared by the present invention has good interface stability and long cycle life during the charge and discharge process, and does not have the safety problems existing in liquid electrolytes, and has excellent safety performance. The preparation method of the all-solid-state lithium battery prepared by the present invention is simple, the conditions are controllable, and it is easy to implement. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is an infrared spectrum of the polymer containing polymetallic-oxygen clusters prepared in Example 1 of the present invention.

[0067] Figure 2 The polymer containing polymetallic oxygen clusters prepared in Example 1 is 1 HNMR.

[0068] Figure 3 This is a thermogravimetric analysis chart of the polymer containing polymetallic-oxygen clusters prepared in Example 1 of the present invention.

[0069] Figure 4 This is the DSC graph of the polymer containing polymetallic oxygen clusters prepared in Example 1 of the present invention.

[0070] Figure 5 Schematic diagram of the structure of the all-solid-state lithium battery.

[0071] Figure 6 This is the AC impedance diagram of the all-solid-state lithium battery prepared in Example 34.

[0072] Figure 7 This is the charge and discharge data diagram of the all-solid-state electrolyte lithium-lithium symmetric battery prepared in Example 34.

[0073] Figure 8 This is a full-battery charge and discharge data diagram of the all-solid-state lithium battery prepared in Example 34. DETAILED DESCRIPTION

[0074] Example 1

[0075] Under argon protection, 0.37 g (0.5 mmol, 0.1 eq) of phenyl molybdenum tetraamine, 1.15 g (5 mmol, 1 eq) of D-230, and 1.33 g (6 mmol, 1.2 eq) of isophorone diisocyanate (IPDI) were added to a two-necked flask containing 20 ml of anhydrous DMF (50 mL). The mixture was then heated in an oil bath at 60° C. for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The mixture was then dried in a vacuum drying oven at 110° C. for 48 h to obtain polymer 1. The polymer was subjected to Fourier transform infrared spectroscopy (FTIR) analysis. Figure 1 )、thermal stability ( Figure 2 ) and phase transition temperature ( Figure 3 )test.

[0076] Example 2

[0077] Under argon protection, 0.37 g (0.5 mmol, 0.1 eq) of phenylmolybdenum tetraamine, 5.00 g (5 mmol, 1 eq) of D-1000, and 1.33 g (6 mmol, 1.2 eq) of IPDI were added to a two-necked flask containing 20 ml of anhydrous DMF (50 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 2 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain polymer 2. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0078] Example 3

[0079] Under argon protection, 0.37 g (0.5 mmol, 0.1 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.33 g (6 mmol, 1.2 eq) of IPDI were added to a two-necked flask containing 50 ml of anhydrous DMF (100 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 3 was then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 3. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0080] Example 4

[0081] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 100 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, the DMF was removed by rotary evaporation, and the polymer was dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 4. The polymer was then subjected to Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests.

[0082] Example 5

[0083] Under argon protection, 1.87 g (2.5 mmol, 0.5 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.22 g (10 mmol, 2.0 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 5 was then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 5. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0084] Example 6

[0085] Under argon protection, 3.73 g (5 mmol, 1.0 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 3.33 g (15 mmol, 3.0 eq) of IPDI were added to a two-necked flask containing 150 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 6 was then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 6. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0086] Example 7

[0087] Under argon protection, 1.57 g (1.5 mmol, 0.3 eq) of 4,4-biphenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 7 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain polymer 7. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0088] Example 8

[0089] Under argon protection, 1.57 g (1.5 mmol, 0.3 eq) of 4,4-biphenylmolybdenumtetraamine, 10.00 g (5 mmol, 1 eq) of PDMS-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer was then dried in a vacuum drying oven at 110 °C for 48 h to obtain polymer 8. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0090] Example 9

[0091] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.35 g (8 mmol, 1.6 eq) of 1,6-hexamethylene diisocyanate were added to a two-necked flask containing 100 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 9 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain polymer 9. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0092] Example 10

[0093] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of PDMS-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 10 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0094] Example 11

[0095] Under argon protection, 1.19 g (1.5 mmol, 0.3 eq) of 2-methylphenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 11 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0096] Example 12

[0097] Under argon protection, 1.22 g (1.5 mmol, 0.3 eq) of 2-fluorophenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 12 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0098] Example 13

[0099] Under argon protection, 1.54 g (1.5 mmol, 0.3 eq) of perfluorophenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 13 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0100] Example 14

[0101] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of PEG-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 14 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0102] Example 15

[0103] Under argon protection, 1.11 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraphenol, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 15 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0104] Example 16

[0105] Under argon protection, 1.21 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetramercaptophenol, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 16 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0106] Example 17

[0107] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.85 g (8 mmol, 1.6 eq) of diisothiocyanate were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 17 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0108] Example 18

[0109] Under argon protection, 1.12 g (1.5 mmol, 0.3 eq) of phenylmolybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of PEG with thiol groups at both ends, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 18 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0110] Example 19

[0111] Under argon protection, 0.74 g (1.5 mmol, 0.3 eq) of methylene molybdenum tetraamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 1.78 g (8 mmol, 1.6 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 19 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0112] Example 20

[0113] Under argon protection, 2.33 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, the DMF was removed by rotary evaporation, and the polymer was dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 20. The polymer was then subjected to Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests.

[0114] Example 21

[0115] Under argon protection, 2.33 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 21 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0116] Example 22

[0117] Under argon protection, 2.49 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 22 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0118] Example 23

[0119] Under argon protection, 2.46 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of PDMS-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60 °C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 23 was then dried in a vacuum drying oven at 110 °C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0120] Example 24

[0121] Under argon protection, 2.46 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 24 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0122] Example 25

[0123] Under argon protection, 2.33 g (1.5 mmol, 0.3 eq) of phenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 25 was then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 25. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0124] Example 26

[0125] Under argon protection, 3.02 g (1.5 mmol, 0.3 eq) of biphenyltitanium hexamine, 10.00 g (5 mmol, 1 eq) of D-2000, and 2.11 g (9.5 mmol, 1.9 eq) of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then heated in an oil bath at 60°C for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer 26 was then dried in a vacuum drying oven at 110°C for 48 h to obtain the product. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0126] Example 27

[0127] Under nitrogen protection, 1.5 mmol of phenylvanadium dodecylamine, 5 mmol of D-2000, and 14.0 mmol of naphthalene diisocyanate were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was reacted at 0°C for 24 h. After the reaction was stopped, the DMF was removed by rotary evaporation and then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 27. The polymer was then subjected to Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests.

[0128] Example 28

[0129] Under nitrogen protection, 1.5 mmol of phenyltungsten hexamine, 5 mmol of D-2000, and 9.5 mmol of 1,3,5-triisocyanate benzene were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was reacted at 30°C for 24 h. After the reaction was stopped, the DMF was removed by rotary evaporation and then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 28. The polymer was then subjected to Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests.

[0130] Example 29

[0131] Under nitrogen protection, 1.5 mmol of phenylthallium hexamine, 5 mmol of D-2000, and 9.5 mmol of 1,4-cyclohexane diisocyanate were added to a two-necked flask containing 120 ml of anhydrous DMF 250 mL, and then placed in an oil bath at 100 ° C for 24 h. The reaction was stopped, and DMF was removed by rotary evaporation. Then, the polymer 29 was dried in a vacuum drying oven at 110 ° C for 48 h to obtain polymer 29, and Fourier transform infrared spectroscopy, thermal stability and phase transition temperature tests were performed on it.

[0132] Example 30

[0133] Under nitrogen protection, 1.5 mmol of phenylniobium octamine, 5 mmol of thiol-terminated PEG-2000, and 11.0 mmol of IPDI were added to a two-necked flask containing 120 ml of anhydrous DMF (250 mL). The mixture was then placed in an 80°C oil bath for 24 h. The reaction was stopped, and the DMF was removed by rotary evaporation. The polymer was then dried in a vacuum drying oven at 110°C for 48 h to obtain polymer 30. Fourier transform infrared spectroscopy, thermal stability, and phase transition temperature tests were performed on the polymer.

[0134] Example 31

[0135] (1) Preparation of solid electrolyte: The prepared polymers 1, 7-13, 15-25, and 27-30 were dissolved in tetrahydrofuran with LiFSI at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0136] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 70° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0137] (3) Commercial cathode sheets and the lithium anode prepared in (2) were assembled into solid-state lithium batteries, which were numbered as batteries 1, 7 to 13, 15 to 25, and 27 to 30 according to the polymer used. The assembly process was carried out in an argon glove box with an oxygen and water content of less than 0.1 ppm.

[0138] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0139] Example 32

[0140] (1) Preparation of solid electrolyte: Polymer 2 prepared in Example 2 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0141] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 70° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0142] (3) The commercial positive electrode sheet and the lithium negative electrode prepared in (2) were assembled into a solid-state lithium battery, numbered as Battery 2. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0143] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0144] Example 33

[0145] (1) Preparation of solid electrolyte: Polymer 3 prepared in Example 3 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 240 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0146] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 80° C., and dried for 8 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0147] (3) The commercial positive electrode sheet and the lithium negative electrode prepared in (2) were assembled into a solid-state lithium battery, numbered as Battery 3. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0148] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0149] Example 34

[0150] (1) Preparation of solid electrolyte: Polymer 4 (500 mg) prepared in Example 4 and LiFSI (600 mg) were dissolved in 10 mL of tetrahydrofuran and stirred for 2 hours at a speed of 400 rpm in an anhydrous environment to obtain a molybdenum-based polymer gel solution.

[0151] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 120° C., and dried for 1 hour to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0152] (3) The commercial positive electrode sheet and the lithium negative electrode prepared in (2) were assembled into a solid-state lithium battery, numbered as battery 4. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0153] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0154] Example 35

[0155] (1) Preparation of solid electrolyte: Polymer 5 prepared in Example 5 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0156] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 30° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0157] (3) The commercial cathode sheet and the lithium anode prepared in (2) were assembled into a solid-state lithium battery, numbered as Battery 5. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0158] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0159] Example 36

[0160] (1) Preparation of solid electrolyte: Polymer 6 in Example 6 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0161] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 70° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0162] (3) The commercial positive electrode sheet and the lithium negative electrode prepared in (2) were assembled into a solid-state lithium battery, numbered as Battery 6. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0163] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0164] Example 37

[0165] (1) Preparation of solid electrolyte: Polymer 14 in Example 14 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0166] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 70° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0167] (3) A commercial positive electrode sheet and the lithium negative electrode prepared in (2) were assembled into a solid-state lithium battery, numbered as battery 14. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0168] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0169] Example 38

[0170] (1) Preparation of solid electrolyte: Polymer 26 in Example 26 and LiFSI were dissolved in tetrahydrofuran at a mass ratio of 1:2 to a concentration of 150 mg / mL, and stirred in an anhydrous environment for 2 hours at a speed of 400 rpm to obtain a molybdenum-based polymer gel solution.

[0171] (2) In a glove box, under nitrogen protection, the molybdenum-based polymer gel solution obtained in (1) was placed on a lithium negative electrode sheet, heated on a heating table at 70° C., and dried for 24 hours to obtain a lithium negative electrode containing a solid polymer electrolyte.

[0172] (3) A commercial cathode sheet and the lithium anode prepared in (2) were assembled into a solid-state lithium battery, numbered Battery 26. The assembly process was carried out in an argon glove box with an oxygen content and a water content of less than 0.1 ppm.

[0173] (4) Perform a cyclic charge and discharge test on the lithium battery assembled in (3) using a blue battery testing system.

[0174] Comparative Example 1

[0175] The preparation method of the solid-state lithium battery in this comparative example is basically the same as that in Example 31, except that in this comparative example, tetraphenylmethanetetramine is used as the connection point instead of the polymetallic-oxygen cluster.

[0176] Batteries 1 to 30 and the battery prepared in Comparative Example 1 were subjected to charge and discharge cycle tests: the batteries were tested at 1C / 1C in the range of 2.0 to 4.4V for 2000 cycles.

[0177] Batteries 1 to 30 and the battery prepared in Comparative Example 1 were subjected to a thermal safety test: they were placed in a 200° C. hot box for heating.

[0178] The test results of batteries 1 to 30 and the battery prepared in comparative example 1 are shown in Table 1:

[0179] Table 1 Comparative table of solid-state lithium battery performance obtained in Examples 31 to 38 and Comparative Example 1

[0180]

[0181]

Claims

1. A polymer containing a polymetallic-oxygen cluster, characterized in that: The structure of the repeating unit of the polymer is: M as the center connects n L segments; in, n is an integer from 1 to 18; M is selected from 、 ; L is ; Among them, X 1 With X 2 Direct connection; X 1 Selected from 、 、 or -(CH2) m -, wherein R is independently selected from a hydrogen atom, a halogen or a C1-C3 alkyl group; m is an integer of 1 to 5; X 2 、X 5 are independently selected from -NH-, an O atom or a S atom; X 3 is an O atom or a S atom; X 4 It is a spacer group between -NCO in polyisocyanate or a spacer group between -NCS in diisothiocyanate; X 6 It is a spacer group between terminal amino groups, between terminal thiol groups or between terminal hydroxyl groups in a polymer with multiple terminals of amino groups, thiol groups or hydroxyl groups.

2. The polymer according to claim 1, characterized in that X 4 The spacer group is selected from the group consisting of -NCO in 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate, o-phenylenediisocyanate, naphthalene diisocyanate, m-phenylene diisocyanate, polyhexamethylene diisocyanate, 3,3'-dichlorobiphenyl-4,4'-diisocyanate or L-lysine diisocyanate; or -NCS in 1,4-cyclohexane diisothiocyanate, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate or p-phenylene diisothiocyanate.

3. The polymer according to claim 1, characterized in that X 6 The spacer is selected from the group consisting of the spacer groups between amino groups in polyetheramine D230, polyetheramine D400, polyetheramine D600, polyetheramine D1000, polyetheramine D2000 and polyetheramine D4000, the spacer groups between hydroxyl groups in PEG200-20000, the spacer groups between sulfhydryl groups in thiol-terminated PEG200-20000, the spacer groups between amino groups in amino-terminated PDMS800-25000, the spacer groups between hydroxyl groups in hydroxyl-terminated PDMS800-25000, and the spacer groups between sulfhydryl groups in thiol-terminated PDMS800-25000.

4. The method for preparing a polymer containing polymetallic oxygen clusters according to any one of claims 1 to 3, characterized in that: The following steps are involved: In an organic solvent, M(Y) n , a polymer having amino, thiol or hydroxyl groups at multiple ends and polyisocyanate or diisothiocyanate are uniformly mixed and reacted at 0°C to 100°C for 0.5 to 24 hours to obtain the product; Among them, M(Y) n wherein M and n are defined as in claim 1, and Y is one of -NH2, -OH or -SH.

5. The preparation method according to claim 4, characterized in that The polymer with multiple amino, thiol or hydroxyl groups is selected from polyetheramine D230, polyetheramine D400, polyetheramine D600, polyetheramine D1000, polyetheramine D2000, polyetheramine D4000, PEG200-20000, thiol-terminated PEG200-20000, amino-terminated PDMS800-25000, hydroxyl-terminated PDMS800-25000, and thiol-terminated PDMS800-25000.

6. The preparation method according to claim 4, characterized in that The organic solvent is selected from one or more of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, dimethyl diethyl ether or diethyl ether.

7. The preparation method according to claim 4, characterized in that The polyisocyanate is selected from 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate, o-phenylenediisocyanate, naphthalene diisocyanate, m-phenylene diisocyanate, polyhexamethylene diisocyanate, 3,3'-dichlorobiphenyl-4,4'-diisocyanate or L-lysine diisocyanate; The diisocyanate is selected from 1,4-cyclohexane diisocyanate, 1,4-diisocyanate butane, 1,6-diisocyanate hexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate or p-phenylene diisocyanate.

8. Use of the polymer containing polymetallic-oxygen clusters according to any one of claims 1 to 3 in the preparation of an all-solid-state electrolyte.

9. The use according to claim 8, characterized in that The all-solid-state polymer electrolyte is used to prepare an all-solid-state lithium battery.

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