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CN112239543A - Cross-linked comb-shaped polymer electrolyte, and preparation method and application thereof - Google Patents

Cross-linked comb-shaped polymer electrolyte, and preparation method and application thereof Download PDF

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CN112239543A
CN112239543A CN202011118656.5A CN202011118656A CN112239543A CN 112239543 A CN112239543 A CN 112239543A CN 202011118656 A CN202011118656 A CN 202011118656A CN 112239543 A CN112239543 A CN 112239543A
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polyethylene glycol
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cyclodextrin
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薛志刚
左偲
陈功
周兴平
解孝林
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Huazhong University of Science and Technology
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Abstract

本发明属于聚合物电解质领域，更具体地，涉及一种交联型梳状聚合物电解质、其制备方法和应用。该聚合物电解质具有梳状交联网络结构，该梳状交联网络结构为由所述巯基化环糊精与大分子交联剂在紫外光辐照条件下通过巯基‑烯反应形成的交联网状结构，且所述金属盐分散在该交联网络结构中。该聚合物电解质中环糊精结构可赋予交联聚合物电解质较好的机械性能及界面稳定性，梳形的拓扑结构则赋予电解质传导锂离子功能以及较好的界面相容性，该聚合物电解质中多种特定的结构和组成同时发挥作用使得该聚合物电解质在确保优异的离子电导率和机械性能的同时，显著提升聚合物电解质界面性能，以提高全电池界面稳定性。

Figure 202011118656

The invention belongs to the field of polymer electrolytes, and more particularly, relates to a cross-linked comb-shaped polymer electrolyte, a preparation method and applications thereof. The polymer electrolyte has a comb-like cross-linked network structure, and the comb-like cross-linked network structure is a cross-linked network formed by the mercapto-ene reaction between the thiolated cyclodextrin and the macromolecular cross-linking agent under the condition of ultraviolet light irradiation like structure, and the metal salt is dispersed in the cross-linked network structure. The cyclodextrin structure in the polymer electrolyte can endow the cross-linked polymer electrolyte with better mechanical properties and interfacial stability, and the comb-shaped topology endows the electrolyte with the lithium ion-conducting function and better interfacial compatibility. A variety of specific structures and compositions in the polymer electrolyte play a role at the same time, so that the polymer electrolyte can significantly improve the polymer electrolyte interface performance while ensuring excellent ionic conductivity and mechanical properties, so as to improve the interfacial stability of the whole battery.

Figure 202011118656

Description

Cross-linked comb-shaped polymer electrolyte, and preparation method and application thereof
Technical Field
The invention belongs to the field of polymer electrolytes, and particularly relates to a cross-linked comb-shaped polymer electrolyte, and a preparation method and application thereof.
Background
The electrolyte, which is an important component of Lithium Ion Batteries (LIBs), plays a role in transferring lithium ions between the positive and negative electrodes of the batteries, and greatly affects the electrochemical performance of the batteries. Most of the currently widely used electrolytes are organic electrolytes, and potential safety hazards such as flammability, explosiveness and the like exist. Solid electrolytes have been widely studied because of their wide electrochemical stability window, light weight, and the like, as compared to liquid electrolytes. The polyethylene oxide (PEO) based solid electrolyte has the advantages of light weight, no toxicity, wide electrochemical stability window, good stability with a lithium metal interface and the like, and is the most researched polymer electrolyte. The functional group and chain structure of the polymer are designed to obtain an amorphous polymer with good flexibility, and a solid polymer electrolyte with high room-temperature ionic conductivity is expected to be obtained.
Patent CN110994013A discloses a hybrid polymer electrolyte comprising metal salt and a cross-linked polymer composed of octamercapto polysilsesquioxane as an inner core and polyethylene glycol dimethacrylate as a cross-linked arm; CN111354975A discloses a triblock hybrid polymer electrolyte prepared by dissolving octa-mercapto polysilsesquioxane, methacrylate-terminated polyester-polyethylene glycol-polyester triblock polymer and metal salt in an organic solvent, carrying out ultraviolet curing reaction, and utilizing ring-opening polymerization reaction of hydroxyl and cyclic lactone and mercapto-alkene reaction without photosensitizer ultraviolet initiation. Although the triblock hybrid polymer electrolyte improves the ionic conductivity and the mechanical strength relative to the traditional polyethylene oxide polyelectrolyte, the interface stability of the full cell assembled by the polymer electrolytes is still to be improved, for example, the cell assembled by the electrolyte in patent CN110994013A can only be cycled for 300 hours, the cell assembled by the electrolyte in patent CN111354975A can only be cycled for 600 hours, the cycle stability of the cell directly determines the service life of the cell, and the cycle performance of the cell assembled by the polymer electrolytes in the prior art is still to be improved so as to further improve the performance of the lithium battery.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention obtains the cross-linked comb-shaped polymer electrolyte applied to metal ion batteries such as lithium ion batteries by improving the key composition and structure in the polymer electrolyte, wherein the polymer electrolyte not only can ensure excellent ionic conductivity and mechanical property, but also can remarkably improve the interface property of the battery assembled by the electrolyte compared with the prior art, thereby solving the technical problems of poor interface property and poor battery cycle property of the battery corresponding to the polymer electrolyte in the prior art.
In order to achieve the purpose, the invention provides a polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol dimethacrylate macromolecular cross-linking agent, which has a structural formula shown as a formula (I):
Figure BDA0002731207740000021
wherein m is an integer of 10-50; n is an integer of 4 to 113; p is an integer of 4 to 113.
According to another aspect of the present invention, there is provided a method for preparing the macromolecular crosslinking agent, comprising the steps of:
(1) adding alkali into a polyethylene glycol monomethyl ether solution obtained by dissolving polyethylene glycol monomethyl ether in an organic solvent, dropwise adding 2-chloro-2-oxo-1, 3, 2-dioxaphospholane, stirring for reaction, removing salt through vacuum filtration, adding a precipitator for precipitation, and then obtaining phosphate-based polyethylene glycol through vacuum filtration and drying;
(2) mixing a polyethylene glycol solution obtained by dissolving polyethylene glycol in an organic solvent with the phosphate-based polyethylene glycol obtained in the step (1) and a catalyst, stirring for reaction, adding a polymer obtained by the solvent dissolution reaction, adding a precipitator for precipitation, and performing vacuum filtration and drying to obtain polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol;
(3) dissolving the polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol obtained in the step (2) in an organic solvent, adding alkali and methacryloyl chloride, stirring for reaction, removing salt through vacuum filtration, adding a precipitator, performing vacuum filtration, and drying to obtain the methacrylate-terminated triblock copolymer polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol shown in the formula (I).
Preferably, the relative molecular mass of the polyethylene glycol monomethyl ether in the step (1) is 200-5000; the precipitant is one or more of diethyl ether, n-heptane and n-hexane; in the step (2), the relative molecular mass of the polyethylene glycol is 200-5000. The catalyst is one or more of stannous octoate, 1, 8-diazabicycloundecen-7-ene (DBU) and aluminum triisopropoxide.
According to another aspect of the present invention, there is provided a crosslinked comb-like polymer electrolyte, which comprises thiolated cyclodextrin, the macromolecular crosslinking agent, and a metal salt, and has a comb-like crosslinked network structure formed by a thiol-ene reaction between the thiolated cyclodextrin and the macromolecular crosslinking agent under ultraviolet irradiation, and the metal salt is dispersed in the crosslinked network structure.
According to another aspect of the present invention, there is provided a method for preparing the crosslinked comb-shaped polymer electrolyte, comprising the steps of:
dissolving sulfhydrylation cyclodextrin, the macromolecular cross-linking agent and metal salt in an organic solvent, and then carrying out ultraviolet curing reaction to obtain a crude product; a photosensitizer does not need to be added into the ultraviolet curing reaction system; and drying the crude product to obtain the cross-linked comb-shaped polymer electrolyte.
Preferably, the preparation method comprises the following steps:
(1) dissolving thiolated cyclodextrin and the macromolecular cross-linking agent in an organic solvent to obtain a mixed solution;
(2) adding metal salt into the mixed solution obtained in the step (1), uniformly stirring, and casting to form a film;
(3) irradiating the film obtained in the step (2) under ultraviolet light to enable the film to generate ultraviolet light curing reaction, and obtaining the crude product;
(4) and drying the crude product to obtain the cross-linked comb-shaped polymer electrolyte.
Preferably, the irradiation temperature of the ultraviolet curing reaction is 10-50 ℃, and the irradiation light intensity is 2-50 mW cm-2The irradiation time is 5-60 minutes; the organic solvent is one or more of tetrahydrofuran, acetonitrile and N, N-dimethylformamide.
Preferably, the mass of the metal salt is 10-30% of the mass of the macromolecular cross-linking agent.
Preferably, the thiolated cyclodextrin is obtained by performing iodo modification on hydroxyl of cyclodextrin, and then performing thiolation modification on the hydroxyl; the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
Preferably, the cyclodextrin is β -cyclodextrin.
According to another aspect of the invention, the application of the crosslinked comb-shaped polymer electrolyte is provided, and the crosslinked comb-shaped polymer electrolyte is used as an electrolyte of a metal ion battery.
By taking metal salt as a lithium salt as an example, through the technical scheme designed by the invention, compared with the prior art, the sulfhydrylation cyclodextrin and the polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol dimethacrylate (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent form a cross-linked comb polymer under ultraviolet irradiation, the cyclodextrin structure in the polymer electrolyte can endow the cross-linked polymer electrolyte with better mechanical property, and the comb side chain endows the electrolyte with better chain segment motion capability to conduct lithium ions; the cyclodextrin endows the polymer electrolyte with better interface stability with a negative electrode, a cross-linked network structure is formed through a sulfydryl-alkene reaction, the mechanical property of the polymer electrolyte can be further improved, and the polymer electrolyte can effectively overcome the technical defect that the traditional polymer electrolyte has poor interface property and poor battery cycle life while ensuring excellent ionic conductivity and mechanical property by simultaneously playing a role in various specific structures.
Through the technical scheme, compared with the prior art, the invention can obtain the following beneficial effects:
(1) the invention provides a polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol dimethacrylate (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent, which is a methacrylate-terminated triblock copolymer, wherein cyclic phosphate-based polyethylene glycol is particularly adopted to utilize the side chain of cyclic phosphate to carry out functionalization, and polyethylene glycol can be connected to the side chain of phosphate on the basis of forming the triblock copolymer to form a copolymer with a comb-shaped structure, so that the possibility is provided for further preparing and obtaining a comb-shaped polymer electrolyte.
(2) The invention prepares the macromolecular cross-linking agent of polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol dimethacrylate (POPPEG-b-PEG-b-POPPEG-DMA) through ring-opening polymerization reaction, the comb-shaped topological structure of the cross-linking agent and the ethoxy chain segment of the side chain can effectively conduct lithium ions, thereby improving the room-temperature conductivity of electrolyte; in addition, the existence of the comb-shaped topological structure enables the electrolyte to have better interface compatibility and show better cycle performance.
(3) The polymer electrolyte provided by the invention has a cross-linked network structure formed by the mercapto-alkene reaction of mercapto cyclodextrin and a macromolecular cross-linking agent under the ultraviolet irradiation condition; metal salt is dispersed in theA cross-linked network structure, and wherein the polyethylene glycol of the macromolecular cross-linking agent side chain forms a comb-like structure. The cyclodextrin structure of the polymer electrolyte can endow the cross-linked polymer electrolyte with better mechanical property and good interface stability, the comb-shaped topological structure endows the electrolyte with better lithium ion conduction capability and interface compatibility, and the two structures play a role simultaneously, so that the mechanical property, the conductivity and the electrochemical property of the polymer electrolyte are greatly improved compared with those of the traditional polymer electrolyte. The ion conductivity of the cross-linked comb polymer electrolyte in the preferred embodiment of the invention can reach 1.77 multiplied by 10 at 30 DEG C-4S cm-1After the lithium-lithium symmetric battery is cycled for 2200 hours, short circuit still does not occur, and the stability of the interface performance is obviously improved compared with the prior polymer electrolyte.
(4) The invention also can optimize and obtain the cross-linked comb-shaped polymer electrolyte film with higher ionic conductivity by screening the chain length of the polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol dimethacrylate (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent and further preferably controlling the mass ratio of the lithium salt to the macromolecular cross-linking agent.
(5) The reaction principle of the method for preparing the cross-linked polymer electrolyte based on photosensitizer-free ultraviolet-initiated mercaptan-alkene reaction is that sulfhydrylated cyclodextrin generates sulfhydryl free radicals under the ultraviolet irradiation condition, the sulfhydryl free radicals attack double bonds to form new chemical bonds, the newly generated free radicals capture hydrogen on the sulfhydrylated cyclodextrin to generate sulfhydryl free radicals for carrying out chain growth reaction, and chain termination is realized through disproportionated hydrogen-capturing or coupling reaction after the chain growth reaction is finished. The influence of the introduction of a photosensitizer and the self-polymerization of double bonds on a crosslinking network is avoided. In addition, the cross-linked polymer electrolyte is prepared by ultraviolet-initiated thiol-ene reaction without photosensitizer, oxygen and moisture are not required to be isolated, and the preparation method is simple and easy to operate. The preparation method of the polymer electrolyte has mild reaction conditions and simple and convenient operation method.
(6) The invention adopts thiol-ene reaction initiated by ultraviolet without photosensitizer to make thiolated cyclodextrin and polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent form cross-linked comb polymer. At present, a crosslinking comb-shaped polymer formed by sulfhydrylation cyclodextrin and polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular crosslinking agent is not reported to be applied to an all-solid-state lithium ion battery as a crosslinking comb-shaped polymer electrolyte film. When the cross-linked polymer electrolyte film is stressed, the stress can be effectively dispersed in a cross-linked network, and the cross-linked comb-shaped polymer electrolyte can bear larger stress by virtue of the cyclodextrin which is a natural high molecular material.
(7) The cross-linked comb-shaped polymer electrolyte provided by the invention can be bent and deformed after being stressed in the use process of the polymer electrolyte of the lithium battery, and can effectively solve the problems of fragmentation of a polymer electrolyte film and the like; effectively solves the problems that the polymer electrolyte in the prior art has low mechanical strength and is easy to crack under the action of external force.
(8) The invention prepares sulfhydrylation cyclodextrin by iodinating and sulfhydrylation cyclodextrin which is a natural high molecular material, and prepares the cross-linked comb-shaped polymer electrolyte by doping lithium salt with a polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol (POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent under ultraviolet illumination. The invention makes the polymer electrolyte meet specific chemical structure by controlling the whole process of the preparation method of the polymer electrolyte, especially by controlling the reactant types in each reaction step, and the like, when the polymer electrolyte is applied to a lithium ion battery, when the polymer meets external force or is bent and folded, the stress can be dispersed, thereby solving the problem that the polymer electrolyte is easy to crack, and improving the comprehensive performance of the lithium battery.
Drawings
FIG. 1 is a NMR spectrum of iodo-cyclodextrin prepared in example 7 of the present invention with chemical shifts on the abscissa;
FIG. 2 is a NMR spectrum of thiolated cyclodextrin prepared in example 7 of the present invention, with chemical shifts on the abscissa;
FIG. 3 is a graph of the conductivity as a function of temperature for crosslinked comb-shaped polymer electrolytes of examples 7, 8 and 9 of the present invention;
FIG. 4 is a lithium deposition curve of a cross-linked comb-shaped polymer electrolyte in example 7 of the present invention;
FIG. 5 is a charge-discharge cycle curve of a crosslinked comb-shaped polymer electrolyte in example 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol dimethacrylate (marked as POPPEG-b-PEG-b-POPPEG-DMA) macromolecular cross-linking agent, which has a structural formula shown in a formula (I):
Figure BDA0002731207740000071
wherein m is an integer of 10-50; n is an integer of 4 to 113; p is an integer of 4 to 113.
The macromolecular cross-linking agent is a methacrylate-terminated triblock copolymer, wherein cyclic phosphate-based polyethylene glycol is particularly adopted to carry out functionalization by utilizing a side chain of cyclic phosphate. On the basis of forming the block copolymer, polyethylene glycol may be further attached to the side chain to form a polymer electrolyte having a comb-like structure.
The invention also provides a preparation method of the macromolecular cross-linking agent, which comprises the following steps:
(1) dissolving polyethylene glycol monomethyl ether in an organic solvent to obtain a polyethylene glycol monomethyl ether solution, adding alkali into the polyethylene glycol monomethyl ether solution, dropwise adding 2-chloro-2-oxo-1, 3, 2-dioxaphospholane, stirring for reaction, removing salt through vacuum filtration, adding a precipitator for precipitation, and then performing vacuum filtration and drying to obtain phosphate-based polyethylene glycol;
(2) dissolving polyethylene glycol in an organic solvent to obtain a polyethylene glycol solution, adding the phosphate-based polyethylene glycol obtained in the step (1) and a catalyst into the polyethylene glycol solution, stirring for reaction, adding a polymer obtained by solvent dissolution reaction, adding a precipitator for precipitation, and performing vacuum filtration and drying to obtain polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol;
(3) dissolving the polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol obtained in the step (2) in an organic solvent, adding alkali and methacryloyl chloride, stirring for reaction, removing salt through vacuum filtration, adding a precipitator, performing vacuum filtration, and drying to obtain the methacrylate-terminated triblock copolymer, namely, the polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol.
In some embodiments, the chemical structure of the methoxypolyethylene glycols of step (1) is represented by formula (ii):
Figure BDA0002731207740000081
the relative molecular mass of the polyethylene glycol monomethyl ether is 200-5000;
in the step (1), the organic solvent is one or more of dichloromethane, acetonitrile and tetrahydrofuran; the alkali is one or more of potassium carbonate, triethylamine and sodium hydroxide; the precipitant is one or more of diethyl ether, n-heptane and n-hexane; the chemical structural formula of the 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) is shown as the formula (III):
Figure BDA0002731207740000082
in the step (2), the chemical structural formula of the polyethylene glycol is shown as the formula (IV):
Figure BDA0002731207740000083
the relative molecular mass of the polyethylene glycol is 200-5000;
in the step (2), the reaction temperature of the reaction is 30-80 ℃; the organic solvent is one or more of dichloromethane, acetonitrile and tetrahydrofuran; the catalyst is one or more of stannous octoate, 1, 8-diazabicycloundecene-7-ene and aluminum triisopropoxide; the precipitant is one or more of diethyl ether, n-heptane and n-hexane.
In the step (3), the reaction temperature of the reaction is 0-50 ℃; the organic solvent is one or more of dichloromethane, acetonitrile and tetrahydrofuran; the alkali is one or more of potassium carbonate, triethylamine and sodium hydroxide; the precipitant is one or more of diethyl ether, n-heptane and n-hexane.
In the preparation process of the macromolecular cross-linking agent, experiments show that the macromolecular cross-linking agent is difficult to prepare under the conditions of overhigh temperature and humidity, probably because the long-chain polyethylene glycol has hygroscopicity. In a preferred embodiment, the ambient humidity is not preferably higher than 40% and the temperature is not preferably higher than 25 ℃.
The invention also provides a cross-linked comb-shaped polymer electrolyte, which comprises thiolated cyclodextrin, the macromolecular cross-linking agent and metal salt, wherein the cross-linked comb-shaped polymer electrolyte has a cross-linked network structure formed by the thiol-alkene reaction of the thiolated cyclodextrin and the macromolecular cross-linking agent under the ultraviolet irradiation condition; the metal salt is dispersed in the cross-linked network structure, and wherein the polyethylene glycol of the side chain of the macromolecular cross-linking agent forms a comb-like structure. Wherein the thiolated cyclodextrin reacts with the macromolecular crosslinking agent according to equimolar amounts of functional groups.
The cross-linking comb polymer can be represented schematically by a chemical structure shown as a formula (V):
Figure BDA0002731207740000091
in the structural schematic, m is an integer of 10-50; n is an integer of 4 to 113; p is an integer of 4 to 113. In a preferred embodiment, m is an integer of 40-50; n is an integer of 10-20; p is an integer of 4 to 9.
The invention also provides a preparation method of the cross-linked comb-shaped polymer electrolyte, which comprises the following steps: dissolving sulfhydrylation cyclodextrin, the macromolecular cross-linking agent and metal salt in an organic solvent, and then carrying out ultraviolet curing reaction to obtain a crude product; a photosensitizer does not need to be added into the ultraviolet curing reaction system; and drying the crude product to obtain the cross-linked comb-shaped polymer electrolyte.
In some embodiments, the preparation method comprises the following steps:
(1) dissolving thiolated cyclodextrin and the macromolecular cross-linking agent in an organic solvent to obtain a mixed solution;
(2) adding metal salt into the mixed solution obtained in the step (1), uniformly stirring, and casting to form a film;
(3) and (3) placing the film obtained in the step (2) under ultraviolet light for irradiation to obtain the crude product.
(4) And drying the crude product to obtain the cross-linked comb-shaped polymer electrolyte.
In some embodiments, the irradiation temperature of the ultraviolet curing reaction is 10-50 ℃, and the irradiation light intensity is 2-50 mW cm-2The irradiation time is 5-60 minutes; the organic solvent is one or more of tetrahydrofuran, acetonitrile and N, N-dimethylformamide.
In some embodiments, the metal salt is a lithium salt, and the lithium salt is one or more of lithium bis (trifluoromethyl) sulfonyl imide, lithium perchlorate, and lithium hexafluorophosphate.
In order to ensure sufficient dissolution and dispersion of the metal lithium salt, in some embodiments, the mass of the metal salt is 10-30% of the mass of the macromolecular crosslinking agent.
In some embodiments, the method of preparing the thiolated cyclodextrin includes the steps of:
(1) dissolving cyclodextrin in an organic solvent, adding triphenylphosphine and iodine simple substance, stirring, refluxing, reacting, and standing to obtain a reaction solution; performing rotary evaporation to remove concentration, adding a methanol solution of potassium tert-butoxide to adjust the pH, continuously stirring, adding a precipitator, and performing vacuum filtration, washing and vacuum drying to obtain iodo-cyclodextrin;
(2) dissolving the iodo-cyclodextrin obtained in the step (1) in an organic solvent, adding thiourea, stirring and refluxing under an argon atmosphere, and performing rotary evaporation to remove the organic solvent to obtain yellow oily liquid; under the protection of argon, adding water and alkali to continue reacting, and adding acid to obtain a white precipitate; vacuum filtering and drying to obtain the thiolated cyclodextrin.
In some embodiments, the stirring reflux reaction temperature in the step (1) is 50-120 ℃; the organic solvent is one or more of tetrahydrofuran, acetonitrile and N, N-dimethylformamide; the precipitant is one or more of methanol, diethyl ether and n-heptane.
In the step (2), the stirring reflux reaction temperature is 50-120 ℃; the solvent is one or more of tetrahydrofuran, acetonitrile and N, N-dimethylformamide; the alkali is sodium hydroxide or potassium hydroxide; the acid is any one of hydrochloric acid, nitric acid and sulfuric acid.
The sulfhydrylation cyclodextrin is obtained by performing iodo modification on hydroxyl of cyclodextrin and then performing sulfhydrylation modification on the hydroxyl. In some embodiments, the cyclodextrin is an alpha-cyclodextrin, beta-cyclodextrin, or gamma-cyclodextrin.
In some embodiments, the cyclodextrin has the chemical formula:
Figure BDA0002731207740000111
the chemical structural formula of the thiolated cyclodextrin is as follows:
Figure BDA0002731207740000112
the chemical synthesis reaction formula of the thiolated cyclodextrin is as follows:
Figure BDA0002731207740000113
in experiments, the ion conductivity of the obtained electrolyte is optimal when beta-cyclodextrin in the three cyclodextrins is used for preparing a polymer electrolyte, which is probably because an asymmetric network structure formed by the beta-cyclodextrin is more favorable for chain segment motion of a polyphosphoester-based polyethylene glycol-b-polyphosphoester-based polyethylene glycol cross-linked chain.
The invention also provides application of the cross-linked comb-shaped polymer electrolyte as an electrolyte of a metal ion battery. In a preferred embodiment, the cross-linked comb-shaped polymer electrolyte is a thin film-shaped polymer electrolyte, and the thickness of the thin film is preferably 50-300 micrometers; the metal ion battery is a lithium ion battery.
Besides adding lithium salt to be applied to the lithium ion battery, the cross-linked comb-shaped polymer electrolyte can also replace the lithium salt with other metal salts, so that the cross-linked comb-shaped polymer electrolyte is suitable for ion batteries of other metal elements.
The invention relates to a preparation method of a cross-linked comb-shaped polymer, which is characterized in that sulfhydrylation cyclodextrin reacts with a polyphosphate polyethylene glycol-b-polyphosphate polyethylene glycol dimethacrylate (POPPEG-b-PEG-b-POPPEG-DMA) macromolecule cross-linking agent to prepare a cross-linked comb-shaped polymer, metal salt (such as lithium salt) is doped to form a cross-linked comb-shaped polymer electrolyte (such as a polymer electrolyte film), the cross-linked comb-shaped polymer electrolyte is prepared on the basis of ring-opening polymerization reaction initiated by polyethylene glycol and sulfydryl-alkene reaction initiated by ultraviolet light, and no photosensitizer is needed to be added in the preparation method. When the metal ion battery is applied to a metal ion battery (such as a lithium ion battery), the metal ion battery has good mechanical property and conductivity, and the comprehensive performance of the lithium battery is improved.
PEO-based comb polymers are generally composed of short PEO side chains, whose segments conduct lithium ions through segmental motion, and a main chain. In addition, the cyclodextrin as a natural polymer material has the advantages of low price, easy obtainment, no toxicity and the like. Cyclodextrin (Cyclodextrin) is prepared from starch under catalysis of Cyclodextrin glycosyltransferase, and is a series of cyclic oligosaccharides formed from D-glucose linked by alpha- (1-4) glycosidic bonds. The cyclodextrin is in a round table structure, and the hydroxyl on the narrower side (main surface) of the cyclodextrin has higher activity and is easy to functionalize. The cyclodextrin and lithium metal can form a stable solid electrolyte interface, thereby prolonging the service life of the lithium battery. The ultraviolet light initiated sulfydryl-alkene reaction is simple and efficient, so that the application is wide, the cross-linking network can be simply and conveniently constructed through the sulfydryl-alkene reaction, and the mechanical strength of the electrolyte is further improved.
The following are examples:
example 1
A cross-linked comb-shaped polymer electrolyte comprises a cross-linked polymer formed by lithium salt, sulfhydrylation cyclodextrin and polyphosphate-based polyethylene glycol-b-polyphosphate-based polyethylene glycol dimethacrylate macromolecular cross-linking agent.
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous gamma-cyclodextrin in 80mL of tetrahydrofuran, mechanically stirring, carrying out reflux reaction at 80 ℃ for 24 hours, removing part of tetrahydrofuran by rotary evaporation, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. And carrying out vacuum filtration, methanol washing and vacuum drying to obtain white powder (octaiodo-gamma-cyclodextrin). Octaiodo-gamma-cyclodextrin (4.35g) and thiourea (1.21g) were dissolved in 80mL of tetrahydrofuran, stirred under argon at 80 ℃ for 24 hours and rotary evaporated to remove tetrahydrofuran to give a yellow oily liquid. Under the protection of argon, adding sodium hydroxide solution for continuous reaction for 1 hour, and then adding nitric acid to obtain white precipitate. Vacuum filtering, and drying to obtain white powder, i.e. octamercapto gamma-cyclodextrin (gamma-CD-SH)8)。
Dissolving 0.4g of polyethylene glycol monomethyl ether 200 and potassium carbonate in 20mL of dichloromethane, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 30 ℃ for reacting for 4 hours, removing salt through vacuum filtration after the reaction is finished, adding 100mL of diethyl ether for precipitation, and obtaining white powder (OPPEG) through vacuum filtration and vacuum drying200) (ii) a Mixing 0.4g polyethylene glycol 200, 12.24g OPPEG200And 64mg of stannous octoate are dissolved in 20mL of dichloromethane, stirred and reacted for 24h at the temperature of 30 ℃, and 10mL of dichloro chloride is added after the reaction is finishedDissolving the polymer obtained by reaction in methane, adding 100mL of diethyl ether for precipitation, vacuum filtering, and vacuum drying to obtain white powder (POPPEG)10-b-PEG200-b-POPPEG10) (ii) a 6.32g of POPPEG10-b-PEG200-b-POPPEG10Heating and melting, adding potassium carbonate, dichloromethane and methacryloyl chloride under the atmosphere of argon, stirring and reacting for 16h at 0 ℃, removing salt through vacuum filtration, adding 100mL of diethyl ether for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG200-b-POPPEG10-DMA); wherein m is 4; n is 10; p is 9.
1.614g of POPPEG are added according to the equivalence ratio10-b-PEG200-b-POPPEG10DMA and 89.05mg of gamma-CD-SH8Adding lithium perchlorate according to 20 percent of mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of DMF for dissolving, stirring for 15min at normal temperature, pouring the solution into a mold, volatilizing the solvent for 2h at room temperature, and then placing the mold under an ultraviolet curing lamp for ultraviolet irradiation for 12 min, wherein the ultraviolet irradiation light intensity is 25mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 1.3 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium-lithium symmetric battery assembled by the electrolyte has no short circuit after 1500 hours of circulation, and has good interface performance stability.
Example 2
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous alpha-cyclodextrin in 80mL of anhydrous acetonitrile, mechanically stirring, carrying out reflux reaction at 80 ℃ for 24 hours, carrying out rotary evaporation to remove part of acetonitrile, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. After vacuum filtration, methanol washing and vacuum drying, white powder (hexaiodo-alpha-cyclodextrin) is obtained.Hexaiodo α -cyclodextrin (3.26g) and thiourea (1.21g) were dissolved in 80mL of anhydrous acetonitrile, stirred under argon at 80 ℃ for 24 hours and rotary evaporated to remove acetonitrile to give a yellow oily liquid. Under the protection of argon, sodium hydroxide solution is added for continuous reaction for 1 hour, and then sulfuric acid is added to obtain white precipitate. Vacuum filtering, drying to obtain white powder, i.e. hexa-mercapto alpha-cyclodextrin (alpha-CD-SH)6)。
Dissolving 1.5g of polyethylene glycol monomethyl ether 750 and triethylamine in 20mL of acetonitrile, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 50 ℃ for reacting for 4h, removing salt through vacuum filtration after the reaction is finished, adding 100mL of n-heptane for precipitation, and obtaining white powder (OPPEG) through vacuum filtration and vacuum drying750) (ii) a 1.5g of polyethylene glycol 750, 34.24g of OPPEG750And 24mg DBU in 20mL acetonitrile, stirring at 50 deg.C for 24h, adding 10mL acetonitrile after reaction to dissolve the obtained polymer, adding 100mL n-heptane for precipitation, vacuum filtering, and vacuum drying to obtain white powder (POPPEG)10-b-PEG750-b-POPPEG10) (ii) a 17.87g of POPPEG10-b-PEG750-b-POPPEG10Heating and melting, adding triethylamine, acetonitrile and methacryloyl chloride in the argon atmosphere, stirring and reacting for 16h at 20 ℃, removing salt through vacuum filtration, adding 100mL of n-heptane for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate end-capped triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG750-b-POPPEG10-DMA); wherein m is 17; n is 10; p is 17.
4.5g of POPPEG are added according to the equivalent ratio10-b-PEG750-b-POPPEG10DMA and 89.05mg of alpha-CD-SH6Respectively adding lithium perchlorate according to 20 percent of the mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of tetrahydrofuran for dissolving, pouring the solution into a mould after stirring for 15min at normal temperature, volatilizing the solvent for 3 h at room temperature, and then placing the mould under an ultraviolet curing lamp for ultraviolet irradiation for 20 min, wherein the ultraviolet irradiation light intensity is 15mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. After completely removing the solvent in the electrolyte, the cross-linked comb-shaped polymer is obtainedA polyelectrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 3.2 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium symmetric battery assembled by the electrolyte has no short circuit after circulating for 1600 hours, and has good interface performance stability.
Example 3
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous gamma-cyclodextrin in 80mL of tetrahydrofuran, mechanically stirring, carrying out reflux reaction at 80 ℃ for 24 hours, removing part of tetrahydrofuran by rotary evaporation, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. And carrying out vacuum filtration, methanol washing and vacuum drying to obtain white powder (octaiodo-gamma-cyclodextrin). Octaiodo-gamma-cyclodextrin (4.35g) and thiourea (1.21g) were dissolved in 80mL of tetrahydrofuran, stirred under argon at 80 ℃ for 24 hours and rotary evaporated to remove tetrahydrofuran to give a yellow oily liquid. Under the protection of argon, adding sodium hydroxide solution for continuous reaction for 1 hour, and then adding nitric acid to obtain white precipitate. Vacuum filtering, and drying to obtain white powder, i.e. octamercapto gamma-cyclodextrin (gamma-CD-SH)8)。
Dissolving 4g of polyethylene glycol monomethyl ether 2000 and sodium hydroxide in 20mL of tetrahydrofuran, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 30 ℃ for reacting for 4h, removing salt through vacuum filtration after the reaction is finished, adding 100mL of n-hexane for precipitation, and obtaining white powder (OPPEG) through vacuum filtration and vacuum drying2000) (ii) a 1g of polyethylene glycol 2000, 21.06g of OPPEG2000And 32mg of triisopropoxyaluminum were dissolved in 20mL of tetrahydrofuran, and the mixture was stirred at 80 ℃ to react for 16 hours, after the reaction was completed, 10mL of a polymer obtained by the dissolution reaction of tetrahydrofuran was added, 100mL of n-hexane was added to precipitate, and white powder (POPPEG) was obtained by vacuum filtration and vacuum drying20-b-PEG2000-b-POPPEG20) (ii) a Mixing 11.03g of POPPEG20-b-PEG2000-b-POPPEG20After heating and melting, under argon atmosphereAdding sodium hydroxide, tetrahydrofuran and methacryloyl chloride, stirring and reacting at 50 ℃ for 8h, removing salt through vacuum filtration, adding 100mL of n-hexane for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown in the formula (I)20-b-PEG2000-b-POPPEG20-DMA); wherein m is 45; n is 20; p is 45.
4.43g of POPPEG are added according to the equivalent ratio10-b-PEG2000-b-POPPEG10DMA and 22.25mg of gamma-CD-SH8Adding lithium perchlorate according to 30 percent of the mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of DMF for dissolving, pouring the solution into a mould after stirring for 15min at normal temperature, volatilizing the solvent for 3 h at room temperature, and then placing the mould under an ultraviolet curing lamp for ultraviolet irradiation for 10 min, wherein the ultraviolet irradiation light intensity is 50mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 3.2 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium-lithium symmetric battery assembled by the electrolyte has no short circuit after 1300 hours of circulation, and has good interface performance stability.
Example 4
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous beta-cyclodextrin in 80mL of anhydrous DMF, mechanically stirring, carrying out reflux reaction at 50 ℃ for 24 hours, carrying out rotary evaporation to remove part of DMF, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. After vacuum filtration, methanol washing and vacuum drying, white powder (heptaiodo-beta-cyclodextrin) is obtained. Heptaiodo β -cyclodextrin (3.86g) and thiourea (1.21g) were dissolved in 80mL of anhydrous DMF and after stirring for 24h under argon atmosphere at 50 ℃ the DMF was removed by rotary evaporation to give a yellow oily liquid. Under the protection of argon, sodium hydroxide solution is added for continuous reaction for 1 hour, and then hydrochloric acid is added to obtain white precipitate. Vacuum filtering and drying to obtainTo a white powder, i.e. heptamercapto beta-cyclodextrin (beta-CD-SH)7)。
Dissolving 10g of polyethylene glycol monomethyl ether 5000 and triethylamine in 20mL of acetonitrile, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 0 ℃ for reacting for 8h, removing salt by vacuum filtration after the reaction is finished, adding 100mL of diethyl ether for precipitation, and obtaining white powder (OPPEG) by vacuum filtration and vacuum drying5000) (ii) a Mixing 1g polyethylene glycol 5000, 20.42g OPPEG2000And 32mg of triisopropoxyaluminum were dissolved in 20mL of acetonitrile, and the mixture was stirred at 50 ℃ for 24 hours, after the reaction was completed, 10mL of acetonitrile was added to dissolve the resulting polymer, 100mL of diethyl ether was added to precipitate, and the precipitate was vacuum-filtered and vacuum-dried to obtain a white powder (POPPEG)10-b-PEG5000-b-POPPEG10) (ii) a 10.71g of POPPEG10-b-PEG5000-b-POPPEG10Heating and melting, adding sodium hydroxide, acetonitrile and methacryloyl chloride under the argon atmosphere, stirring and reacting for 16h at 30 ℃, removing salt through vacuum filtration, adding 100mL of diethyl ether for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG5000-b-POPPEG10-DMA); wherein m is 112; n is 10; p 112.
6.695g of POPPEG are added according to the equivalent ratio10-b-PEG5000-b-POPPEG10DMA and 22.25mg beta-CD-SH7Adding lithium hexafluorophosphate according to 10% of mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of tetrahydrofuran for dissolving, pouring the solution into a mould after stirring for 15min at normal temperature, volatilizing the solvent for 3 h at room temperature, and then placing the mould under an ultraviolet curing lamp for ultraviolet irradiation for 12 min, wherein the ultraviolet irradiation light intensity is 25mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 5.3 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. After the test, the test paper is tested,the lithium-lithium symmetrical battery assembled by the electrolyte has no short circuit after circulating for 1800 hours, and has good interface performance stability.
Example 5
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous alpha-cyclodextrin in 80mL of anhydrous acetonitrile, mechanically stirring, carrying out reflux reaction at 120 ℃ for 16 hours, carrying out rotary evaporation to remove part of acetonitrile, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. After vacuum filtration, methanol washing and vacuum drying, white powder (hexaiodo-alpha-cyclodextrin) is obtained. Hexaiodo α -cyclodextrin (3.26g) and thiourea (1.21g) were dissolved in 80mL of anhydrous acetonitrile, stirred under argon at 120 ℃ for 24 hours and rotary evaporated to remove acetonitrile to give a yellow oily liquid. Under the protection of argon, sodium hydroxide solution is added for continuous reaction for 1 hour, and then sulfuric acid is added to obtain white precipitate. Vacuum filtering, drying to obtain white powder, i.e. hexa-mercapto alpha-cyclodextrin (alpha-CD-SH)6)。
Dissolving 0.4g of polyethylene glycol monomethyl ether 200 and potassium carbonate in 20mL of dichloromethane, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 50 ℃ for reacting for 4 hours, removing salt by vacuum filtration after the reaction is finished, adding 100mL of n-heptane for precipitation, and obtaining white powder (OPPEG) by vacuum filtration and vacuum drying200) (ii) a Mixing 0.4g polyethylene glycol 200, 12.24g OPPEG200And 64mg of stannous octoate are dissolved in 20mL of dichloromethane, the mixture is stirred and reacted for 16h at 50 ℃, 10mL of dichloromethane is added after the reaction is finished to dissolve the polymer obtained by the reaction, 100mL of n-heptane is added for precipitation, and white powder (POPPEG) is obtained after vacuum filtration and vacuum drying10-b-PEG200-b-POPPEG10) (ii) a 6.32g of POPPEG10-b-PEG200-b-POPPEG10Heating and melting, adding potassium carbonate, dichloromethane and methacryloyl chloride in the argon atmosphere, stirring and reacting for 16h at 20 ℃, removing salt through vacuum filtration, adding 100mL of n-heptane for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG200-b-POPPEG10-DMA); wherein m is 4; n is 10; p is 4.
1.614g of POPPEG are added according to the equivalence ratio10-b-PEG200-b-POPPEG10DMA and 89.05mg of alpha-CD-SH6Adding lithium hexafluorophosphate according to 10% of mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of tetrahydrofuran for dissolving, pouring the solution into a mold after stirring for 15min at normal temperature, volatilizing the solvent for 3 h at room temperature, and then placing the mold under an ultraviolet curing lamp for ultraviolet irradiation for 20 min, wherein the ultraviolet irradiation light intensity is 15mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 1.6 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium symmetric battery assembled by the electrolyte has no short circuit after being cycled for 1460 hours, and has good interface performance stability.
Example 6
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous gamma-cyclodextrin in 80mL of tetrahydrofuran, mechanically stirring, carrying out reflux reaction at 80 ℃ for 24 hours, removing part of tetrahydrofuran by rotary evaporation, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. And carrying out vacuum filtration, methanol washing and vacuum drying to obtain white powder (octaiodo-gamma-cyclodextrin). Octaiodo-gamma-cyclodextrin (4.35g) and thiourea (1.21g) were dissolved in 80mL of tetrahydrofuran, stirred under argon at 80 ℃ for 24 hours and rotary evaporated to remove tetrahydrofuran to give a yellow oily liquid. Under the protection of argon, adding sodium hydroxide solution for continuous reaction for 1 hour, and then adding nitric acid to obtain white precipitate. Vacuum filtering, and drying to obtain white powder, i.e. octamercapto gamma-cyclodextrin (gamma-CD-SH)8)。
Dissolving 1.5g of polyethylene glycol monomethyl ether 750 and triethylamine in 20mL of tetrahydrofuran, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 50 ℃ for reacting for 4h,after the reaction is finished, the salt is removed by vacuum filtration, 100mL of n-heptane is added for precipitation, and white powder (OPPEG) is obtained by vacuum filtration and vacuum drying750) (ii) a 1.5g of polyethylene glycol 750, 34.24g of OPPEG750And 24mg of DBU is dissolved in 20mL of tetrahydrofuran, the mixture is stirred and reacted for 16h at the temperature of 80 ℃, after the reaction is finished, 10mL of tetrahydrofuran is added to dissolve the polymer obtained by the reaction, 100mL of n-heptane is added to precipitate, and white powder (POPPEG) is obtained through vacuum filtration and vacuum drying10-b-PEG750-b-POPPEG10) (ii) a 17.87g of POPPEG10-b-PEG750-b-POPPEG10Heating and melting, adding triethylamine, tetrahydrofuran and methacryloyl chloride under the argon atmosphere, stirring and reacting for 12 hours at the temperature of 30 ℃, removing salt through vacuum filtration, adding 100mL of n-heptane for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG750-b-POPPEG10-DMA); wherein m is 17; n is 10; p is 17.
4.5g of POPPEG are added according to the equivalent ratio10-b-PEG750-b-POPPEG10DMA and 89.05mg of gamma-CD-SH8Adding lithium bis (trifluoromethyl) sulfonyl imide according to 30% of mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of DMF (dimethyl formamide) for dissolving, stirring for 15min at normal temperature, pouring the solution into a mold, volatilizing the solvent for 2h at room temperature, and then placing the mold under an ultraviolet curing lamp for ultraviolet irradiation for 12 min, wherein the ultraviolet irradiation light intensity is 25mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 1.3 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium symmetric battery assembled by the electrolyte has no short circuit after 1320-hour circulation, and has good interface performance stability.
Example 7
The preparation method of the cross-linked polymer electrolyte comprises the following steps: 13.3g of trisPhenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous beta-cyclodextrin are dissolved in 80mL of anhydrous DMF, the mixture is mechanically stirred and subjected to reflux reaction at 50 ℃ for 24 hours, after part of DMF is removed by rotary evaporation, a methanol solution of potassium tert-butoxide is added to adjust the pH, and 500mL of methanol is added for precipitation. After vacuum filtration, methanol washing and vacuum drying, white powder (heptaiodo-beta-cyclodextrin) is obtained. Heptaiodo β -cyclodextrin (3.86g) and thiourea (1.21g) were dissolved in 80mL of anhydrous DMF and after stirring for 24h under argon atmosphere at 50 ℃ the DMF was removed by rotary evaporation to give a yellow oily liquid. Under the protection of argon, sodium hydroxide solution is added for continuous reaction for 1 hour, and then hydrochloric acid is added to obtain white precipitate. Vacuum filtering, drying to obtain white powder, i.e. heptamercapto beta-cyclodextrin (beta-CD-SH)7). FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of prepared iodo-beta-cyclodextrin with chemical shifts on the abscissa. FIG. 2 is a NMR spectrum of the prepared thiolated beta-cyclodextrin, with chemical shifts on the abscissa.
Dissolving 4g of polyethylene glycol monomethyl ether 2000 and potassium carbonate in 20mL of dichloromethane, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 50 ℃ for reacting for 4 hours, removing salt by vacuum filtration after the reaction is finished, adding 100mL of n-hexane for precipitation, and obtaining white powder (OPPEG) by vacuum filtration and vacuum drying500) (ii) a 1g of polyethylene glycol 2000 and 20.42g of OPPEG2000And 32mg of triisopropoxyaluminum were dissolved in 20mL of dichloromethane, the reaction was stirred at 50 ℃ for 24 hours, 10mL of dichloromethane was added after the reaction was completed to dissolve the resulting polymer, 100mL of n-hexane was added to precipitate, and white powder (POPPEG) was obtained by vacuum filtration and vacuum drying10-b-PEG2000-b-POPPEG10) (ii) a Mixing 11.03g of POPPEG10-b-PEG2000-b-POPPEG10Heating and melting, adding triethylamine, tetrahydrofuran and methacryloyl chloride under the argon atmosphere, stirring and reacting for 12 hours at the temperature of 30 ℃, removing salt through vacuum filtration, adding 100mL of normal hexane for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG2000-b-POPPEG10-DMA); wherein m is 45; n is 10; p is 9.
4.43g of POPPEG are added according to the equivalent ratio10-b-PEG2000-b-POPPEG10DMA and 22.25mg beta-CD-SH7Adding lithium bis (trifluoromethyl) sulfonyl imide into the polymer according to the mass fractions of 10%, 20% and 30% of the macromolecular cross-linking agent in the polymer, adding 3ml of acetonitrile to dissolve the lithium bis (trifluoromethyl) sulfonyl imide, stirring the mixture for 15min at normal temperature, pouring the solution into a mold, volatilizing the solvent for 3 h at room temperature, and then placing the mold under an ultraviolet curing lamp to perform ultraviolet irradiation for 5min at the ultraviolet irradiation intensity of 2mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 1.77 multiplied by 10 at room temperature-4S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Fig. 4 is a lithium deposition curve of the crosslinked comb-shaped polymer electrolyte in the present example. It can be seen that the overpotential of the lithium-lithium symmetric battery is basically unchanged, and the lithium-lithium symmetric battery is not short-circuited after 2200 hours of cycling, which indicates that the polymer electrolyte and the lithium negative electrode have better interface stability. However, the battery assembled with the electrolyte in patent CN110994013A can only cycle for 300 hours, and the battery assembled with the electrolyte in patent CN111354975A can only cycle for 600 hours, so that the cycle stability of the lithium ion battery assembled with the polymer electrolyte provided in this embodiment is significantly improved. FIG. 5 is a charge-discharge cycle curve of the crosslinked comb-shaped polymer electrolyte in example 1 of the present invention. It can be seen that the capacity retention rate of the full battery is higher, and the discharge specific capacity attenuation is smaller.
Example 8
Other conditions were the same as in example 7 except that the beta-cyclodextrin in example 7 was replaced with alpha-cyclodextrin.
Example 9
Other conditions were the same as in example 7 except that β -cyclodextrin in example 7 was replaced with γ -cyclodextrin.
Fig. 3 is a graph of conductivity versus temperature for crosslinked comb polymer electrolytes prepared from example 7, example 8, and example 9 under different cyclodextrin core species. It can be seen that the crosslinked comb-shaped polymer electrolyte prepared from the β -cyclodextrin core has the highest ionic conductivity.
Example 10
The preparation method of the cross-linked polymer electrolyte comprises the following steps: dissolving 13.3g of triphenylphosphine, 13.5g of iodine elementary substance particles and 4.0g of anhydrous beta-cyclodextrin in 80mL of anhydrous DMF, mechanically stirring, carrying out reflux reaction at 50 ℃ for 24 hours, carrying out rotary evaporation to remove part of DMF, adding a methanol solution of potassium tert-butoxide to adjust the pH, and adding 500mL of methanol for precipitation. After vacuum filtration, methanol washing and vacuum drying, white powder (heptaiodo-beta-cyclodextrin) is obtained. Heptaiodo β -cyclodextrin (3.86g) and thiourea (1.21g) were dissolved in 80mL of anhydrous DMF and after stirring for 24h under argon atmosphere at 50 ℃ the DMF was removed by rotary evaporation to give a yellow oily liquid. Under the protection of argon, sodium hydroxide solution is added for continuous reaction for 1 hour, and then hydrochloric acid is added to obtain white precipitate. Vacuum filtering, drying to obtain white powder, i.e. heptamercapto beta-cyclodextrin (beta-CD-SH)7)。
Dissolving 10g of polyethylene glycol monomethyl ether 5000 and triethylamine in 20mL of acetonitrile, slowly dropwise adding 285mg of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP), stirring at 20 ℃ for reacting for 6h, removing salt through vacuum filtration after the reaction is finished, adding 100mL of diethyl ether for precipitation, and obtaining white powder (OPPEG) through vacuum filtration and vacuum drying5000) (ii) a Mixing 1g polyethylene glycol 5000, 20.42g OPPEG2000And 32mg of triisopropoxyaluminum were dissolved in 20mL of acetonitrile, and the mixture was stirred at 50 ℃ for 24 hours, after the reaction was completed, 10mL of acetonitrile was added to dissolve the resulting polymer, 100mL of diethyl ether was added to precipitate, and the precipitate was vacuum-filtered and vacuum-dried to obtain a white powder (POPPEG)10-b-PEG5000-b-POPPEG10) (ii) a 10.71g of POPPEG10-b-PEG5000-b-POPPEG10Heating and melting, adding sodium hydroxide, acetonitrile and methacryloyl chloride under the argon atmosphere, stirring and reacting for 24h at 0 ℃, removing salt through vacuum filtration, adding 100mL of diethyl ether for precipitation, vacuum filtration and vacuum drying to obtain the methacrylate-terminated triblock copolymer (POPPEG) shown as the formula (I)10-b-PEG5000-b-POPPEG10-DMA); wherein m is 112；n＝10； p＝9。
6.695g of POPPEG are added according to the equivalent ratio10-b-PEG5000-b-POPPEG10DMA and 22.25mg beta-CD-SH7Adding lithium perchlorate according to 20 percent of the mass fraction of macromolecular cross-linking agent in the polymer, adding 3ml of tetrahydrofuran for dissolving, pouring the solution into a mould after stirring for 15min at normal temperature, volatilizing the solvent for 3 h at room temperature, and then placing the mould under an ultraviolet curing lamp for ultraviolet irradiation for 12 min, wherein the ultraviolet irradiation light intensity is 25mW cm-2And finally, putting the mixture into a vacuum drying oven for drying for 24 hours. And completely removing the solvent in the electrolyte to obtain the cross-linked comb-shaped polymer electrolyte film.
The lithium ion conductivity of the cross-linked comb-shaped polymer electrolyte film is 7.7 multiplied by 10 at room temperature-5S cm-1. And assembling the lithium ion battery according to the sequence of the lithium sheet, the electrolyte film and the lithium iron phosphate positive plate. Tests show that the lithium-lithium symmetric battery assembled by the electrolyte has no short circuit after being cycled for 1900 hours, and has good interface performance stability.
Because the polymer electrolyte in the invention can be applied to a lithium ion battery, the lithium salt used in the process of the invention can be a lithium salt (such as one or more of lithium perchlorate, lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide) used in a lithium battery in the prior art. In addition, the thickness of the cross-linking comb-shaped polymer electrolyte film prepared by the invention can be flexibly adjusted according to actual needs, and certainly, the cross-linking comb-shaped polymer electrolyte with a non-film shape can also be prepared according to actual application requirements. Finally, in addition to the crosslinked polymer electrolyte suitable for lithium ion batteries obtained in the above embodiments, the present invention may also replace lithium salt with other metal salts, so as to obtain a crosslinked comb-shaped polymer electrolyte suitable for other metal ion batteries.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1.一种聚磷酸酯基聚乙二醇-b-聚乙二醇-b-聚磷酸酯基聚乙二醇二甲基丙烯酸酯大分子交联剂，其特征在于，其具有如式(一)所示的结构式：1. a polyphosphate-based polyethylene glycol-b-polyethylene glycol-b-polyphosphate-based polyethylene glycol dimethacrylate macromolecular cross-linking agent, is characterized in that, it has such as formula ( 1) The structural formula shown:
Figure FDA0002731207730000011
Figure FDA0002731207730000011
 其中，m为10～50的整数；n为4～113的整数；p为4～113的整数。Wherein, m is an integer of 10-50; n is an integer of 4-113; p is an integer of 4-113. 2.如权利要求1所述的大分子交联剂的制备方法，其特征在于，包括如下步骤：2. the preparation method of macromolecular cross-linking agent as claimed in claim 1, is characterized in that, comprises the steps: (1)向聚乙二醇单甲醚溶解于有机溶剂中得到的聚乙二醇单甲醚溶液中加入碱，滴加2-氯-2-氧-1,3,2-二氧磷杂环戊烷，搅拌反应，经真空抽滤除去盐，加入沉淀剂进行沉淀，然后经真空抽滤、干燥得到磷酸酯基聚乙二醇；(1) Add alkali to the polyethylene glycol monomethyl ether solution obtained by dissolving polyethylene glycol monomethyl ether in an organic solvent, and dropwise add 2-chloro-2-oxo-1,3,2-dioxaphosphine Cyclopentane, stirring and reacting, removing salt by vacuum filtration, adding a precipitant for precipitation, then vacuum filtration and drying to obtain phosphate-based polyethylene glycol; (2)将聚乙二醇溶解于有机溶剂中得到的聚乙二醇溶液与步骤(1)得到的磷酸酯基聚乙二醇和催化剂混合，搅拌反应，加入溶剂溶解反应得到的聚合物，加入沉淀剂进行沉淀，经真空抽滤、干燥得到聚磷酸酯基聚乙二醇-b-聚乙二醇-b-聚磷酸酯基聚乙二醇；(2) the polyethylene glycol solution obtained by dissolving polyethylene glycol in an organic solvent is mixed with the phosphate-based polyethylene glycol obtained in step (1) and the catalyst, stirring the reaction, adding the polymer obtained by the solvent dissolving reaction, adding The precipitation agent is precipitated, and the polyphosphate-based polyethylene glycol-b-polyethylene glycol-b-polyphosphate-based polyethylene glycol is obtained by vacuum filtration and drying; (3)将步骤(2)得到的聚磷酸酯基聚乙二醇-b-聚乙二醇-b-聚磷酸酯基聚乙二醇溶解于有机溶剂中，加入碱和甲基丙烯酰氯，搅拌反应，经真空抽滤去除盐、加入沉淀剂、真空抽滤、干燥得到如式(一)所示的甲基丙烯酸酯封端的三嵌段共聚物聚磷酸酯基聚乙二醇-b-聚乙二醇-b-聚磷酸酯基聚乙二醇。(3) the polyphosphate-based polyethylene glycol-b-polyethylene glycol-b-polyphosphate-based polyethylene glycol obtained in step (2) is dissolved in an organic solvent, and alkali and methacryloyl chloride are added, Stirring the reaction, removing salt through vacuum filtration, adding precipitant, vacuum filtration, and drying to obtain the methacrylate-terminated triblock copolymer polyphosphate-based polyethylene glycol-b- Polyethylene glycol-b-polyphosphate-based polyethylene glycol. 3.如权利要求2所述的制备方法，其特征在于，步骤(1)聚乙二醇单甲醚的相对分子质量为200～5000；所述沉淀剂为乙醚、正庚烷、正己烷中的一种或多种；步骤(2)中，所述聚乙二醇的相对分子质量为200～5000；所述催化剂为辛酸亚锡、1,8-二氮杂二环十一碳-7-烯(DBU)、三异丙氧基铝中的一种或多种。3. preparation method as claimed in claim 2 is characterized in that, the relative molecular mass of step (1) polyethylene glycol monomethyl ether is 200～5000; Described precipitation agent is in ether, n-heptane, n-hexane in step (2), the relative molecular mass of the polyethylene glycol is 200-5000; the catalyst is stannous octoate, 1,8-diazabicycloundec-7 - One or more of alkene (DBU), aluminum triisopropoxide. 4.一种交联型梳状聚合物电解质，其特征在于，其包括巯基化环糊精、如权利要求1所述的大分子交联剂与金属盐，其具有梳状交联网络结构，该梳状交联网络结构为由所述巯基化环糊精与所述大分子交联剂在紫外光辐照条件下通过巯基-烯反应形成的交联网状结构，且所述金属盐分散在该交联网络结构中。4. A cross-linked comb-shaped polymer electrolyte, characterized in that it comprises a thiolated cyclodextrin, a macromolecular cross-linking agent as claimed in claim 1 and a metal salt, which has a comb-shaped cross-linked network structure, The comb-like cross-linked network structure is a cross-linked network structure formed by the thiol-ene reaction of the thiolated cyclodextrin and the macromolecular cross-linking agent under the condition of ultraviolet light irradiation, and the metal salt is dispersed in the in the cross-linked network structure. 5.如权利要求4所述的交联型梳状聚合物电解质的制备方法，其特征在于，包括如下步骤：5. The preparation method of cross-linked comb polymer electrolyte as claimed in claim 4, is characterized in that, comprises the steps: 将巯基化环糊精、权利要求1所述的大分子交联剂与金属盐溶解在有机溶剂中，然后进行紫外光固化反应，得到粗产物；所述紫外光固化反应体系中无需添加光敏剂；将所述粗产物干燥，得到交联型梳状聚合物电解质。The thiolated cyclodextrin, the macromolecular cross-linking agent according to claim 1 and the metal salt are dissolved in an organic solvent, and then subjected to ultraviolet light curing reaction to obtain a crude product; no photosensitizer needs to be added to the ultraviolet light curing reaction system ; Dry the crude product to obtain a cross-linked comb-shaped polymer electrolyte. 6.如权利要求5所述的制备方法，其特征在于，包括如下步骤：6. preparation method as claimed in claim 5, is characterized in that, comprises the steps: (1)将巯基化环糊精与所述大分子交联剂溶解在有机溶剂中，得到混合溶液；(1) dissolving the thiolated cyclodextrin and the macromolecular cross-linking agent in an organic solvent to obtain a mixed solution; (2)向步骤(1)得到的混合溶液中加入金属盐，搅拌均匀后浇铸成膜；(2) adding metal salt to the mixed solution obtained in step (1), and casting to form a film after stirring evenly; (3)将步骤(2)得到的膜置于紫外光下辐照，使其发生紫外光固化反应，得到所述粗产物；(3) placing the film obtained in step (2) under ultraviolet light irradiation to make it undergo an ultraviolet light curing reaction to obtain the crude product; (4)将所述粗产物干燥，得到所述交联型梳状聚合物电解质。(4) drying the crude product to obtain the cross-linked comb-shaped polymer electrolyte. 7.如权利要求5或6所述的制备方法，其特征在于，所述紫外光固化反应的辐照温度为10～50℃，辐照光强为2～50mW cm-2，辐照时间为5～60分钟；所述有机溶剂为四氢呋喃、乙腈、N，N-二甲基甲酰胺中的一种或多种。7. The preparation method according to claim 5 or 6, wherein the irradiation temperature of the ultraviolet light curing reaction is 10-50° C., the irradiation light intensity is 2-50 mW cm −2 , and the irradiation time is 5 to 60 minutes; the organic solvent is one or more of tetrahydrofuran, acetonitrile, and N,N-dimethylformamide. 8.如权利要求5或6的制备方法，其特征在于，所述金属盐的质量为所述大分子交联剂的质量的10～30％。8. The preparation method according to claim 5 or 6, wherein the mass of the metal salt is 10-30% of the mass of the macromolecular cross-linking agent. 9.如权利要求5或6所述的制备方法，其特征在于，所述巯基化环糊精为环糊精的羟基先经碘代修饰，然后再经巯基化修饰得到；所述环糊精为α-环糊精、β-环糊精或γ-环糊精。9. The preparation method according to claim 5 or 6, wherein the thiolated cyclodextrin is obtained by modifying the hydroxyl group of the cyclodextrin with iodine first, and then thiolated modification; the cyclodextrin For α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin. 10.如权利要求4所述的交联型梳状聚合物电解质的应用，其特征在于，用作金属离子电池的电解质。10. The application of the cross-linked comb polymer electrolyte according to claim 4, characterized in that it is used as an electrolyte for metal ion batteries.
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