CN111540948A - Composite solid polymer electrolyte membrane and preparation method and application thereof - Google Patents
Composite solid polymer electrolyte membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite solid polymer electrolyte membrane and a preparation method and application thereof. The composite solid polymer electrolyte membrane includes: the lithium ion battery comprises a polymer component, a lithium salt, 0-25 parts by mass of a plasticizer and 0-15 parts by mass of inorganic particles, wherein the polymer component comprises 10-30 parts by mass of a thermoplastic polymer and 20-50 parts by mass of a cross-linked reticular polymer, and the molar ratio of the lithium salt to a lithium ion complexing dissociation group in the polymer component is 1 (1-16). The composite solid polymer electrolyte membrane has high ionic conductivity and good mechanical strength, is simple in preparation process, and can be applied to large-scale production. In some embodiments of the invention, the composite solid polymer electrolyteThe film has a thickness of 10 to 500 μm, a tensile strength of 0.2MPa or more, and a lithium ion conductivity of 1 × 10‑5The electrolyte has the advantages that the S/cm is higher than that, the electrochemical window is higher than 3.8V, and the electrolyte can be used in the fields of solid lithium batteries, electrochromic devices and the like, and can ensure that short circuit does not occur when the electrolyte is used for a long time at high temperature.
Description
Technical Field
The invention relates to the field of electrochemical devices, in particular to a composite solid polymer electrolyte membrane and a preparation method and application thereof.
Background
The lithium ion battery is generally applied to the fields of consumer electronics, power energy storage and the like, but has larger potential safety hazard and lower energy density due to the use of flammable liquid electrolyte, and the application range is greatly limited. The solid lithium battery adopts a solid electrolyte which is not easy to burn, and has the characteristics of high energy density, wide working temperature range, high safety and flexibility. The development of high-safety and high-energy-density solid-state lithium batteries is a hotspot in both academia and the business industry.
The solid electrolyte is the most important difference between the solid lithium battery and the liquid lithium ion battery, and the synthesis preparation technology of the solid electrolyte membrane is also the core technology of the solid lithium battery. The solid electrolyte should have high ionic conductivity, dielectric properties, wide electrochemical window, good mechanical strength and processability, and good compatibility with electrodes. According to the current research, solid electrolytes are divided into two types, one type is inorganic solid electrolyte taking oxides and sulfides as main materials, and the problems that the solid electrolytes have poor contact with electrodes, large interface resistance and can not realize large-capacity battery cores exist; the other type is solid polymer electrolyte formed by complexing high molecular polymer and lithium salt, has the advantages of light weight, good viscoelasticity, good film forming property and strong processability, can realize roll-to-roll production, and is suitable for being used as lithium battery electrolyte materials, and the polymer matrix comprises polyethers, polycarbonates, polyacrylates, polynitriles, polyolefins and the like. However, existing solid polymer electrolytes still remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to propose a composite solid polymer electrolyte membrane, a method for its preparation and its use. The composite solid polymer electrolyte membrane has high ionic conductivity and good mechanical strength, is simple in preparation process, and can be applied to large-scale production.
In one aspect of the invention, a composite solid polymer electrolyte membrane is provided. According to an embodiment of the present invention, the composite solid polymer electrolyte membrane includes: the lithium ion battery comprises a polymer component, a lithium salt, 0-25 parts by mass of a plasticizer and 0-15 parts by mass of inorganic particles, wherein the polymer component comprises 10-30 parts by mass of a thermoplastic polymer and 20-50 parts by mass of a cross-linked reticular polymer, and the molar ratio of the lithium salt to a lithium ion complexing dissociation group in the polymer component is 1 (1-16).
The inventors have found in studies on solid polymer electrolytes that, on the one hand, thermoplastic polymers are widely used as solid polymer electrolytes due to their good lithium salt-dissolving ability and high dielectric constant. However, the thermoplastic polymer has a relatively high crystallinity, resulting in very low room temperature conductivity and poor mechanical strength, and is easily broken by lithium dendrite or melt short-circuiting occurs at about 60 ℃. On the other hand, a polymer obtained by curing a crosslinking monomer having a functional group polymerizable by a radical as a terminal cap can form a three-dimensional network structure, and has high mechanical strength and high temperature resistance, but has low ionic conductivity, poor wettability with an electrode, and high interfacial resistance.
Further, the inventors have made extensive studies and have proposed a solid electrolyte membrane in which a thermoplastic polymer and a crosslinked network polymer are compounded, wherein the polymer having a crosslinked network structure serves as a skeleton of a polymer solid electrolyte and the thermoplastic polymer is filled therein, whereby the mechanical properties and temperature resistance are greatly improved, and the problems that the thermoplastic polymer has poor mechanical properties and is easily short-circuited at high temperatures are solved. Meanwhile, the crosslinked network structure can also inhibit crystallization of the thermoplastic polymer, thereby improving the lithium ion conductivity. In addition, the polymer adopted in the composite solid polymer electrolyte membrane comprises two parts, namely thermoplastic polymer and cross-linked reticular polymer, when the composite solid polymer electrolyte membrane is used in a solid lithium battery, a hot pressing process can be adopted to be compounded with the positive pole piece and the negative pole piece, the thermoplastic part is melted again and then solidified, the solid-solid interface wettability can be effectively improved, and the interface impedance is reduced. On the other hand, the lithium ion conductivity of the composite solid polymer electrolyte membrane can be effectively improved and the electrochemical window can be widened by adopting the inorganic particles and the plasticizer in the optimized proportion.
In addition, the composite solid polymer electrolyte membrane according to the above-described embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the thermoplastic polymer is present in an amount of 50% to 400% relative to the crosslinked network polymer.
In some embodiments of the invention, the thermoplastic polymer is selected from at least one of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polycarbonate.
In some embodiments of the present invention, the crosslinked network polymer is crosslinked by at least one of photo-curing and thermal curing of the crosslinking monomer.
In some embodiments of the invention, the crosslinking monomer comprises at least one of ethoxy, propoxy, and butoxy groups.
In some embodiments of the invention, the crosslinking monomer contains at least two ethylenically unsaturated bonds (carbon-carbon double bonds) or at least two acetylenically unsaturated bonds (carbon-carbon triple bonds).
In some embodiments of the invention, the crosslinking monomers include at least one first crosslinking monomer containing at least two epoxy groups, and at least one second crosslinking monomer containing at least two amino groups.
In some embodiments of the invention, the lithium salt is selected from LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiSCN、LiC(CF3SO2)3、(CF3SO2)2NLi、(FSO2)2At least one of NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl boric acid lithium, and imino lithium.
In some embodiments of the present invention, the plasticizer is selected from at least one of imidazole-based ionic liquids, quaternary ammonium-based ionic liquids, piperidine-based ionic liquids, pyrrole-based ionic liquids, propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, tetraglyme (tetraglyme).
In some embodiments of the invention, the inorganic particles are selected from at least one of alumina, silica, molecular sieves.
In some embodiments of the present invention, the inorganic particles have an average particle size of 5 to 100nm, preferably 5 to 50 nm.
In some embodiments of the present invention, the thickness of the composite solid polymer electrolyte membrane is 10 to 500 μm, preferably 50 to 200 μm.
In some embodiments of the present invention, the composite solid polymer electrolyte membrane has a tensile strength of 0.2MPa or more, preferably 0.5MPa or more, and a lithium ion conductivity of 1 × 10-5The S/cm is above, and the electrochemical window is above 3.8V.
In another aspect of the present invention, the present invention provides a method of preparing the composite solid polymer electrolyte membrane of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a thermoplastic polymer with a solvent to obtain a polymer solution; adding inorganic particles to the polymer solution to obtain a dispersion; (2) adding lithium salt, a crosslinking monomer and a plasticizer into the dispersion liquid to obtain slurry; (3) and coating the slurry on a release film, removing the solvent, and carrying out photocuring crosslinking or thermocuring crosslinking to obtain the composite solid polymer electrolyte membrane. Therefore, the method is simple and efficient, large-scale production can be realized in a coating mode, and the prepared composite solid polymer electrolyte membrane has high ionic conductivity, high mechanical strength and wide application range.
In addition, the method of manufacturing a composite solid polymer electrolyte membrane according to the above-described embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the solvent is selected from at least one of acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, acetone.
In some embodiments of the invention, the concentration of the polymer solution is 5% to 30%.
In a further aspect of the invention, the invention proposes the use of the composite solid polymer electrolyte membrane of the above embodiments in a solid lithium battery and/or an electrochromic device. The solid lithium battery and the electrochromic device adopting the composite solid polymer electrolyte membrane provided by the invention have the advantages of high energy density, wide working temperature range and higher stability and electrochemical cycle performance at high temperature.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, a composite solid polymer electrolyte membrane is provided. According to an embodiment of the present invention, the composite solid polymer electrolyte membrane includes: the lithium ion battery comprises a polymer component, lithium salt, 0-25 parts by mass of plasticizer and 0-15 parts by mass of inorganic particles, wherein the polymer component comprises 10-30 parts by mass of thermoplastic polymer and 20-50 parts by mass of cross-linked reticular polymer, and the molar ratio of lithium salt to lithium ion complexing dissociation groups in the polymer component is 1 (1-16).
Specifically, in the composite solid polymer electrolyte membrane, the mass fraction of the thermoplastic polymer may be 10, 15, 20, 25, 30, or the like. The mass fraction of the crosslinked network polymer may be 20, 25, 30, 35, 40, 45, 50, etc. The molar ratio of the lithium salt to the lithium ion complex dissociation groups in the polymer component may be 1:1, 1:2, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, and the like. The mass fraction of the plasticizer may be 0, 0.1, 0.5, 1, 5, 10, 15, 20, 25, etc. The inorganic particles may be present in a mass fraction of 0, 0.1, 0.5, 1, 5, 10, 15, etc.
According to some embodiments of the present invention, in the composite solid polymer electrolyte membrane of the present invention, the content of the thermoplastic polymer with respect to the crosslinked network polymer may be 50% to 400%, for example, 50%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, and the like. Thereby, the mechanical strength and the interface properties of the composite solid polymer electrolyte membrane can be further improved.
According to some embodiments of the present invention, the thermoplastic polymer may be at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polycarbonate.
According to some embodiments of the present invention, the crosslinked network polymer is crosslinked by at least one of photo-curing and thermal curing of the crosslinking monomer. According to some embodiments of the invention, the crosslinking monomer comprises at least one of ethoxy, propoxy, and butoxy groups. According to some embodiments of the invention, the crosslinking monomer contains at least two ethylenically unsaturated bonds (carbon-carbon double bonds) or at least two acetylenically unsaturated bonds (carbon-carbon triple bonds). According to some embodiments of the invention, the crosslinking monomer comprises at least one first crosslinking monomer comprising at least two epoxy groups, and at least one second crosslinking monomer comprising at least two amino groups. Specifically, the crosslinking monomer may be preferably selected from trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, polyether amine, and the like.
According to some embodiments of the invention, the lithium salt is selected from LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiSCN、LiC(CF3SO2)3、(CF3SO2)2NLi、(FSO2)2At least one of NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl boric acid lithium, and imino lithium.
According to some embodiments of the present invention, the plasticizer may be at least one selected from imidazole ionic liquid, quaternary ammonium ionic liquid, piperidine ionic liquid, pyrrole ionic liquid, propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, and tetraglyme, and is preferably N-methyl-butylpyrrolidine bistrifluoromethane imide salt, 1-hexyl-3-methylimidazolium tetrafluoroborate, and tetraglyme (tetraglyme).
According to some embodiments of the present invention, the inorganic particles may be at least one selected from alumina, silica, and molecular sieves.
According to some embodiments of the present invention, the inorganic particles may have an average particle diameter of 5 to 100nm, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, and the like, and preferably 5 to 50 nm. By using the inorganic particles having the above particle size range, the crystallinity of the polymer can be further reduced, and the inorganic particles are facilitated to provide a lithium ion conduction channel, and the lithium ion conductivity is improved. The inventor finds in research that if the particle size of the inorganic particles is too large, the mechanical properties and lithium ion conductivity of the polymer are reduced; if the particle diameter of the inorganic particles is too small, the problem of non-uniform agglomeration and dispersion is easily caused.
According to some embodiments of the present invention, the thickness of the composite solid polymer electrolyte membrane may be 10 to 500 μm, for example, 10 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, etc., preferably 50 to 200 μm. Thereby, the mechanical strength and the interface properties of the composite solid polymer electrolyte membrane can be further improved.
According to some embodiments of the present invention, the composite solid polymer electrolyte membrane has a tensile strength of 0.2MPa or more, preferably 0.5MPa or more, and a lithium ion conductivity of 1 × 10-5The S/cm is above, and the electrochemical window is above 3.8V.
In another aspect of the present invention, the present invention provides a method of preparing the composite solid polymer electrolyte membrane of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a thermoplastic polymer with a solvent to obtain a polymer solution; adding inorganic particles to the polymer solution to obtain a dispersion; (2) adding lithium salt, a crosslinking monomer and a plasticizer into the dispersion liquid to obtain slurry; (3) and coating the slurry on a release film, removing the solvent, and carrying out photocuring crosslinking or thermocuring crosslinking to obtain the composite solid polymer electrolyte membrane. Therefore, the method is simple and efficient, large-scale production can be realized in a coating mode, and the prepared composite solid polymer electrolyte membrane has high ionic conductivity, high mechanical strength and wide application range.
According to some embodiments of the present invention, the solvent may be at least one selected from acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, and acetone.
According to some embodiments of the present invention, the concentration of the polymer solution may be 5% to 30%, such as 5%, 10%, 15%, 20%, 25%, 30%, and the like.
In a further aspect of the invention, the invention proposes the use of the composite solid polymer electrolyte membrane of the above embodiments in a solid lithium battery and/or an electrochromic device. The solid lithium battery and the electrochromic device adopting the composite solid polymer electrolyte membrane provided by the invention have the advantages of high energy density, wide working temperature range and higher stability and electrochemical cycle performance at high temperature.
Specifically, according to an embodiment of the present invention, the present invention provides a solid-state lithium ion battery, including: the composite solid polymer electrolyte membrane comprises a positive electrode, a negative electrode and a composite solid polymer electrolyte membrane arranged between the positive electrode and the negative electrode, wherein the composite solid polymer electrolyte membrane is the composite solid polymer electrolyte membrane of the embodiment. The positive electrode includes a current collector, and a positive active material, a positive conductive agent, and a binder coated on the current collector. LiCoO can be selected as the positive electrode active material2、LiFePO4Or nickel-cobalt-manganese ternary cathode materials and the like. The positive electrode conductive agent can be selected from acetylene black, graphite and Super P or conductive fibers, etc. The negative electrode may be made of lithium metal or the like. Thus, the solid state lithium ion battery has all the features and advantages described above for the composite solid polymer electrolyte membrane, and thus, the details are not repeated here. In general, the solid-state lithium ion battery has higher stability and electrochemical cycle performance at high temperature.
Specifically, according to an embodiment of the present invention, there is provided an electrochromic device including a tungsten oxide coloring layer, a nickel oxide coloring layer, and a composite solid polymer electrolyte membrane interposed between tungsten oxide and nickel oxide, the composite solid polymer electrolyte membrane being the composite solid polymer electrolyte membrane of the above-described embodiment. Wherein, the nickel oxide and tungsten oxide discoloring layer is deposited on the surface of Indium Tin Oxide (ITO) glass or an ITO film by adopting the processes of magnetron sputtering, electron beam evaporation and the like. Thus, the electrochromic device has all the features and advantages described above for the composite solid polymer electrolyte membrane, and will not be described in detail here. In general, the electrochromic device has high stability and electrochemical cycle performance at high temperature.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Dissolving polymer polyethylene oxide (PEO) with lithium ion conductivity into an acetonitrile solution according to the concentration of 8%, adding cross-linking monomers trimethylolpropane triglycidyl ether (TMPEG) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid which accounts for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI in a molar ratio of 1:5 with EO groups in the polymer and the monomer; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, crosslinking monomers in the material, and volatilizing the solvent to obtain the composite solid polymer electrolyte film.
Example 2
Dissolving polymer polyethylene oxide (PEO) with lithium ion conductivity into an acetonitrile solution according to the concentration of 8%, adding cross-linking monomer polypropylene glycol diglycidyl ether (DY-3601) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid which accounts for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI in a molar ratio of 1:5 to EO groups in the polymer and the monomer; and after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 100 ℃, crosslinking monomers in the material, and volatilizing a solvent to obtain the composite solid polymer electrolyte film.
Example 3
The polymer polyethylene oxide (PEO) with lithium ion conductivity is dissolved in acetonitrile solution according to the concentration of 8%, gas phase nano-silica (the average particle diameter is 10nm) with the mass of 20% of PEO is added, and the mixture is dispersed uniformly by ultrasonic. Adding crosslinking monomers trimethylolpropane triglycidyl ether (TMPEG) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid which accounts for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI, wherein the molar ratio of the added lithium salt LiTFSI to EO groups in the polymer and the monomer is 1: 5; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, crosslinking monomers in the material, and volatilizing the solvent to obtain the composite solid polymer electrolyte film.
Example 4
The polymer polyethylene oxide (PEO) with lithium ion conductivity is dissolved in acetonitrile solution according to the concentration of 8%, gas phase nano-silica (the average particle diameter is 10nm) with the mass of 20% of PEO is added, and the mixture is dispersed uniformly by ultrasonic. Adding crosslinking monomers trimethylolpropane triglycidyl ether (TMPEG) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid which accounts for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI, wherein the molar ratio of the added lithium salt LiTFSI to EO groups in the polymer and the monomer is 1: 10; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, crosslinking monomers in the material, and volatilizing the solvent to obtain the composite solid polymer electrolyte film.
Example 5
The polymer polyethylene oxide (PEO) with lithium ion conductivity is dissolved in acetonitrile solution according to the concentration of 8%, gas phase nano-silica (the average particle diameter is 10nm) with the mass of 20% of PEO is added, and the mixture is dispersed uniformly by ultrasonic. Adding crosslinking monomers trimethylolpropane triglycidyl ether (TMPEG) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid accounting for 50% of the mass of the PEO and Propylene Carbonate (PC) accounting for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI according to the molar ratio of the lithium salt to EO groups in the polymer and the monomers being 1: 5; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, crosslinking monomers in the material, and volatilizing the solvent to obtain the composite solid polymer electrolyte film.
Example 6
The polymer polyethylene oxide (PEO) with lithium ion conductivity is dissolved in acetonitrile solution according to the concentration of 8%, gas phase nano-silica (the average particle diameter is 10nm) with the mass of 20% of PEO is added, and the mixture is dispersed uniformly by ultrasonic. Adding crosslinking monomers trimethylolpropane triglycidyl ether (TMPEG) and polyether amine (ED900) which account for 100% of the mass of the PEO, adding N-methyl-butyl pyrrolidine bistrifluoromethanesulfonic acid imide salt ionic liquid accounting for 50% of the mass of the PEO and tetraethyleneglycol dimethyl ether (TEGDME) accounting for 50% of the mass of the PEO under stirring, and finally adding lithium salt LiTFSI according to the molar ratio of the lithium salt LiTFSI to EO groups in the polymer and the monomers being 1: 5; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, crosslinking monomers in the material, and volatilizing the solvent to obtain the composite solid polymer electrolyte film.
Example 7
Dissolving polymethyl methacrylate (PMMA) with lithium ion conductivity into acetonitrile solution according to the concentration of 20%, adding a molecular sieve (the average particle size is 20nm) with the mass of 20% of PMMA, and performing ultrasonic dispersion uniformly. Adding a crosslinking monomer polyethylene glycol diacrylate (PEG600DA) with the mass of 100% of PMMA, adding lithium salt LiTFSI with the molar ratio of EO groups in the polymer to COO groups in the crosslinking monomer being 1:5, and finally adding tetraethyleneglycol dimethyl ether (TEGDME) with the mass of 50% of PMMA; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, completely volatilizing the solvent, and moving to an ultraviolet lamp to perform UV crosslinking curing to obtain the composite solid polymer electrolyte film.
Example 8
Dissolving polypropylene carbonate (PPC) with lithium ion conductivity into acetonitrile solution according to the concentration of 30%, adding molecular sieve (with the average particle size of 20nm) with the mass of 20% of the PPC, and performing ultrasonic dispersion uniformly. Adding 100% of cross-linking monomer polyethylene glycol diacrylate (PEG600DA) by mass of PPC, adding lithium salt LiTFSI in a molar ratio of 1:5 to EO groups in the polymer and COO groups in the cross-linking monomer, and finally adding 50% of tetraethyleneglycol dimethyl ether (TEGDME) by mass of PPC; and (3) after uniformly mixing, coating the solid polymer electrolyte slurry on a release film, heating at 80 ℃, completely volatilizing the solvent, and moving to an ultraviolet lamp to perform UV crosslinking curing to obtain the composite solid polymer electrolyte film.
Comparative example 1
Dissolving a lithium ion-conducting polymer polyethylene oxide (PEO) in acetonitrile according to the concentration of 8%, adding lithium salt LiTFSI in a molar ratio of 1:10 to EO groups in the polymer, fully and uniformly mixing, coating on a release film, and performing vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte film.
Comparative example 2
Dissolving a polymer polymethyl methacrylate (PMMA) capable of guiding lithium ions into acetonitrile according to the concentration of 20%, adding lithium salt LiTFSI according to the molar ratio of 1:10 to COO groups in the polymer, fully and uniformly mixing, coating on a release film, and performing vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte film.
Comparative example 3
Dissolving a Polymer Polypropylene Carbonate (PPC) for leading lithium ions into acetonitrile according to the concentration of 20%, then adding lithium salt LiTFSI in a molar ratio of 1:10 to COO groups in the polymer, fully and uniformly mixing, coating on a release film, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the solid polymer electrolyte film.
Example 9
Electrochromic device
The electrochromic device includes a color-changing layer and the composite solid polymer electrolyte membrane prepared in example 6. Firstly, depositing ITO on glass by adopting a magnetron sputtering process, then respectively depositing tungsten oxide and nickel oxide on the ITO, arranging a composite solid polymer electrolyte membrane between the tungsten oxide and the nickel oxide, and carrying out hot pressing for 20min at 60 ℃.
Example 10
Solid state lithium battery
The solid lithium battery includes a positive electrode, a lithium metal negative electrode, and the composite solid polymer electrolyte membrane prepared in example 6, which is disposed between the positive electrode and the negative electrode. The anode active material is selected from lithium iron phosphate (LiFePO)4) The conductive agent is Super P, the binder is polyvinylidene fluoride (PVDF), and LiFePO is adopted according to the mass ratio4Mixing SuperP (PVDF) 8:1:1 in N-methylpyrrolidone (NMP) to obtain positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and carrying out vacuum drying at 110 ℃ for 24 hours to obtain a positive electrode piece. A button cell was assembled with lithium metal under an argon atmosphere using the composite solid polymer electrolyte membrane prepared in example 6.
Test example
(1) Lithium ion conductivity test
Forming an ss/solid polymer electrolyte/ss blocking battery by using a stainless steel sheet and a solid polymer electrolyte (thickness l, area S), testing the disturbance voltage of 5mV in a frequency range of 0.1-1000 kHz to obtain an EIS map, and obtaining the bulk resistance R of the solid polymer electrolytebAccording to the formula σ ═ l/(R)b× S) to obtain the lithium ion conductivity σ of the solid polymer electrolyte.
(2) Electrochemically stable window
The ss/solid polymer electrolyte/Li semi-blocking battery is formed by a stainless steel sheet, a solid polymer electrolyte and a lithium sheet, a sample is processed for 2 hours at 80 ℃ and under certain pressure for standby, and the sample is tested by linear sweep voltammetry, wherein the sweep rate is 2mV/S, and the open-circuit voltage in the voltage sweep range is 0V to 6V.
(3) Interface impedance
By lithium flake and solid state polymerizationThe electrolyte is formed into Li// solid polymer electrolyte// Li non-blocking battery, the sample is processed for 2h at 80 ℃ and under certain pressure for standby, 5mV disturbance voltage and 0.1-1000 kHz frequency range are tested to obtain EIS map, and SEI membrane resistance R of solid polymer electrolyte and lithium sheet is obtained after fittingseiAnd an interface reaction resistance RctThe interfacial resistance R ═ Rsei+Rct。
(4) Tensile strength
Referring to the test method of the tensile property of the plastic film in the standard GB/T13022-1991, the speed is 50mm/min, the electrolyte film is cut into sample pieces with the width of 15mm and the length of more than 18cm for standby, the thickness of the sample pieces is measured by a thickness gauge, and then the average thickness of the sample pieces is calculated.
Calculation formula of tensile strength: tensile strength-maximum force/cross-sectional area
(5) Electrochromic device cycling
And (3) testing by using an electrochemical workstation and a timing current method, wherein square wave voltage is +/-2V, the color change time and the color fading time are respectively 30s, and the cycle time is 300 times.
(6) Solid state lithium battery cycling
And carrying out a charge-discharge test on the assembled solid lithium battery within the range of 2.5-3.7V in the environment of 60 ℃.
The test results are shown in table 1.
TABLE 1 Performance test results for examples 1-8
In comparative examples 1, 2, and 3, the mechanical properties were poor due to the use of a polymer that conducts lithium ions only, and the electrolyte membrane made of PEO had low tensile strength and was prone to short-circuiting; the electrolyte membrane made of PMMA and PPC is brittle and hard, has poor contact with stainless steel and a lithium sheet, has poor bonding performance and large interface impedance.
The performance of the examples 1 to 8 is superior to that of the comparative examples 1 to 3, because the composite solid polymer electrolyte adopts a thermosetting-thermoplastic composite mode, the advantages of the two are combined, and the mechanical performance and the electrochemical performance are both considered. The specific analysis is as follows: example 2 compared to example 1, the ionic conductivity increased, but the electrochemical window and tensile strength decreased, since example 2 used a crosslinking monomer containing two functionalities, resulting in a thermoset polymer with a low degree of crosslinking, and therefore a lower electrochemical window and tensile strength than example 1. Compared with the embodiment 1, the embodiment 3 has the advantages that the nano inorganic particles are added, the crystallization is inhibited, the lithium ion conduction path is increased, and the ion conductivity, the tensile strength and other properties are improved. Compared with the embodiment 3, the embodiment 4 has the advantages that the content of lithium salt is reduced, the lithium salt can reduce the crystallinity, the state of the solid polymer electrolyte is changed, the adhesiveness of the film is improved, and the interface performance is improved; so that the ion conductivity and the interfacial property of example 4 are degraded. In comparison with example 3, in example 5, PC was added as a plasticizer, and the ionic conductivity was improved by PC, but PC was partially volatilized during the crosslinking and curing process, and only a part of PC remained to function. Example 6 compared with examples 3 and 5, the TEGDME is added as a plasticizer, so that volatilization loss is avoided, the ionic conductivity can be remarkably improved, the interface impedance is reduced, and part of mechanical properties can also be reduced. The thermosetting polymer in the composite solid polymer electrolytes of examples 7 and 8 is obtained by adopting a UV curing process, has high crosslinking degree, so that the ionic conductivity and the interface performance are slightly lower than those of a solid polymer electrolyte membrane crosslinked by a thermal crosslinking process, but the electrochemical window and the tensile strength are better.
Examples 9 and 10 are applications of composite solid polymer electrolyte membranes, and the electrochromic device was cycled 300 cycles at ± 2V without problems of bubbles, short circuits, etc., and the discoloration and fading current decay was small. The solid-state lithium battery is circulated at 60 ℃, has no problems of short circuit and the like, and has higher stability and electrochemical cycle performance at high temperature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A composite solid polymer electrolyte membrane, comprising: the lithium ion battery comprises a polymer component, a lithium salt, 0-25 parts by mass of a plasticizer and 0-15 parts by mass of inorganic particles, wherein the polymer component comprises 10-30 parts by mass of a thermoplastic polymer and 20-50 parts by mass of a cross-linked reticular polymer, and the molar ratio of the lithium salt to a lithium ion complexing dissociation group in the polymer component is 1 (1-16).
2. The composite solid polymer electrolyte membrane according to claim 1, wherein the content of the thermoplastic polymer with respect to the crosslinked network polymer is 50% to 400%.
3. The composite solid polymer electrolyte membrane according to claim 1, wherein the thermoplastic polymer is selected from at least one of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polycarbonate.
4. The composite solid polymer electrolyte membrane according to claim 1, wherein the crosslinked network polymer is crosslinked by at least one of photocuring and thermocuring from a crosslinking monomer;
optionally, the crosslinking monomer contains at least one of ethoxy, propoxy, butoxy;
optionally, the crosslinking monomer contains at least two ethylenically unsaturated bonds or at least two acetylenically unsaturated bonds;
optionally, the crosslinking monomers include at least one first crosslinking monomer containing at least two epoxide groups, and at least one second crosslinking monomer containing at least two amino groups.
5. The composite solid polymer electrolyte membrane according to claim 1, wherein the lithium salt is selected from the group consisting of LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiSCN、LiC(CF3SO2)3、(CF3SO2)2NLi、(FSO2)2At least one of NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl boric acid lithium, and imino lithium.
6. The composite solid polymer electrolyte membrane according to claim 1, wherein the plasticizer is at least one selected from the group consisting of imidazole-based ionic liquids, quaternary ammonium-based ionic liquids, piperidine-based ionic liquids, pyrrole-based ionic liquids, propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, and tetraglyme.
7. The composite solid polymer electrolyte membrane according to claim 1, wherein the inorganic particles are selected from at least one of alumina, silica, molecular sieves;
optionally, the inorganic particles have an average particle size of 5 to 100 nm.
8. The composite solid polymer electrolyte membrane according to any one of claims 1 to 7, wherein the thickness is 10 to 500 μm.
9. A method of producing the composite solid polymer electrolyte membrane according to any one of claims 1 to 8, comprising:
(1) mixing a thermoplastic polymer with a solvent to obtain a polymer solution; adding inorganic particles to the polymer solution to obtain a dispersion;
(2) adding lithium salt, a crosslinking monomer and a plasticizer into the dispersion liquid to obtain slurry;
(3) coating the slurry on a release film, removing the solvent, and carrying out photocuring crosslinking or thermocuring crosslinking to obtain the composite solid polymer electrolyte membrane;
optionally, the solvent is selected from at least one of acetonitrile, ethanol, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, acetone;
optionally, the concentration of the polymer solution is 5% to 30%.
10. Use of the composite solid polymer electrolyte membrane according to any one of claims 1 to 8 in a solid lithium battery and/or an electrochromic device.
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