Composition, polymer membrane comprising same, and secondary battery

Abstract

The objective of the present invention is to enhance the low lithium-ion conductivity of the prior art and improve problems related to the performance and stability of secondary batteries. The present invention relates to: a composition comprising a polysiloxane derivative and a polymer including a repeating unit represented by chemical formula 1 described in the present specification; a polymer membrane comprising same; and a secondary battery.

Description

Composition, polymer film and secondary battery comprising the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0101981, filed July 31, 2024, and Korean Patent Application No. 10-2024-0101982, filed July 31, 2024, the entire contents of which are incorporated herein by reference.

[0003]

[0004] Technology field

[0005] The present invention relates to a composition for improving the ionic conductivity and electrochemical properties of a solid electrolyte or forming a film on an electrode surface, a polymer film comprising the same, and a secondary battery.

[0006]

[0007] High-energy-density lithium secondary batteries, currently primarily used in laptops and smartphones, consist of a lithium oxide anode, a carbon-based cathode, a separator, and a liquid or solid electrolyte. However, lithium secondary batteries composed of flammable liquid electrolytes have safety issues such as leakage, ignition, and explosion, and the design of these batteries becomes more complex to prevent these issues.

[0008] Therefore, to solve the problems of these liquid electrolytes, research on solid electrolytes having non-flammable or flame-retardant properties is in progress, and the solid electrolytes can be classified into sulfide-based electrolytes, oxide-based electrolytes, and polymer electrolytes.

[0009] The above sulfide-based electrolyte has the advantages of high ionic conductivity, low interfacial resistance, and stability over a wide voltage range, but there are cases where trace impurities such as moisture mixed inside the battery react with the sulfide-based electrolyte to generate hydrogen sulfide inside the battery, and there is a risk of hydrogen sulfide being generated even when charging and discharging the battery, so it has the problem of being poor in terms of stability.

[0010] In addition, although the oxide-based electrolyte has high chemical stability, it has the disadvantages of having low ionic conductivity compared to the sulfide-based electrolyte, requiring high-temperature sintering treatment, and making it difficult to manufacture large-area batteries.

[0011] Accordingly, since the polymer electrolyte has the advantages of being a solid electrolyte material due to its characteristics of low cost, flexibility, and process convenience, research on the polymer electrolyte is being actively conducted.

[0012] The polymer electrolytes described above are broadly categorized into gel and solid types. Gel polymer electrolytes exhibit conductivity by impregnating a high-boiling-point liquid electrolyte within a polymer film and fixing it together with a lithium salt. Because they contain a large amount of liquid electrolyte, they possess ionic conductivity similar to that of pure liquid electrolytes, but electrochemical stability issues still remain.

[0013] On the other hand, solid polymer electrolytes, which do not contain liquid electrolytes, not only improve stability issues related to leakage, but also offer the advantage of high chemical and electrochemical stability. However, their ionic conductivity at room temperature is lower than that of liquid electrolytes, and extensive research is being conducted to improve this.

[0014] Currently, the most widely used solid polymer electrolyte is polyethylene oxide (PEO), which possesses the ability to conduct lithium ions despite its solid state. However, linear PEO polymer electrolytes suffer from limitations in chain mobility due to their high crystallinity, a low dielectric constant (5.0), which prevents the dissociation of large amounts of lithium ions, and very low ionic conductivity at room temperature, making them difficult to apply to lithium secondary batteries.

[0015] (Patent Document 001) JP 2006-199646 A

[0016]

[0017] The problem to be solved by the present invention is to provide a composition for improving the ionic conductivity of a polymer membrane and the performance, mechanical properties and electrochemical stability of a secondary battery, and a polymer membrane and a secondary battery including the same.

[0018] In addition, the problem to be solved by the present invention is to provide a composition for suppressing the growth of lithium dendritic crystals, i.e., dendrites, that occur on the surface of a lithium metal negative electrode, a polymer film including the same, and a secondary battery.

[0019]

[0020] The present invention provides a composition, a polymer film comprising the same, and a secondary battery.

[0021] (1) The present invention provides a composition comprising a polymer including a repeating unit represented by the following chemical formula 1; and a polysiloxane derivative.

[0022] [Chemical Formula 1]

[0023]

[0024] In the above chemical formula 1,

[0025] The above * indicates a connecting portion or terminal portion between repeating units,

[0026] Above L1 to L4, R a and R bare each independently, directly bonded; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0027] The above x and y are each independently integers greater than or equal to 1.

[0028] (2) The present invention provides a composition in the above (1), wherein L1 to L4 are each independently a substituted or unsubstituted C1-C5 alkylene group.

[0029] (3) The present invention provides a composition in which, in the above (1) or (2), the polymer includes a repeating unit represented by the following chemical formula 1-a.

[0030] [Chemical Formula 1-a]

[0031]

[0032] In the above chemical formula 1-a,

[0033] The above x and y are each independently integers greater than or equal to 1.

[0034] (4) The present invention provides a composition according to any one of the above (1) to (3), wherein the polysiloxane derivative is represented by the following chemical formula A.

[0035] [Chemical Formula A]

[0036]

[0037] In the above chemical formula A,

[0038] The above R 11 Inland R 15 and R 17 are each independently a hydrogen element; a halogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group; substituted or unsubstituted C2-C 10an alkenyl group of; or a substituted or unsubstituted C2-C 10 is an alkynyl group,

[0039] The above R 16 is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0040] The above R 18 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group,

[0041] Above L a and L b are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0042] The above q is an integer greater than or equal to 1,

[0043] The above o, p and r are each independently an integer greater than or equal to 0 or 1.

[0044] (5) The present invention is one of the above (1) to (4), wherein the R 11 Inland R 15 and R 17 are each independently a hydrogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; or substituted or unsubstituted A composition is provided which is an alkyl group of C1-C5.

[0045] (6) The present invention is one of the above (1) to (5), wherein the R 16 provides a composition in which the silver is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group.

[0046] (7) The present invention provides a composition in which, in any one of the above (1) to (6), the polysiloxane derivative is represented by at least one chemical formula selected from the group consisting of the following chemical formulas A-1 to A-8.

[0047] [Chemical Formula A-1]

[0048]

[0049] [Chemical Formula A-2]

[0050]

[0051] [Chemical Formula A-3]

[0052]

[0053] [Chemical Formula A-4]

[0054]

[0055] [Chemical Formula A-5]

[0056]

[0057] [Chemical Formula A-6]

[0058]

[0059] [Chemical Formula A-7]

[0060]

[0061] [Chemical Formula A-8]

[0062]

[0063] In the above chemical formulas A-1 to A-8,

[0064] The above q and o2 are each independently an integer greater than or equal to 1,

[0065] Above o, o 1, p and r are each independently an integer greater than or equal to 0 or 1.

[0066] (8) The present invention provides a composition according to any one of (1) to (7), wherein the polysiloxane derivative is represented by the following chemical formula B.

[0067] [Chemical Formula B]

[0068]

[0069] In the above chemical formula B,

[0070] The above R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group; substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 an alkynyl group; or a functional group represented by the following chemical formula B,

[0071] The above R 26 is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0072] The above R 20 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group,

[0073] Above L c , L d , L e and L f are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0074] The above s is an integer greater than or equal to 1,

[0075] The above v1, v2, v3 and w are each independently integers greater than or equal to 0 or 1,

[0076] [Chemical Formula C]

[0077]

[0078] In the above chemical formula C,

[0079] Above L g and L hare each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0080] The above R 31 Silver is a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 an alkoxy group; or a substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 is an alkynyl group,

[0081] The above t is an integer greater than or equal to 0 or 1.

[0082] (9) The present invention, in the above (8), the R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; or substituted or unsubstituted A composition is provided which is an alkyl group of C1-C5.

[0083] (10) The present invention, in the above (8) or (9), the R 26 provides a composition in which the silver is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group.

[0084] (11) The present invention provides a composition in which, in any one of the above (8) to (10), v1, v2 and v3 are each independently an integer of 3 or more.

[0085] (12) The present invention provides a composition in which, in any one of the above (1) to (11), the polysiloxane derivative is represented by at least one chemical formula selected from the group consisting of the following chemical formulas B-1 to B-7.

[0086] [Chemical Formula B-1]

[0087]

[0088] [Chemical Formula B-2]

[0089]

[0090] [Chemical Formula B-3]

[0091]

[0092] [Chemical Formula B-4]

[0093]

[0094] [Chemical Formula B-5]

[0095]

[0096] [Chemical Formula B-6]

[0097]

[0098] [Chemical Formula B-7]

[0099]

[0100] In the above chemical formulas B-1 to B-7,

[0101] The above s and w are each independently integers greater than or equal to 1,

[0102] The above v1, v2 and v3 are each independently integers greater than or equal to 3.

[0103] The above t is an integer greater than or equal to 0 or 1.

[0104] (13) The present invention provides a composition according to any one of the above (1) to (12), wherein the composition further comprises a polyether derivative.

[0105] (14) The present invention provides a composition comprising a polymer having a crosslinking functional group at at least one terminal of at least one polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl ether, and combinations thereof, in the above (13).

[0106] (15) The present invention is any one of the above (1) to (14), wherein the composition comprises LiCl, LiBr, LiI, LiBF4, LiClO4, LiB 10 Cl 10 , LiAlCl4, LiAlO4, LiPF6, LiCF3SO3, LiCH3CO2, LiCF3CO2, LiAsF6, LiSbF6, LiCH3SO3, LiFSI (lithium bis(fluorosulfonyl)imide, LiN(SO2F)2), LiBETI (lithium bisperfluoroethanesulfonimide, LiN(SO2CF2CF3)2) and LiTFSI (lithium (bis)trifluoromethanesulfonimide, LiN(SO2CF3)2).

[0107] (16) The present invention provides a composition according to any one of the above (1) to (15), wherein the composition comprises inorganic particles.

[0108] (17) The present invention provides a composition comprising solid electrolyte particles including one or more elements selected from the group consisting of constituent elements Li, Al, Ti, La, Zr, O, P, Ge, and S, in any one of the above (1) to (16).

[0109] (18) The present invention provides a polymer film comprising a composition according to any one of (1) to (17).

[0110] (19) The present invention provides a polymer membrane comprising a porous substrate including at least one material selected from the group consisting of polyethylene, polypropylene, polyimide, polybenzimidazole, cellulose, and glass fiber, in the above (18).

[0111] (20) The present invention provides a secondary battery including a polymer film according to (18) or (19).

[0112]

[0113] According to the present invention, when a composition comprising a polymer having a lithium-friendly structure capable of chelating lithium ions and a lithium salt thereof and a polyether polymer is applied to a battery, the ion conductivity and ion transport rate can be improved.

[0114] According to the present invention, when a composition having excellent lithium ion transport rate and smoothly performing curing is applied to an electrolyte, it can have the effect of suppressing the growth of lithium dendrite crystals occurring on the surface of a negative electrode.

[0115]

[0116] Hereinafter, the present invention will be described in more detail to facilitate understanding. The terms and words used in this specification and claims should not be interpreted based on their conventional or dictionary meanings. Rather, they should be interpreted based on the principle that the inventor can appropriately define the concepts of terms to best explain his or her invention. Therefore, they should be interpreted based on meanings and concepts consistent with the technical spirit of the present invention.

[0117] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0118] In this specification, it should be understood that the terms “include,” “comprising,” or “having” are intended to specify the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0119] The term "substituted or unsubstituted" in this specification means substituted with one or more substituents selected from among deuterium, halogen, hydroxy, amino, thiol, nitro, nitrile, silyl, and straight or branched C1-C6 alkoxy groups, or has no substituents.

[0120] The term “alkyl group” used herein may mean, unless otherwise specified, a straight or branched acyclic group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms; a cyclic group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms; or a saturated hydrocarbon group combined therewith.

[0121] The term “alkenyl group” used herein may mean, unless otherwise specified, a straight-chain branched acyclic group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms and having one or more double bonds; a cyclic group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms and having one or more double bonds; or an unsaturated hydrocarbon group combined therewith.

[0122] The term “alkynyl group” used herein may mean, unless otherwise specified, a straight or branched chain acyclic group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms and having one or more triple bonds; a cyclic group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms and having one or more triple bonds; or an unsaturated hydrocarbon group combined therewith.

[0123] In this specification, “*” is a connecting portion or terminal portion between repeating units, and in the case of a terminal, a hydrogen atom; -CN; -NH 2; Halogen elements; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group; substituted or unsubstituted C2-C 10 an alkenyl group of; or a substituted or unsubstituted C2-C 10 It may mean one or more selected from the group consisting of alkynyl groups.

[0124]

[0125] Composition

[0126] The present invention provides a composition comprising a polymer including a repeating unit represented by the following chemical formula 1; and a polysiloxane derivative.

[0127] [Chemical Formula 1]

[0128]

[0129] In the above chemical formula 1,

[0130] The above * indicates a connecting portion or terminal portion between repeating units,

[0131] Above L1 to L4, R a and R b are each independently, directly bonded; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0132] The above x and y are each independently integers greater than or equal to 1.

[0133]

[0134] Conventional liquid electrolytes are flammable, which causes safety issues such as ignition. Solid electrolytes have excellent process stability because they do not cause liquid leakage problems, and they can be processed into thin films and films, which makes them excellent in process convenience. However, as described above, they have the disadvantage that ionic conductivity is significantly reduced compared to conventional liquid electrolytes. Accordingly, the inventors of the present invention have developed a polymer having a lithium ion-friendly structure, a composition, and an ion-conducting polymer membrane (solid electrolyte) comprising the same.

[0135] In addition, among the compositions of the present invention, the polyether polymer can be used as a main material constituting a solid electrolyte. However, as described above, the polyether polymer has lower ionic conductivity at room temperature than a liquid electrolyte, and can exhibit high interfacial resistance between the electrode and the electrolyte. In order to solve these problems, the inventor of the present invention developed an ion conductive composition comprising a polysiloxane derivative as a matrix resin and a polymer including a repeating unit represented by Chemical Formula 1, thereby providing a solid electrolyte having excellent electrochemical properties and high ionic conductivity.

[0136]

[0137] The polymer including the repeating unit represented by the above chemical formula 1 is a compound having a lithium-friendly structure capable of chelating lithium ions. The polymer including the repeating unit represented by the above chemical formula 1 contains an anion of sulfonimide in which a proton bonded to a nitrogen atom in sulfonimide is detached, and therefore, when used as a material for a solid electrolyte, it may have high affinity for lithium ions. In a process for manufacturing a solid electrolyte including the polymer including the repeating unit represented by the above chemical formula 1, the proton bonded to the nitrogen atom in sulfonimide may be detached, enabling anionization of sulfonimide. In addition, the anion of the sulfonimide has a relatively small electron density compared to anions of other organic groups such as carboxylate, and thus has a weak electrostatic attraction with lithium ions, and therefore, the transport rate of lithium ions in the solid electrolyte can be increased. In particular, the polymer may have the effect of improving the lithium ion transference number compared to using a material obtained by hydrogenating an existing ethylene oxide-based material or a material mixed with a lithium salt separately, for example, a PEO mixture mixed with a lithium salt, alone.

[0138] In addition, the polymer comprising the repeating unit represented by the above chemical formula 1 can delocalize the electrons of the sulfonimide anion, thereby further improving the ionic conductivity of the solid electrolyte. In addition, the polymer according to the present invention also functions as a conventional lithium salt in the solid electrolyte, and thus can replace the conventional lithium salt, thereby reducing the manufacturing cost of the secondary battery.

[0139]

[0140] In addition, lithium metal anodes, which are anode materials that are in the spotlight in next-generation batteries including conventional secondary batteries, have chronic problems such as shortened lifespan and side reactions due to the formation of lithium dendrites, i.e., lithium dendritic crystals. However, the polymer film (layer) positioned on the solid electrolyte or metal electrode layer including the composition of the present invention has a high lithium ion transference number, thereby suppressing the dendrite phenomenon and improving the lifespan of the battery. In addition, in a rapid charging environment, lithium dendrite formation is accelerated, making it difficult to introduce rapid charging in a conventional lithium metal battery composition, but in the case of a secondary battery including the composition of the present invention, since the dendrite phenomenon is suppressed, rapid charging may be possible. The composition of the present invention may include a polymer including a repeating unit represented by Chemical Formula 1 and a polysiloxane derivative, and in particular, as shown in the experimental results described below, the polymer has a significantly high lithium ion transference number, thereby suppressing dendrite formation more effectively.

[0141] According to one embodiment of the present invention, the L1 to L4, R a and R b Each independently may be a substituted or unsubstituted C1-C5 alkylene group. Here, L1 to L4, R a and R bThe definition of may be different for each repeating unit or block. When L1 to L4 satisfy the above definition, carbon atoms may be positioned on both sides of the sulfur atom based on the disulfonimide group. If oxygen atoms are positioned on both sides of the sulfur atoms constituting the disulfonimide group, the hydrolysis energy is significantly lowered, and in this case, a problem of reduced stability against moisture and stability in the battery environment may occur. The polymer of the present invention has a structure in which oxygen atoms do not exist on both sides of the sulfur atoms, thereby preventing the reduction in moisture stability.

[0142] In addition, the polymer can further improve ionic conductivity by including an ethylene oxide structure between disulfonimides. The polymer can have higher ionic conductivity than conventional alkylene oxide polymers, and when used in secondary batteries, can have electrochemical stability even at high voltages.

[0143] In addition, according to one embodiment of the present invention, a composition is provided wherein the polymer includes a repeating unit represented by the following chemical formula 1-a.

[0144] [Chemical Formula 1-a]

[0145]

[0146] In the above chemical formula 1-a,

[0147] The above x and y are each independently integers greater than or equal to 1.

[0148] When the polymer including the repeating unit represented by the above chemical formula 1 is represented by the above chemical formula 1-a, it can have a higher lithium ion conductivity compared to the polymer material of the solid electrolyte or polymer membrane that has been used previously.

[0149]

[0150] According to one embodiment of the present invention, the polysiloxane derivative may be represented by the following chemical formula A.

[0151] [Chemical Formula A]

[0152]

[0153] In the above chemical formula A,

[0154] The above R 11 Inland R 15 and R 17 are each independently a hydrogen element; a halogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group; substituted or unsubstituted C2-C 10 an alkenyl group of; or a substituted or unsubstituted C2-C 10 is an alkynyl group,

[0155] The above R 16 is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0156] The above R 18 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group,

[0157] Above L a and L b are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0158] The above q is an integer greater than or equal to 1,

[0159] The above o, p and r are each independently an integer greater than or equal to 0 or 1.

[0160]

[0161] According to one embodiment of the present invention, the R 11 Inland R 15 and R 17are each independently a hydrogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; or substituted or unsubstituted It may be a C1-C5 alkyl group. In addition, the R 16 is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group. The polysiloxane derivative contains siloxane in the main chain, and an ethylene oxide organic group can be connected to the main chain as a side chain. The polysiloxane derivative of the present invention has an advantage in that it can improve ion conductivity compared to polyethylene oxide by having an ethylene oxide organic group connected to the side chain compared to existing polysiloxane. Specifically, polysiloxane is an amorphous polymer without crystallinity, and can reduce the crystallinity of polyethylene oxide, thereby improving ion conductivity. In addition, due to ethylene oxide connected to the side chain of polysiloxane, it can improve miscibility with a hydrophilic polymer like polyethylene oxide, which is originally not mixed well. Through this, when a polysiloxane in which ethylene oxide is substituted in the side chain is used, the mobility of lithium ions can be increased compared to existing polyethylene oxide, and thereby ion conductivity can be further improved.

[0162] Furthermore, polyethylene oxide (PE) is known to have a lithium ion transport rate of around 0.2, making it necessary to improve its properties. Improving the lithium ion transport rate can further enhance practical lithium ion conductivity and improve all electrochemical properties within the battery. Furthermore, when lithium metal is used as the anode, uneven lithium dendrite growth on the surface can cause various problems. Using a protective film with improved lithium ion transport can make the lithium ion flow more uniform, thereby mitigating dendrite growth.

[0163] Therefore, to increase lithium ion transport rates while maintaining compatibility with polyethylene oxide, a single ion conductor can be introduced by substituting both terminals of polyethylene oxide. Specifically, the method of modifying the terminals using ethylene oxide, which is capable of conducting ions, can be easily manufactured, and lithium ion counterions can be directly introduced into the structure.

[0164] Additionally, according to one embodiment of the present invention, in the chemical formula A, each block including Si-O may be sequentially or randomly arranged and connected to each other.

[0165] According to one embodiment of the present invention, the polysiloxane derivative may be represented by one or more chemical formulas selected from the group consisting of the following chemical formulas A-1 to A-8.

[0166] [Chemical Formula A-1]

[0167]

[0168] [Chemical Formula A-2]

[0169]

[0170] [Chemical Formula A-3]

[0171]

[0172] [Chemical Formula A-4]

[0173]

[0174] [Chemical Formula A-5]

[0175]

[0176] [Chemical Formula A-6]

[0177]

[0178] [Chemical Formula A-7]

[0179]

[0180] [Chemical Formula A-8]

[0181]

[0182] In the above chemical formulas A-1 to A-8,

[0183] The above q and o2 are each independently an integer greater than or equal to 1,

[0184] Above o, o 1, p and r are each independently an integer greater than or equal to 0 or 1.

[0185] When the above polysiloxane derivative is represented by one or more chemical formulas selected from the group consisting of A-1 to A-8, it can have higher lithium ion conductivity compared to the polymer material of the solid electrolyte previously used.

[0186]

[0187] According to one embodiment of the present invention, the polysiloxane derivative may be represented by the following chemical formula B.

[0188] [Chemical Formula B]

[0189]

[0190] In the above chemical formula B,

[0191] The above R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group; substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 an alkynyl group; or a functional group represented by the following chemical formula B,

[0192] The above R 26is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group,

[0193] The above R 20 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group,

[0194] Above L c , L d , L e and L f are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0195] The above s is an integer greater than or equal to 1,

[0196] The above v1, v2, v3 and w are each independently integers greater than or equal to 0 or 1,

[0197] [Chemical Formula C]

[0198]

[0199] In the above chemical formula C,

[0200] Above L g and L h are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group,

[0201] The above R 31 Silver is a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 an alkoxy group; or a substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 is an alkynyl group,

[0202] The above t is an integer greater than or equal to 0 or 1.

[0203]

[0204] According to one embodiment of the present invention, the R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; or substituted or unsubstituted It may be a C1-C5 alkyl group. In addition, the R 26 is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group. The polysiloxane derivative contains dimethylsilane in the main chain, and an ethylene oxide organic group can be connected to the main chain as a side chain. The polysiloxane derivative of the present invention has an advantage in that it can improve ion conductivity compared to polyethylene oxide by having an ethylene oxide organic group connected to the side chain compared to existing polysiloxanes. Specifically, polysiloxane is an amorphous polymer without crystallinity, and can reduce the crystallinity of polyethylene oxide, thereby improving ion conductivity. In addition, due to ethylene oxide connected to the side chain of polysiloxane, it can improve miscibility with a hydrophilic polymer like polyethylene oxide, which is originally not mixed well. Through this, when a polysiloxane in which ethylene oxide is substituted in the side chain is used, the mobility of lithium ions can be increased compared to existing polyethylene oxide, and thereby ion conductivity can be further improved.

[0205] Additionally, according to one embodiment of the present invention, in the chemical formula B, each block including Si-O may be sequentially or randomly arranged and connected to each other.

[0206] According to one embodiment of the present invention, the polysiloxane derivative may be represented by one or more chemical formulas selected from the group consisting of the following chemical formulas B-1 to B-7.

[0207] [Chemical Formula B-1]

[0208]

[0209] [Chemical Formula B-2]

[0210]

[0211] [Chemical Formula B-3]

[0212]

[0213] [Chemical Formula B-4]

[0214]

[0215] [Chemical Formula B-5]

[0216]

[0217] [Chemical Formula B-6]

[0218]

[0219] [Chemical Formula B-7]

[0220]

[0221] In the above chemical formulas B-1 to B-7,

[0222] The above s and w are each independently integers greater than or equal to 1,

[0223] The above v1, v2 and v3 are each independently integers greater than or equal to 3.

[0224] The above t is an integer greater than or equal to 0 or 1.

[0225] When the above polysiloxane derivative is represented by one or more chemical formulas selected from the group consisting of B-1 to B-7, it can have higher lithium ion conductivity compared to the polymer material of the polymer membrane (solid electrolyte) previously used.

[0226]

[0227] In addition, according to one embodiment of the present invention, v1, v2, and v3 may be v1+v2+v3 ≥ 9, and v1, v2, and v3 may each independently be an integer of 3 or more. The compound including the polysiloxane derivative includes an ethylene oxide structure as a side chain in a dimethylsilane or hydrosilane main chain, wherein the total number of repeating units of the ethylene oxide structure may be 9 or more. When the total number of repeating units of the ethylene oxide or the number of each repeating unit satisfies the above range, ionic conductivity and mechanical strength can be effectively improved. The compound may have higher ionic conductivity than existing alkylene oxide-based polymers, and may have electrochemical stability even at high voltage when used in a secondary battery.

[0228]

[0229] According to one embodiment of the present invention, the composition may further include a polyether derivative, and the polyether polymer may include a polymer having a crosslinking functional group at at least one terminal of at least one polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl ether, and combinations thereof. Specifically, the polyether polymer may include at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and combinations thereof. Here, the combination may have the form of a random copolymer, a block copolymer, or a graft copolymer, and for example, may be a random copolymer of polyethylene oxide and polypropylene oxide.

[0230] In addition, the crosslinking functional group here may include a functional group having a structure derived from an acrylate group, a methacrylate group, or a vinyl group, and by including the crosslinking functional group, the formation of a network between the compounds and polymers included in the composition can be facilitated. By forming the network, the weight average molecular weight of the polymer can be significantly increased, and thus, when the composition is applied to a solid electrolyte, the mechanical strength of the solid electrolyte can be improved.

[0231] Additionally, according to one embodiment of the present invention, the weight average molecular weight of the polyether polymer may be 50,000 g / mol or more and 5,000,000 g / mol or less. For example, the weight average molecular weight of the polyether polymer may be 50,000 g / mol or more, 60,000 g / mol or more, 70,000 g / mol or more, 90,000 g / mol or more, 100,000 g / mol or more, 120,000 g / mol or more, 140,000 g / mol or more, 150,000 g / mol or more, 5,000,000 g / mol or less, 4,500,000 g / mol or less, 4,000,000 g / mol or less, 3,500,000 g / mol or less, 3,000,000 g / mol or less, 2,500,000 g / mol or less, 2,000,000 g / mol or less, and specifically, 100,000 g / mol or more It may be 2,000,000 g / mol or less. When the weight average molecular weight of the polyether polymer satisfies the above range, the mechanical properties and electrochemical stability of the polymer electrolyte can be secured, while the ion transfer capability of the polymer electrolyte can be improved.

[0232] According to one embodiment of the present invention, the composition may include a lithium compound. The polymer including the repeating unit represented by the above chemical formula 1 may be bonded to the lithium compound by electrostatic attraction, and the composition of the present invention may further include the lithium compound, thereby increasing the transport rate of lithium ions, thereby improving ion conductivity, and achieving the effect of reducing the diffusion resistance of lithium ions, thereby implementing the effect of improving the cycle capacity characteristics of the secondary battery. The lithium compound may be a lithium salt (Li) in the composition. + A - ) may exist in the form of, for example, the lithium compound may be LiCl, LiBr, LiI, LiBF4, LiClO4, LiB 10 Cl 10 , LiAlCl4, LiAlO4, LiPF6, LiCF3SO3, LiCH3CO2, LiCF3CO2, LiAsF6, LiSbF6, LiCH3SO3, LiFSI (lithium bis(fluorosulfonyl)imide, LiN(SO2F)2), LiBETI (lithium bisperfluoroethanesulfonimide, LiN(SO2CF2CF3)2) and LiTFSI (lithium (bis)trifluoromethanesulfonimide, LiN(SO2CF3)2).

[0233] According to one embodiment of the present invention, the composition may include inorganic particles. The inorganic particles may be included in the composition to enhance the mechanical strength and thermal stability of the polymer film, thereby improving the cycle characteristics of the secondary battery. In addition, the inorganic particles may effectively suppress the formation of defects inside the polymer film including the composition by alleviating local imbalances that may occur between particles. The inorganic particles may be a metal oxide, and for example, may be a binary metal oxide including one type of metal element and an oxygen atom. More specifically, the inorganic particles may include at least one selected from the group consisting of MgO, SiO2, Al2O3, TiO2, Ti2O3, ZrO2, ZnO, B2O, B2O3, Ga2O3, TeO, TeO3, Cs2O, SnO, SnO2, CrO3, Cr2O3, BeO, FeO, Fe2O3, BaO, PbO, PbO2, Pb2O3, and Pb3O4.

[0234] In addition, according to one embodiment of the present invention, the composition may include solid electrolyte particles including one or more elements selected from the group consisting of constituent elements Li, Al, Ti, La, Zr, O, P, Ge, and S. For example, the composition may include oxide-based solid electrolyte particles including lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium aluminum germanium phosphate (LAGP), lithium lanthanum titanite oxide (LLTO), etc., and / or sulfide-based solid electrolyte particles including germanium phosphorus sulfide (LGP), lithium phosphorus sulfide (LPS), etc. In addition, the solid electrolyte particles may be included in an amount of 0.5 to 95.0 parts by weight based on 100 parts by weight of the total composition. In addition, the solid electrolyte particles may further include a doping element material to improve electrochemical characteristics.

[0235]

[0236] polymer membrane

[0237] The present invention provides a polymer membrane comprising the above composition. The polymer membrane may comprise a solid electrolyte. Specifically, the composition may comprise a polymer comprising a repeating unit represented by the above chemical formula 1 or a lithium salt thereof, and a polysiloxane derivative. Since the polymer membrane comprises a polymer comprising a lithium ion-friendly structure, lithium ion mobility may be enhanced, thereby enhancing ion conductivity.

[0238]

[0239] Meanwhile, the present invention can prepare a mixed solution by mixing a solvent and the composition, and form an ion-conducting polymer electrolyte film through a film manufacturing process using the mixed solution. The solvent may be at least one selected from the group consisting of methanol, ethanol, 2-propanol, butanol, 2-ethoxyethanol, isopropyl alcohol, ethyl acetate, butyl acetate, acetone, dichloroethane, acetonitrile, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphamide, 1,3-dimethyl-2-imidazolidinone, triethyl phosphate, and gamma-butyrolactone. The content of the solvent may be determined in consideration of the viscosity of the mixed solution, etc.

[0240]

[0241] In addition, the film manufacturing process may be a solution casting method (solution casting method), a melt extrusion method, a calendar method, or a compression molding method, and more specifically, may be a solution casting method. The solution casting method may be performed by coating on a separate substrate, separating it, and then laminating it with the positive and negative electrodes. The substrate may be a glass substrate or a plastic substrate. Examples of the plastic substrate include various plastic films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly(meth)acrylic acid alkyl ester, poly(meth)acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. The thickness of the support is preferably 5 to 150 μm, more preferably 10 to 50 μm. In addition, the coating may be applied by any of the following methods: spin coating, dip coating, solvent casting, slot die coating, spray coating, roll coating, extrusion coating, curtain coating, die coating, wire bar coating, or knife coating.

[0242]

[0243] secondary batteries

[0244] The present invention provides a secondary battery including the polymer film.

[0245] According to one embodiment of the present invention, the secondary battery includes a positive electrode, a negative electrode (or anode-less), and a solid electrolyte layer including a polymer membrane disposed between the positive electrode and the negative electrode. The secondary battery according to the present invention has a small decrease in ionic conductivity, and the electronic conductivity of the included solid electrolyte is low, so that the initial efficiency, lifespan characteristics, and output characteristics of the secondary battery can be excellent. At this time, the secondary battery of the present invention can be manufactured according to a conventional method known in the art. For example, it can be manufactured by laminating and pressing so that the solid electrolyte layer is present between the positive electrode and the negative electrode.

[0246]

[0247] (1) Bipolar

[0248] The above positive electrode can be manufactured by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive agent, a solvent, etc. on a positive electrode current collector.

[0249] The positive electrode current collector is not particularly limited as long as it is conductive and does not cause a chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver, etc. may be used. In addition, the bonding strength of the positive electrode active material may be strengthened by forming fine irregularities on the surface, and may be used in various forms such as a film, sheet, foil, net, porous body, foam, or non-woven fabric.

[0250]

[0251] The above-mentioned positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically may include a lithium metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. More specifically, the lithium metal oxide may be a lithium-manganese oxide (e.g., LiMnO2, LiMn2O4, etc.), a lithium-cobalt oxide (e.g., LiCoO2, etc.), a lithium-nickel oxide (e.g., LiNiO2, etc.), a lithium-nickel-manganese oxide (e.g., LiNi 1-Y Mn Y O2 (here, 0 <Y<1), LiMn 2-z Ni z O4 (where 0<Z<2), etc.), lithium-nickel-cobalt oxides (e.g., LiNi 1-Y1 Co Y1 O2 (here, 0 <Y1<1) 등), 리튬-망간-코발트계 산화물(예를 들면, LiCo 1-Y2 Mn Y2 O2 (here, 0 <Y2<1), LiMn 2-z1 Co z1 O4 (wherein, 0<Z1<2) etc.), lithium-nickel-manganese-cobalt oxides (e.g., Li(Ni p Co q Mn r1 )O2(wherein, 0<p<1, 0<q<1, 0<r1<1, p+q+r1=1) or Li(Ni p1 Co q1 Mn r2 )O4 (wherein, 0<p1<2, 0<q1<2, 0<r2<2, p1+q1+r2=2) etc.), or lithium-nickel-cobalt-transition metal (M) oxide (e.g., Li(Ni p2 Co q2 Mn r3 M S2)O2 (wherein, M is selected from the group consisting of Al, Fe, V, Cr, Ti, Ta, Mg and Mo, and p2, q2, r3 and s2 are atomic fractions of independent elements, respectively, 0<p2<1, 0<q2<1, 0<r3<1, 0<s2<1, p2+q2+r3+s2=1), etc.), and one or more compounds of these may be included.

[0252] Among these, the lithium metal oxides are LiCoO2, LiMnO2, LiNiO2, lithium nickel manganese cobalt oxide (e.g., Li(Ni)) in that they can improve the capacity characteristics and stability of the battery. 1 / 3 Mn 1 / 3 Co 1 / 3 )O2, Li(Ni 0.6 Mn 0.2 Co 0.2 )O2, Li(Ni) 0.5 Mn 0.3 Co 0.2 )O2, Li(Ni 0.7 Mn 0.15 Co 0.15 )O2 and Li(Ni 0.8 Mn 0.1 Co 0.1 )O2, etc.), or lithium nickel cobalt aluminum oxide (e.g., Li(Ni 0.8 Co 0.15 Al 0.05 )O2, etc.), and considering the remarkable improvement effect according to the control of the type and content ratio of the constituent elements forming the lithium composite metal oxide, the lithium composite metal oxide may be Li(Ni 0.6 Mn 0.2 Co 0.2 )O2, Li(Ni) 0.5 Mn 0.3 Co 0.2 )O2, Li(Ni 0.7 Mn 0.15 Co 0.15 )O2 and Li(Ni 0.8 Mn 0.1 Co 0.1)O2, etc., and any one of these or a mixture of two or more of them may be used.

[0253] The above positive electrode active material may be included in an amount of 60 wt% or more, 70 wt% or more, 80 wt% or more, or 99 wt% or less, or 98 wt% or less, based on the total weight of the solid content excluding the solvent in the positive electrode slurry.

[0254] The above binder is a component that assists in bonding between the conductive material, the active material, and the current collector. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, and various copolymers thereof.

[0255] Typically, the binder may be included in an amount of 1 wt% to 20 wt%, preferably 1 wt% to 15 wt%, and more preferably 1 wt% to 10 wt%, based on the total weight of solids excluding the solvent in the positive electrode slurry.

[0256] The above-mentioned conductive agent is a component for further improving the conductivity of the positive electrode active material.

[0257] The conductive material is not particularly limited as long as it is conductive and does not cause a chemical change in the battery, and for example, carbon-based materials such as graphite; carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers or metal fibers; metal powders such as fluorinated carbon, aluminum, and nickel powders; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives can be used.

[0258] Typically, the conductive material may be included in an amount of 1 wt% or more, 20 wt% or less, 15 wt% or less, or 10 wt% or less based on the total weight of solids excluding the solvent in the positive electrode slurry.

[0259] The solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that provides a desirable viscosity when including the positive electrode active material, and optionally a binder and a conductive material. For example, the positive electrode active material, and optionally a binder and a conductive material, may be included so that the solid concentration is 50 wt% or more, 60 wt% or more, 70 wt% or more, 95 wt% or less, 90 wt% or less, or 85 wt% or less.

[0260]

[0261] (2) Cathode

[0262] The above negative electrode can be manufactured, for example, by coating a negative electrode slurry containing a negative electrode active material, a binder, a conductive material, and a solvent on a negative electrode current collector, or a graphite electrode made of carbon (C) or lithium metal itself having a thickness of 50 μm or less can be used as the negative electrode, or the negative electrode can be excluded as an anode-less electrode.

[0263] For example, when manufacturing a negative electrode by coating a negative electrode slurry on the negative electrode current collector, the negative electrode current collector generally has a thickness of 3 to 500 ㎛. The negative electrode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, etc. can be used. In addition, like the positive electrode current collector, the bonding strength of the negative electrode active material can be strengthened by forming fine unevenness on the surface, and can be used in various forms such as a film, sheet, foil, net, porous body, foam, non-woven fabric, etc.

[0264] The above negative active materials include natural graphite, artificial graphite, carbonaceous materials; lithium-containing titanium composite oxide (LTO), Si, SiO x , Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe; alloys composed of the above metals (Me); oxides (MeO) of the above metals (Me) x ); and one or more types of negative electrode active materials selected from the group consisting of complexes of the above metals (Me) and carbon. Specifically, the negative electrode active materials include silicon (Si), silicon oxide (SiO x ) or a silicon-based negative electrode active material or lithium metal including a silicon alloy, etc. can be used. In the case of a silicon-based negative electrode active material, a thin and stable SEI layer including a siloxane bond is formed, which can further improve the high-temperature stability and lifespan characteristics of the battery.

[0265] In addition, in the case of the lithium metal, it may be a conventional one including lithium metal or a lithium alloy (for example, an alloy of lithium with a metal such as aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, or indium). The lithium metal negative electrode active material may be in the form of a foil, and by depositing the lithium metal negative electrode active material on one surface of the negative electrode current collector, the lithium metal negative electrode active material may form a separate layer from the negative electrode current collector.

[0266] The above negative electrode active material may be included in an amount of 60 wt% or more, 70 wt% or more, 80 wt% or more, 99 wt% or less, or 98 wt% or less based on the total weight of solids excluding the solvent in the negative electrode slurry.

[0267] The above binder is a component that assists in bonding between the conductive material, the active material, and the current collector. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, and various copolymers thereof.

[0268] Typically, the binder may be included in an amount of 1 wt% or more, 20 wt% or less, 15 wt% or less, or 10 wt% or less based on the total weight of solids excluding the solvent in the slurry for the negative electrode.

[0269] The above conductive agent is a component for further improving the conductivity of the negative electrode active material. The conductive agent is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and examples thereof include graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber or metal fiber; metal powders such as fluorocarbon, aluminum, and nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

[0270] The above-mentioned conductive agent may be included in an amount of 1 wt% or more, 20 wt% or less, 15 wt% or less, or 10 wt% or less based on the total weight of solids excluding the solvent in the negative electrode slurry.

[0271] The solvent may include water or an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that provides a desirable viscosity when including the negative electrode active material, and optionally a binder and a conductive material. For example, the concentration of the solid content including the negative electrode active material, and optionally a binder and a conductive material may be 50 wt% or more, 60 wt% or more, 70 wt% or more, 95 wt% or less, 90 wt% or less, or 85 wt% or less.

[0272] When using the metal itself as the above-mentioned cathode, it can be manufactured by physically bonding, rolling, or depositing the metal onto the metal thin film itself or the cathode current collector. The deposition method can use an electrical deposition method or a chemical vapor deposition method.

[0273] For example, the metal film itself or the metal bonded / rolled / deposited on the negative electrode current collector may include one or more metals selected from the group consisting of lithium (Li), nickel (Ni), tin (Sn), copper (Cu), and indium (In), or an alloy of two metals.

[0274]

[0275] (3) Solid electrolyte layer

[0276] The solid electrolyte layer may further include a binder in addition to a polymer film (solid electrolyte) comprising the composition according to the present invention.

[0277] The above binder is a component that assists in the bonding between solid electrolyte particles. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, and various copolymers thereof.

[0278] The above binder may be included in an amount of 0.1 wt% or more, 5 wt% or less, 3 wt% or less, or 2 wt% or less based on the total weight of the solid electrolyte layer.

[0279]

[0280] The present invention provides a battery module including the secondary battery as a unit cell and a battery pack including the same. The battery module and battery pack include the secondary battery having high capacity, high rate characteristics, and cycle characteristics, and thus can be used as a power source for medium- to large-sized devices selected from the group consisting of electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage systems.

[0281]

[0282] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be implemented in various different forms, and the following embodiments are merely illustrative examples to aid understanding of the present invention and do not limit the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is natural that such modifications and variations fall within the claims of this specification.

[0283]

[0284] <Synthesis example>

[0285] Synthesis Example 1

[0286] In a 3-Neck Round Bottom Flask (3-Neck RBF), 3 equivalents of NaH were dissolved in a THF (tetrahydrofuran) solution in which 1 equivalent of polyethylene glycol (number average molecular weight: 200) was dispersed, and the mixture was stirred. To the stirred material, a THF solution containing 1,3-propane sultone was added dropwise at 45°C. After stirring under reflux heating conditions, the conversion was confirmed to be complete through 1H NMR, and the solution was cooled to room temperature. After this, methanol (MeOH) was added to quench the remaining NaH. The solvent was removed under reduced pressure using a rotary evaporator to obtain a crude material, and the crude material was purified by washing with hexane and ether to obtain a primary intermediate material, (poly(ethylene glycol) bis(sodium propane-1-sulfonate).

[0287] After the above first intermediate material was dispersed in a DCM (dichloromethane) solvent, 3 equivalents of PCl5 were added. The mixture was stirred at 40°C for about 12 hours to obtain a crude solution, and the solvent was removed under reduced pressure using a rotary evaporator. The solution was then washed with hexane and ether and purified to obtain poly(ethylene glycol) bis(sodium propane-1-sulfonyl chloride), a compound represented by chemical formula a1.

[0288] [Chemical formula a1]

[0289]

[0290] Whether the compound represented by chemical formula a1 is synthesized 1 It was confirmed through H-NMR spectrum (Bruker, AVANCE NEO). The compound represented by the chemical formula a1 above 1 H-NMR data are as follows.

[0291] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.55~3.4(m, 20H), 2.6(m, 4H), 1.8(m, 4H)

[0292]

[0293] Next, 7 equivalents of NH4OH aqueous solution was added to the 3-Neck RBF under a nitrogen atmosphere and stirred at room temperature. The substance represented by the chemical formula a1 was dispersed in acetonitrile, and the dispersed solution was slowly added to the stirred substance over 7 hours, and the solution was stirred at 40°C for about 12 hours. After that, water was added and the mixture was extracted several times with ethyl acetate. The organic layer was dried over Na2SO4, and the solvent was removed under reduced pressure using a rotary evaporator, washed and purified with ether, and dried to obtain poly(ethylene glycol) bis(propane-1-sulfonamide), a compound represented by the chemical formula a2.

[0294] [Chemical formula a2]

[0295]

[0296] Whether the compound represented by chemical formula a2 is synthesized 1 It was confirmed through H-NMR spectrum (Bruker, AVANCE NEO). The compound represented by the chemical formula a2 above 1 H-NMR data are as follows.

[0297] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 6.87(broad S, 4H), 3.43(m, 23H), 3.03(m, 4H), 1.89(m, 4H)

[0298]

[0299] Synthesis Example 2

[0300] Among the methods for producing a compound represented by chemical formula a1 of the above Synthesis Example 1, a compound represented by chemical formula a3 was produced by performing the same procedure except that polyethylene glycol (number average molecular weight: 200) was replaced with polyethylene glycol (number average molecular weight: 1000).

[0301] [Chemical formula a3]

[0302]

[0303] Whether the compound represented by chemical formula a3 can be synthesized 1 It was confirmed through H-NMR spectrum (Bruker, AVANCE NEO). The compound represented by the chemical formula a3 1 H-NMR data are as follows.

[0304] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.5(m, 80H), 3.4(m, 4H), 3.03(m, 4H), 1.9(m, 4H)

[0305]

[0306] Synthesis Example 3

[0307] Among the methods for producing a compound represented by chemical formula a1 of the above Synthesis Example 1, a compound represented by chemical formula a4 was produced by performing the same procedure except that polyethylene glycol (number average molecular weight: 200) was replaced with polyethylene glycol (number average molecular weight: 200).

[0308] [Chemical formula a4]

[0309]

[0310] Whether the compound represented by chemical formula a4 can be synthesized 1 It was confirmed through H-NMR spectrum (Bruker, AVANCE NEO). The compound represented by the chemical formula a4 above 1 H-NMR data are as follows.

[0311] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.5~3.4(m, 184H), 3.03(m, 4H), 1.9(m, 4H)

[0312]

[0313] <Manufacturing Example>

[0314] Manufacturing Example 1 - Manufacturing of a compound represented by Chemical Formula 1-a1

[0315] 3 equivalents of triethylamine and 1 equivalent of the compound represented by the above chemical formula a2 were dispersed in a DMF (Dimethylformamide) solution, and 1 equivalent of the compound represented by the above chemical formula a1 was added dropwise, followed by stirring at 120°C for 24 hours. Afterwards, the solution was cooled to room temperature, and water and dichloromethane were added, and the precipitate was separated by filtration from the obtained mixture. Thereafter, the obtained solid material was washed with methanol and then vacuum-dried. The vacuum-dried solid material was dispersed in anhydrous DMF, and 5 equivalents of lithium hydride were slowly added, followed by stirring at room temperature for 24 hours. Thereafter, unreacted lithium hydride was filtered, and the precipitate was separated by filtration from the obtained filtrate using an excess of tetrahydrofuran (THF).

[0316] The precipitate obtained by filtration and 3 equivalents of ammonia solution (7 M in MEOH, Sigma-Aldrich) were dispersed in a DMF (Dimethylformamide) solution, and stirred at 50°C for 24 hours. Thereafter, the stirred solution was cooled to room temperature, and dichloromethane was added. The precipitate was separated by filtration from the resulting mixture, thereby obtaining a compound represented by the following chemical formula 1-a1.

[0317] [Chemical Formula 1-a1]

[0318]

[0319] The synthesis of the compound represented by the above chemical formula 1-a1 was confirmed through GPC (Waters, e2695 GPC). The number-average molecular weight (Mn) was analyzed to be 1800 g / mol, PDI=1.2.

[0320] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.5~3.4(m, 40H), 2.45(m, 8H), 1.75(m, 8H)

[0321]

[0322] Manufacturing Example 2 - Manufacturing of a compound represented by Chemical Formula 1-a2

[0323] A compound represented by chemical formula 1-a2 was manufactured in the same manner as in Manufacturing Example 1, except that a compound represented by chemical formula a3 was used instead of the compound represented by chemical formula a1 in Manufacturing Example 1.

[0324] [Chemical Formula 1-a2]

[0325]

[0326] The synthesis of the compound represented by the above chemical formula 1-a2 was confirmed through GPC (Waters, e2695 GPC). The number-average molecular weight (Mn) was analyzed to be 2400 g / mol, PDI=1.9.

[0327] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.6~3.4(m, 104H), 2.45(m, 8H), 1.75(m, 8H)

[0328]

[0329] Manufacturing Example 3 - Manufacturing of a compound represented by Chemical Formula 1-a3

[0330] A compound represented by chemical formula 1-a3 was prepared in the same manner as in Manufacturing Example 1, except that the compound represented by chemical formula a4 was used instead of the compound represented by chemical formula a1 in Manufacturing Example 1.

[0331] [Chemical Formula 1-a3]

[0332]

[0333] The synthesis of the compound represented by the above chemical formula 1-a3 was confirmed through GPC (Waters, e2695 GPC). The number-average molecular weight (Mn) was analyzed to be 3000 g / mol, PDI=2.0.

[0334] 1 H-NMR (500 MHZ. d6-Dimethyl sulfoxide): δ(ppm) = 3.6~3.4(m, 204H), 2.45(m, 8H), 1.75(m, 8H)

[0335]

[0336] Examples and Comparative Examples

[0337] Example 1

[0338] 0.3 g of a compound represented by the chemical formula 1-a1 prepared from Manufacturing Example 1, 1.35 g of a polysiloxane derivative represented by the chemical formula Aa below, and 1.35 g of trimethylolpropane ethoxylate triacrylate Mn 428 were dispersed in 30 mL of acetonitrile to obtain a transparent solution, and 0.01 g of 2,2`-azobis(2-methylpropionitrile) and 0.04 g of bis(trifluoromethane)sulfonimide lithium salt were added.

[0339] [Chemical formula Aa]

[0340]

[0341] After this, the solution was uniformly cast onto a flat glass plate. It was then dried at 40°C for approximately 12 hours, followed by drying in a vacuum oven at 70°C for 24 hours. This resulted in the production of an ion-conducting polymer electrolyte film with a thickness of 20-40 μm.

[0342]

[0343] Example 2

[0344] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a compound represented by Chemical Formula 1-a2 was used instead of the compound represented by Chemical Formula 1-a1 in Example 1.

[0345]

[0346] Example 3

[0347] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a compound represented by Chemical Formula 1-a3 was used instead of the compound represented by Chemical Formula 1-a1 in Example 1.

[0348]

[0349] Example 4

[0350] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a polysiloxane derivative represented by the following chemical formula Ab was used instead of the polysiloxane derivative represented by the chemical formula Aa in Example 1.

[0351] [Chemical formula Ab]

[0352]

[0353]

[0354] Example 5

[0355] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a polysiloxane derivative represented by the following chemical formula Ac was used instead of the polysiloxane derivative represented by the chemical formula Aa in Example 1.

[0356] [Chemical formula Ac]

[0357]

[0358]

[0359] Example 6

[0360] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a polysiloxane derivative represented by the following chemical formula Ba was used instead of the polysiloxane derivative represented by the chemical formula Aa in Example 1.

[0361] [chemical formula Ba]

[0362]

[0363]

[0364] Example 7

[0365] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 6, except that the compound represented by Chemical Formula 1-a2 was used instead of the compound represented by Chemical Formula 1-a1 in Example 6.

[0366]

[0367] Example 8

[0368] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that a polysiloxane derivative represented by the following chemical formula Bb was used instead of the polysiloxane derivative represented by the chemical formula Aa in Example 1.

[0369] [chemical formula Bb]

[0370]

[0371]

[0372] Comparative Example 1

[0373] Lithium bis(Trifluoromethyl)sulfonylimide (EO:Li + After dissolving PEO (20 wt% vs. Acetonitrile) in acetonitrile (molar ratio = 20:1), 3 g of PEO (20 wt% vs. Acetonitrile) was added. At this time, the PEO has a composition in which PEO (Sigma-Aldrich) with Mw = 100,000 and PEO (Sigma-Aldrich) with Mw = 600,000 are mixed in a weight ratio of 9:1. The mixture was stirred at room temperature for 2 hours using an overhead stirrer. After that, air bubbles were removed by sonication (exposure to sonication conditions) in a bath sonicator for 20 minutes, and a PEO-LiTFSI solution was obtained. After that, the PEO-LiTFSI solution was dropwise applied onto an MRF-38 release film using a film applicator and coated. First, it was dried for about 12 hours under room temperature conditions, and then vacuum-dried in a vacuum oven at 40°C for 8 hours. Through this, a PEO-LiTFSI polymer electrolyte film with a thickness of 10-50 μm was manufactured.

[0374]

[0375] Comparative Example 2

[0376] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-a1 was not added.

[0377] Comparative Example 3

[0378] An ion-conducting polymer electrolyte film was manufactured in the same manner as in Example 6, except that the compound represented by Chemical Formula 1-a1 was not added.

[0379]

[0380] Experimental Example 1 - Measurement of ionic conductivity

[0381] Inside a glove box, the polymer electrolyte film manufactured in the above examples and comparative examples was soaked in a solvent of EC / PC (1:1 volume ratio), and the polymer electrolyte film was sandwiched between two stainless steel electrodes (used as a negative electrode and a positive electrode) in a battery case to manufacture a coin cell including an electrode assembly.

[0382] The above-mentioned coin cell was measured at room temperature (25°C) using a potentiostat (Biologics SP-200) with an amplitude of 10 mV over a frequency range of 0.1 Hz to 7 MHz. The impedance was measured, and the ionic conductivity was measured by substituting it into the equation L=I / RS (L= ionic conductivity, I= electrode thickness, R= measured impedance value, S= electrode area). The measured ionic conductivity is shown in Table 1 below.

[0383]

[0384] Experimental Example 2 - Measurement of lithium ion transport rate

[0385] In a glove box, the polymer electrolyte film manufactured in the above examples and comparative examples was soaked in a solvent of EC / PC (1:1 volume ratio), and the polymer electrolyte film was sandwiched between lithium foil electrodes (used as negative and positive electrodes) having a thickness of 200 ㎛ in a battery case, and a coin cell including an electrode assembly was manufactured by storing the polymer electrolyte film at a temperature of 60° C. for about 12 hours.

[0386] The resistance of the passivation layer of the coin cell manufactured above was measured before and after the chronoamperometry experiment using a potentiostat (Biologics SP-200). Li+ = I s (△V - I o R o ) / I o (△V - I S R S)(△V= voltage applied to the cell = 3 mV, I o = Initial current, I S = Steady-state current, R o = Initial resistance of the passivation layer on the lithium electrode surface, R S = steady-state resistance of the passivation layer on the lithium electrode surface) and substituted into the equation to obtain the lithium ion transport rate (t Li+ ) was measured. The measured lithium ion transport rate is shown in Table 1 below.

[0387] Polymer PDMS Derivative Polyether Polymer Type Ion Conductivity (S / cm) Lithium Ion Transport Rate Example 1 Chemical Formula 1-a1 Chemical Formula Aa Trimethylolpropane ethoxylate triacrylate 2.8 × 10 -5 0.43 Example 2 Chemical Formula 1-a2 Chemical Formula Aa Trimethylolpropane ethoxylate triacrylate 2.0 × 10 -5 0.45 Example 3 Chemical Formula 1-a3 Chemical Formula Aa Trimethylolpropane ethoxylate triacrylate 2.5 × 10 -5 0.40 Example 4 Chemical Formula 1-a1 Chemical Formula Ab Trimethylolpropane ethoxylate triacrylate 2.2 × 10 -5 0.43 Example 5 Chemical Formula 1-a1 Chemical Formula Ac-trimethylolpropane ethoxylate triacrylate 2.0 × 10 -5 0.43 Example 6 Chemical Formula 1-a1 Chemical Formula Ba Trimethylolpropane Ethoxylate Triacrylate 2.0 × 10 -5 0.41 Example 7 Chemical Formula 1-a2 Chemical Formula Ba Trimethylolpropane Ethoxylate Triacrylate 2.5 × 10 -5 0.42 Example 8 Chemical Formula 1-a1 Chemical Formula Bb Trimethylolpropane ethoxylate triacrylate 3.0 × 10 -5 0.43 Comparative example 1XXPEO-LiTFSI containing solid electrolyte 2.6 × 10 -6 0.20 Comparative Example 2X Chemical Formula Aa Trimethylolpropane Ethoxylate Triacrylate 1.0 × 10-5 0.20 Comparative Example 3X Chemical Formula Ba Trimethylolpropane Ethoxylate Triacrylate 1.0 × 10 -5 0.20

[0388] Referring to Table 1, it can be confirmed that Examples 1 to 5 have higher lithium ion conductivity and ion transport rate than Comparative Example 1. The above examples include ion-conducting polymers in which sulfonimide anions, which are friendly to lithium ions but have low electron density, are fixed to the main chain. Since such ion-conducting polymers can move dissociated lithium ions in the electrolyte with higher efficiency, the above examples can have higher ion conductivity and ion transport rate characteristics than the Comparative Example including the existing alkylene oxide-based polymer.

[0389] In addition, the solid electrolytes of Examples 1 to 5 include a composition including a polymer represented by Chemical Formulae 1-a1 to 1-a3, a polysiloxane derivative, and a polyether polymer, whereas the solid electrolyte of Comparative Example 2 does not include a polymer represented by Chemical Formulae 1-a1 to 1-a3, and thus the ion transport rate is inferior compared to Example 1, and thus it can be confirmed that the actual ion conductivity is inferior.

[0390]

[0391] Experimental Example 3 - Evaluation of Stability in Moisture and Battery Environments

[0392] The stability against moisture and in the battery environment was evaluated for Reference Examples a and b below. Reference Example a corresponds to the structure of a Li salt form of a disulfonimide group, in which oxygen atoms do not exist on both sides of the disulfonimide group, and Reference Example b corresponds to the structure of a Li salt form of a disulfonimide group, but has oxygen atoms present on both sides of the disulfonimide group.

[0393] [Reference Example a]

[0394]

[0395] [Reference example b]

[0396]

[0397] As a result of measuring the hydrolysis energy in the form of a Li salt, when calculated as a Li salt, the SN bond of Reference Example a was measured to have a hydrolysis energy of 4.80 kcal / mol, and the SO bond of Reference Example b was measured to have a hydrolysis energy of -0.59 kcal / mol. Accordingly, it was determined that the oxygen atom bonded next to the sulfur atom of the disulfonimide group was considerably vulnerable to hydrolysis, and through this, it can be confirmed that Reference Example a has superior moisture stability and stability within a battery compared to Reference Example b. Consequently, it can be confirmed that the polymer represented by any one of the chemical formulas 1-a1 to 1-a3 of the present invention having a structure that does not include oxygen atoms on both sides of the disulfonimide group, like Reference Example a, has superior moisture stability and stability within a battery.

Claims

A composition comprising a polymer comprising a repeating unit represented by the following chemical formula 1; and a polysiloxane derivative: [Chemical Formula 1] In the above chemical formula 1, The above * indicates a connecting portion or terminal portion between repeating units, Above L1 to L4, R a and R b are each independently, directly bonded; or substituted or unsubstituted C1-C 10 is an alkylene group, The above x and y are each independently integers greater than or equal to 1. In claim 1, A composition wherein the above L1 to L4 are each independently a substituted or unsubstituted C1-C5 alkylene group. In claim 1, The above polymer is a composition comprising a repeating unit represented by the following chemical formula 1-a: [Chemical Formula 1-a] In the above chemical formula 1-a, The above x and y are each independently integers greater than or equal to 1. In claim 1, The above polysiloxane derivative is a composition represented by the following chemical formula A: [Chemical Formula A] In the above chemical formula A, The above R 11 Inland R 15 and R 17 are each independently a hydrogen element; a halogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group of; substituted or unsubstituted C2-C 10 an alkenyl group of; or a substituted or unsubstituted C2-C 10 is an alkynyl group, The above R 16 is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group, The above R 18 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group, Above L a and L b are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group, The above q is an integer greater than or equal to 1, The above o, p and r are each independently an integer greater than or equal to 0 or 1. In claim 1, The above R 11 Inland R 15 and R 17 are each independently a hydrogen element; -Si(R 18 )3; -O-Si(R 18 )3; -C(=O)R 18 ; or substituted or unsubstituted A composition having an alkyl group of C1-C5. In claim 1, The above R 16 A composition in which the silver is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group. In claim 1, The polysiloxane derivative is a composition represented by at least one chemical formula selected from the group consisting of the following chemical formulas A-1 to A-8: [Chemical Formula A-1] [Chemical Formula A-2] [Chemical Formula A-3] [Chemical Formula A-4] [Chemical Formula A-5] [Chemical Formula A-6] [Chemical Formula A-7] [Chemical Formula A-8] In the above chemical formulas A-1 to A-8, The above q and o2 are each independently an integer greater than or equal to 1, Above o, o 1, p and r are each independently an integer greater than or equal to 0 or 1. In claim 1, The above polysiloxane derivative is a composition represented by the following chemical formula B: [Chemical Formula B] In the above chemical formula B, The above R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 Alkoxy group of; substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 an alkynyl group; or a functional group represented by the following chemical formula B, The above R 26 is a direct bond; or substituted or unsubstituted C1-C 10 is an alkylene group, The above R 20 is a hydrogen element; a halogen element; or a substituted or unsubstituted C1-C 10 is an alkyl group, Above L c , L d , L e and L f are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group, The above s is an integer greater than or equal to 1, The above v1, v2, v3 and w are each independently integers greater than or equal to 0 or 1, [Chemical Formula C] In the above chemical formula C, Above L g and L h are each independently, -O-; direct bond; substituted or unsubstituted C1-C 10 is an alkylene group, The above R 31 Silver is a hydrogen element; a halogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; substituted or unsubstituted C1-C 10 Alkyl group of; substituted or unsubstituted C1-C 10 an alkoxy group; or a substituted or unsubstituted C2-C 10 Alkenyl group of; substituted or unsubstituted C2-C 10 is an alkynyl group, The above t is an integer greater than or equal to 0 or 1. In claim 8, The above R 21 Inland R 25 and R 27 Inland R 29 are each independently a hydrogen element; -Si(R 20 )3; -O-Si(R 20 )3; -C(=O)R 20 ; or substituted or unsubstituted A composition having an alkyl group of C1-C5. In claim 8, The above R 26 A composition in which the silver is a direct bond; or a substituted or unsubstituted C1-C5 alkylene group. In claim 8, A composition wherein the above v1, v2 and v3 are each independently an integer of 3 or more. In claim 1, The above polysiloxane derivative is a composition represented by at least one chemical formula selected from the group consisting of the following chemical formulas B-1 to B-7: [Chemical Formula B-1] [Chemical Formula B-2] [Chemical Formula B-3] [Chemical Formula B-4] [Chemical Formula B-5] [Chemical Formula B-6] [Chemical Formula B-7] In the above chemical formulas B-1 to B-7, The above s and w are each independently integers greater than or equal to 1, The above v1, v2 and v3 are each independently integers greater than or equal to 3. The above t is an integer greater than or equal to 0 or 1. In claim 1, A composition wherein the composition further comprises a polyether derivative. In claim 13, A composition comprising a polymer having a crosslinking functional group at at least one terminal of at least one polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diglycidyl ether, and combinations thereof. In claim 1, The above composition comprises LiCl, LiBr, LiI, LiBF4, LiClO4, LiB 10 Cl 10 A composition comprising a lithium compound comprising at least one compound selected from the group consisting of LiAlCl4, LiAlO4, LiPF6, LiCF3SO3, LiCH3CO2, LiCF3CO2, LiAsF6, LiSbF6, LiCH3SO3, LiFSI (lithium bis(fluorosulfonyl)imide, LiN(SO2F)2), LiBETI (lithium bisperfluoroethanesulfonimide, LiN(SO2CF2CF3)2) and LiTFSI (lithium (bis)trifluoromethanesulfonimide, LiN(SO2CF3)2). In claim 1, The above composition is a composition comprising inorganic particles. In claim 1, The composition comprises solid electrolyte particles comprising one or more elements selected from the group consisting of constituent elements Li, Al, Ti, La, Zr, O, P, Ge, and S. A polymer membrane comprising the composition of claim 1. In claim 18, A polymer membrane comprising a porous substrate comprising one or more materials selected from the group consisting of polyethylene, polypropylene, polyimide, polybenzimidazole, cellulose, and glass fiber. A secondary battery comprising a polymer membrane according to claim 18.

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