Composition for ion-conductive film and battery comprising ion-conductive film manufactured therefrom

Abstract

The present invention relates to a composition for an ion-conductive film and a battery comprising an ion-conductive film manufactured therefrom, wherein the composition for an ion-conductive film comprises a phosphorus-based polymer, a compound represented by chemical formula 2, and a lithium salt compound, and comprises 80.00-90.00 parts by weight of the polymer with respect to 100 parts by weight of the sum of the polymer and the compound represented by chemical formula 2.

Description

Composition of ion-conducting membrane and battery including ion-conducting membrane manufactured thereby

[0001] [Cross-citation with related applications]

[0002] This invention claims the benefit of priority to Korean Patent Application No. 10-2024-0099133, filed July 26, 2024, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a composition of an ion-conducting membrane and a battery including an ion-conducting membrane manufactured thereby.

[0005] 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. Addressing these safety concerns complicates battery design.

[0006] To address these stability issues, research is underway on solid electrolytes possessing non-flammable or flame-retardant properties. These solid electrolytes can be categorized into sulfide electrolytes, oxide electrolytes, and polymer electrolytes. Among these, polymer electrolytes are inexpensive, have excellent flexibility, and are easy to process.

[0007] The polymer electrolytes mentioned above are broadly categorized into gel and solid types. Among these, solid polymer electrolytes can improve stability issues related to leakage because they do not contain a liquid electrolyte. Furthermore, they exhibit high chemical and electrochemical stability. However, their ionic conductivity at room temperature is lower than that of liquid electrolytes. Currently, the most commonly used material for solid polymer electrolytes is polyethylene oxide (PEO). Despite being a solid, PEO possesses the ability to conduct lithium ions. However, when linear PEO is used as an electrolyte, its high crystallinity limits chain mobility. Furthermore, linear PEO has a low dielectric constant (5.0), preventing it from dissociating a large amount of lithium ions. Furthermore, linear PEO has very low ionic conductivity at room temperature, making it difficult to apply to lithium secondary batteries.

[0008] Meanwhile, lithium metal batteries are attracting attention as next-generation batteries, boasting a theoretical capacity more than 10 times higher than that of graphite batteries. However, they suffer from the problem of uneven movement of lithium ions on the surface of the lithium metal, which leads to dendrite growth. This problem has hindered the commercialization of lithium metal batteries. Therefore, research is needed on materials that can act as a protective layer for lithium metal, while also providing ion conductivity and uniformly increasing lithium ion transport rates.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] (Patent Document 1) KR2017-111270A

[0012] The problem to be solved by the present invention is to provide a composition of an ion-conducting film that implements excellent ion conductivity, has low interfacial resistance between components, has a long lifespan, and has excellent stability, and a battery including an ion-conducting film manufactured thereby.

[0013] In order to solve the above-mentioned problem, 1) the present invention provides a composition of an ion conductive membrane comprising a polymer including a structural unit represented by the following chemical formula 1; a compound represented by the following chemical formula 2; and a lithium salt compound, wherein the composition comprises 80.00 to 90.00 parts by weight of the polymer relative to 100 parts by weight of the sum of the polymer and the compound represented by the following chemical formula 2:

[0014] <Chemical Formula 1>

[0015]

[0016] In the above chemical formula 1

[0017] R 11 and R 12 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group, C2 to C 20 alkynyl group of *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2,

[0018] L 11 Inland L 15 are each independently bonded directly, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group,

[0019] X 11 and X 12 are each independently a direct bond or *-O-*,

[0020] R 13 is hydrogen or C1 to C 20 is an alkyl group,

[0021] n 11 and n 12 are each independently selected from 1.0 to 30.0;

[0022] <Chemical Formula 2>

[0023]

[0024] In the above chemical formula 2,

[0025] M1 is an alkali metal,

[0026] L 21 Silver direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group, C6 to C 20 Arylene group or *-L 22 -OC(=O)-*,

[0027] L 22 is a direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group or C6 to C 20 is an arylene group,

[0028] R 21 and R 22 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

[0029] 2) The present invention provides a composition of an ion conductive film, wherein the structural unit represented by the chemical formula 1 in the above 1) comprises at least one structural unit selected from the structural unit represented by the following chemical formula 1-1 to the structural unit represented by the following chemical formula 1-8:

[0030] <Chemical Formula 1-1>

[0031]

[0032] <Chemical Formula 1-2>

[0033]

[0034] In the above chemical formula 1-2,

[0035] n 11-1 is selected from 1.0 to 30.0;

[0036] <Chemical Formula 1-3>

[0037]

[0038] In the above chemical formula 1-3,

[0039] n 12-1 is selected from 1.0 to 30.0;

[0040] <Chemical Formula 1-4>

[0041]

[0042] In the above chemical formula 1-4,

[0043] n 11-2 and n 11-3 are each independently selected from 1.0 to 30.0;

[0044] <Chemical Formula 1-5>

[0045]

[0046] In the above chemical formula 1-5,

[0047] n 11-4 and n 12-2 are each independently selected from 1.0 to 30.0;

[0048] <Chemical Formula 1-6>

[0049]

[0050] In the above chemical formula 1-6,

[0051] n 12-3 and n 12-4 are each independently selected from 1.0 to 30.0;

[0052] <Chemical Formula 1-7>

[0053]

[0054] In the above chemical formula 1-7,

[0055] n 11-5 , n 11-6 , n 12-5 and n 12-6 are each independently selected from 1.0 to 30.0.

[0056] <Chemical Formula 1-8>

[0057]

[0058] In the above chemical formula 1-8,

[0059] n 11-7 , n 11-8 , n 11-9 , n 12-7 , n 12-8 and n 12-9 are each independently selected from 1.0 to 30.0.

[0060] 3) The present invention can provide a composition of an ion conductive film in the above 1) or 2), wherein the polymer has a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0061] 4) The present invention can provide a composition of an ion conductive film in which the compound represented by the chemical formula 2 in any one of the above 1) to 3) is selected from the compound represented by the following chemical formula 2-1 and the compound represented by the following chemical formula 2-2:

[0062] <Chemical Formula 2-1>

[0063]

[0064] <Chemical Formula 2-2>

[0065]

[0066] 5) The present invention can provide a composition of an ion conductive film comprising at least one selected from among the compounds represented by the following chemical formula 3, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium bis(oxalato)borate, in any one of the above 1) to 4):

[0067] <Chemical Formula 3>

[0068]

[0069] In the above chemical formula 3,

[0070] R 31 and R 32 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

[0071] 6) The present invention can provide a composition of an ion conductive film comprising at least one compound selected from among the compounds represented by the following chemical formula 3-1 or the compounds represented by the following chemical formula 3-2 in the above 5):

[0072] <Chemical Formula 3-1>

[0073]

[0074] <Chemical Formula 3-2>

[0075]

[0076] 7) The present invention can provide a composition of an ion conductive film comprising 1.00 to 60.00 parts by weight of the lithium salt compound relative to 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2 in any one of 1) to 6).

[0077] 8) The present invention can provide a composition of an ion conductive film comprising a compound represented by the following chemical formula 4 in any one of 1) to 7):

[0078] <Chemical Formula 4>

[0079]

[0080] In the above chemical formula 4,

[0081] L 41 and L 42 are each independently, directly bonded, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group,

[0082] R 41 Inland R 45 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group,

[0083] y is chosen from 1.0 to 30.0.

[0084] 9) The present invention can provide a composition of an ion conductive film in which the compound represented by the chemical formula 4 in the above 8) is a compound represented by the following chemical formula 4-1:

[0085] <Chemical Formula 4-1>

[0086]

[0087] In the above chemical formula 4-1,

[0088] y' is chosen from 1.0 to 30.0.

[0089] 10) The present invention can provide a composition of an ion conductive film comprising 1.00 to 35.00 parts by weight of a compound represented by the chemical formula 4, based on 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2 in the above 8) or 9).

[0090] 11) The present invention can provide a composition of an ion conductive film including a crosslinking agent in any one of 1) to 10).

[0091] 12) The present invention can provide a composition of an ion conductive film, wherein in the above 11), the crosslinking agent includes at least one selected from among poly(ethylene glycol) diacrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, or pentaerythritol tetraacrylate.

[0092] 13) The present invention can provide a composition of an ion conductive membrane comprising 0.50 to 50.00 parts by weight of the crosslinking agent relative to 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2 in the above 11) or 12).

[0093] 14) The present invention provides a battery including an ion conductive membrane manufactured with a composition of an ion conductive membrane according to any one of 1) to 13).

[0094] The composition of the ion-conducting membrane according to the present invention exhibits excellent ion conductivity. Furthermore, a battery comprising an ion-conducting membrane manufactured using the composition of the ion-conducting membrane according to the present invention exhibits low interfacial resistance between components, a long lifespan, and excellent stability.

[0095] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best possible manner.

[0096]

[0097] In this specification, the term 'on' means not only when a configuration is formed directly on the top surface of another configuration, but also when a third configuration is interposed between these configurations.

[0098]

[0099] In the present invention, an alkyl group means a linear or cyclic alkyl group, and the number of carbon atoms is not particularly limited, but is C1 to C 20 An alkyl group, preferably C1 to C 15 An alkyl group, more preferably C1 to C 10 An alkyl group, most preferably an alkyl group of C1 to C5, may be used. The alkyl group may be further substituted with another substituent. Specific examples of the above alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, Examples include, but are not limited to, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0100]

[0101] In the present invention, the alkylene group is as defined in the above alkyl group, except that it is a divalent group.

[0102]

[0103] In the present invention, the alkenyl group means a linear or cyclic alkenyl group, and the number of carbon atoms is not particularly limited, but is C2 to C 20 Alkenyl group, preferably C2 to C 15 Alkenyl group of, more preferably C2 to C 10 An alkenyl group may be an alkenyl group, most preferably a C2 to C5 alkenyl group. The alkenyl group may be further substituted with another substituent. Examples of the alkenyl group include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl, and styrenyl.

[0104]

[0105] In the present invention, the alkenylene group is as defined in the alkenyl group above, except that it is a divalent group.

[0106]

[0107] In the present invention, an alkynyl group means a linear or cyclic alkynyl group, and the number of carbon atoms is not particularly limited, but is C2 to C 20 an alkynyl group, preferably C2 to C 15 an alkynyl group, more preferably C2 to C 10 An alkynyl group, most preferably a C2 to C5 alkynyl group, may be used. The alkynyl group may include, but is not limited to, alkynyl groups such as ethynyl, propynyl, 2-methyl-2propynyl, 2-butynyl, and 2-pentynyl.

[0108]

[0109] In the present invention, the alkynylene group is as defined in the above alkynyl group, except that it is a divalent group.

[0110]

[0111] In the present invention, the aryl group means a monocyclic or polycyclic aryl group, and the number of carbon atoms is not particularly limited, but is C6 to C 20 Aryl group of, preferably C6 to C 18 Aryl group of, more preferably C6 to C 16 Aryl group of, most preferably C6 to C 14 It can be an aryl group. The aryl group can be further substituted by another substituent. Here, polycyclic means a group in which an aryl group is directly connected to or condensed with another ring group. Specific examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, and anthryl group.

[0112]

[0113] In the present invention, the alkali metal may include one or more of Li, Na, K, Rb, Cs, and Fr.

[0114]

[0115] In the present invention, halogen may include one or more of F, Cl, Br, I, and At.

[0116]

[0117] In the present invention, '*' indicates a binding position.

[0118]

[0119] In the present invention, C1 to C substituted with halogen 20 The alkyl group of is C1 to C, which is either wholly or partially substituted with halogen. 20 It may be an alkyl group. Specifically, it may be a primary to tertiary halogenated alkyl group. And, C1 to C substituted with halogen 20 Examples of alkyl groups include trifluoromethyl groups.

[0120]

[0121] 1. Composition of ion conductive membrane

[0122]

[0123] A composition of an ion conductive film according to one embodiment of the present invention comprises a polymer including a structural unit represented by the following chemical formula 1; a compound represented by the following chemical formula 2; and a lithium salt compound, and comprises 80.00 to 90.00 parts by weight of the polymer relative to 100 parts by weight of the sum of the polymer and the compound represented by the following chemical formula 2:

[0124] <Chemical Formula 1>

[0125]

[0126] In the above chemical formula 1

[0127] R 11 and R 12 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group, C2 to C 20 alkynyl group of *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2,

[0128] L 11 Inland L 15 are each independently bonded directly, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group,

[0129] X 11 and X 12 are each independently a direct bond or *-O-*,

[0130] R 13 is hydrogen or C1 to C 20 is an alkyl group,

[0131] n 11 and n 12 are each independently selected from 1.0 to 30.0;

[0132] <Chemical Formula 2>

[0133]

[0134] In the above chemical formula 2,

[0135] M1 is an alkali metal,

[0136] L 21 Silver direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group, C6 to C 20 Arylene group or *-L 22 -OC(=O)-*,

[0137] L 22 is a direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group or C6 to C 20 is an arylene group,

[0138] R 21 and R 22 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

[0139]

[0140] In addition, the composition of the ion conductive film according to one embodiment of the present invention may include a compound represented by the following chemical formula 4:

[0141] <Chemical Formula 4>

[0142]

[0143] In the above chemical formula 4,

[0144] L 41 and L 42 are each independently, directly bonded, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group,

[0145] R 41 Inland R 45 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group,

[0146] y is chosen from 1.0 to 30.0.

[0147]

[0148] Additionally, the composition of the ion conductive film according to one embodiment of the present invention may include a crosslinking agent.

[0149]

[0150] Additionally, the composition of the ion conductive film according to one embodiment of the present invention may further include an additive.

[0151]

[0152] Hereinafter, the composition of an ion conductive film according to one embodiment of the present invention will be described in detail.

[0153]

[0154] 1) A polymer comprising a structural unit represented by chemical formula 1

[0155]

[0156] The polymer including the structural unit represented by the above chemical formula 1 has a structure that imparts ion conductivity to a backbone having flame retardancy, and plays a role in transferring alkali metal ions, specifically, in transferring lithium ions.

[0157]

[0158] The above R 11 and R 12 One of them is preferably C2 to C 15 Alkenyl group of or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2; more preferably C2 to C 10 Alkenyl group of or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2; Most preferably, an alkenyl group of C2 to C5 or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2 may be.

[0159] Here L 14 and L 15 are each independently preferably C1 to C 15 An alkylene group, more preferably C1 to C 10 An alkylene group, most preferably C1 to C 10 It may be an alkylene group.

[0160]

[0161] The above R 11 and R 12 The remaining one is preferably C1 to C substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, halogen. 15 Alkyl group, C2 to C 15 Alkenyl group, C2 to C 15 alkynyl group or *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 ; More preferably, C1 to C substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, halogen 10 Alkyl group, C2 to C10 Alkenyl group, C2 to C 10 alkynyl group or *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 ; Most preferably, hydrogen, halogen, *-CN, *-OH, C1 to C5 alkyl group unsubstituted or substituted with halogen, C2 to C5 alkenyl group, C2 to C5 alkynyl group or *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 It could be.

[0162] Meanwhile, the above R 11 and R 12 The remaining one is to combine with alkali metal ions to dissolve alkali metal salts or to move alkali metal ions, specifically to combine with lithium ions to dissolve lithium salts or to move lithium ions, *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 It is most desirable that

[0163]

[0164] Above L 11 Inland L 15 are each independently preferably directly bonded, C1 to C 15 alkylene group, C2 to C 15 Alkenylene group or C2 to C 15 Alkynylene group of; more preferably direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group or C2 to C 10 Alkynylene group; most preferably a direct bond, an alkylene group having C1 to C5, an alkenylene group having C2 to C5, or an alkynylene group having C2 to C5.

[0165]

[0166] The above R 13 is preferably hydrogen or C1 to C 15 an alkyl group of; more preferably hydrogen or C1 to C 10 An alkyl group; most preferably, it may be hydrogen or an alkyl group of C1 to C5.

[0167]

[0168] n 11 and n 12 can each be independently selected preferably from 1.0 to 25.0, more preferably from 1.0 to 20.0, and most preferably from 1.0 to 10.0.

[0169]

[0170] The structural unit represented by the above chemical formula 1 may include one or more structural units selected from the structural unit represented by the following chemical formula 1-1 to the structural unit represented by the following chemical formula 1-8:

[0171] <Chemical Formula 1-1>

[0172]

[0173] <Chemical Formula 1-2>

[0174]

[0175] In the above chemical formula 1-2,

[0176] n 11-1 is selected from 1.0 to 30.0;

[0177] <Chemical Formula 1-3>

[0178]

[0179] In the above chemical formula 1-3,

[0180] n 12-1 is selected from 1.0 to 30.0;

[0181] <Chemical Formula 1-4>

[0182]

[0183] In the above chemical formula 1-4,

[0184] n 11-2 and n 11-3 are each independently selected from 1.0 to 30.0;

[0185] <Chemical Formula 1-5>

[0186]

[0187] In the above chemical formula 1-5,

[0188] n 11-4 and n 12-2 are each independently selected from 1.0 to 30.0;

[0189] <Chemical Formula 1-6>

[0190]

[0191] In the above chemical formula 1-6,

[0192] n 12-3 and n 12-4 are each independently selected from 1.0 to 30.0;

[0193] <Chemical Formula 1-7>

[0194]

[0195] In the above chemical formula 1-7,

[0196] n 11-5 , n 11-6 , n 12-5 and n 12-6 are each independently selected from 1.0 to 30.0.

[0197] <Chemical Formula 1-8>

[0198]

[0199] In the above chemical formula 1-8,

[0200] n 11-7 , n 11-8 , n 11-9 , n 12-7 , n 12-8 and n 12-9are each independently selected from 1.0 to 30.0.

[0201]

[0202] above n 11-1 Inland n 11-9 , n 12-1 Inland n 12-9 Each independently preferably may be selected from 1.0 to 25.0, more preferably from 1.0 to 20.0, and most preferably from 2.0 to 8.0. When the above conditions are satisfied, the polymer can be easily synthesized and the yield can also be increased.

[0203]

[0204] The polymer may include a terminal group represented by the following chemical formula 1-9:

[0205] <Chemical Formula 1-9>

[0206]

[0207] In the above chemical formula 1-9,

[0208] L 16 is a direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group,

[0209] R 14 Inland R 16 are each independently hydrogen or halogen.

[0210]

[0211] Above L 16 is preferably a direct bond, C1 to C 15 alkylene group, C2 to C 15 Alkenylene group or C2 to C 15 Alkynylene; more preferably a direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group or C2 to C 10Alkynylene; most preferably a direct bond, an alkylene group having C1 to C5, an alkenylene group having C2 to C5, or an alkynylene group having C2 to C5.

[0212]

[0213] The above polymer may have a weight average molecular weight of 1,000 to 10,000,000 g / mol, preferably 10,000 to 10,000,000 g / mol, more preferably 50,000 to 5,000,000 g / mol. When the above conditions are satisfied, the polymer can be easily synthesized, the yield can be increased, and the process cost can also be reduced.

[0214] Here, the weight average molecular weight can be measured by gel permeation chromatography. When measuring gel permeation chromatography, an Agilent 1200 series HPLC system can be used, and the specific measurement conditions are as follows.

[0215] Refractive Index Detector: Waters 2414

[0216] Temperature of refractive index detector: 25 ℃

[0217] Data processing: Agilent Chem Station S / W

[0218] Dissolution solution: A mixed solution of 0.05 M LiBr and dimethylformamide

[0219] Column Model: Agilent's PL Mixed C & Mixed D

[0220] Column temperature: 60 ℃

[0221] Flow rate: 1.0 ml / min

[0222] Standard sample: polystyrene

[0223] Concentration of standard sample: 1.0 mg / ml

[0224]

[0225] The content of the polymer may be 80.00 to 90.00 parts by weight, preferably 83.00 to 90.00 parts by weight, and more preferably 85.00 to 90.00 parts by weight, based on 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2. When the above-described conditions are satisfied, the composition of the ion conductive membrane can have strength and ionic conductivity suitable for use as an electrolyte membrane. If the content of the polymer is less than the above-described conditions, the compound represented by the chemical formula 2 cannot help but be included in a relatively excessive amount, so that the molar ratio of *-(-CH2-CH2-O)-* and lithium ions deviates from the optimal value, resulting in a significant decrease in ionic conductivity. If the content of the polymer is more than the above-described conditions, the compound represented by the chemical formula 2 cannot help but be included in a relatively small amount, so that the ion conductive membrane does not have appropriate mechanical strength, is easily damaged, and is not capable of self-standing.

[0226]

[0227] Meanwhile, a polymer including a structural unit represented by the above chemical formula 1 can be manufactured by a manufacturing method including a step of polymerizing a monomer represented by the following chemical formula 5 to manufacture an intermediate including a structural unit represented by the following chemical formula 6; and a step of replacing the halogen of the intermediate with at least one selected from a monomer represented by the following chemical formula 7 and a monomer represented by the following chemical formula 8.

[0228] <Chemical Formula 5>

[0229]

[0230] In the above chemical formula 5,

[0231] X is a halogen.

[0232] <Chemical Formula 6>

[0233]

[0234] In the above chemical formula 6,

[0235] X is a halogen.

[0236] <Chemical Formula 7>

[0237]

[0238] In the above chemical formula 7,

[0239] R 11 is as defined in the above chemical formula 1.

[0240] <Chemical Formula 8>

[0241]

[0242] In the above chemical formula 8,

[0243] R 12 is as defined in the above chemical formula 1.

[0244]

[0245] The above polymerization can be selected from solution polymerization and bulk polymerization.

[0246]

[0247] 2) Compound represented by chemical formula 2

[0248]

[0249] Since the compound represented by the above chemical formula 2 includes a crosslinkable functional group, an anion is fixed to the chain of the compound. As a result, the compound represented by the above chemical formula 2 can improve the transport rate of alkali metal ions, specifically, the transport rate of lithium ions.

[0250]

[0251] In the above chemical formula 2, in terms of increasing the degree of dissociation of alkali metal ions, specifically, the degree of dissociation of lithium ions, L 21 is preferably a direct bond, C1 to C 15 alkylene group, C2 to C 15 Alkenylene group of C2 to C 15 Alkynylene group, C6 to C 18 Arylene group or *-L 22-OC(=O)-*; more preferably direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group of C2 to C 10 Alkynylene group, C6 to C 16 Arylene group or *-L 22 -OC(=O)-*; Most preferably a direct bond, an alkylene group of C1 to C5, an alkenylene group of C2 to C5, an alkynylene group of C2 to C5, an alkynylene group of C6 to C 14 Arylene group or *-L 22 -OC(=O)-* may be.

[0252]

[0253] Above L 22 is preferably a direct bond, C1 to C 15 alkylene group, C2 to C 15 Alkenylene group of C2 to C 15 Alkynylene group or C6 to C 15 Arylene group of; more preferably direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group of C2 to C 10 Alkynylene group or C6 to C 10 An arylene group; most preferably a direct bond, an alkylene group having C1 to C5, an alkenylene group having C2 to C5, an alkynylene group having C2 to C5, or an arylene group having C6 to C5.

[0254] Above L 22 can be combined with S of the compound represented by the above chemical formula 2.

[0255]

[0256] The above R 21 and R 22 are each independently, preferably hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 15 Alkyl group, C2 to C 15 Alkenyl group or C2 to C 15Alkynyl group of; more preferably C1 to C substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, halogen 10 Alkyl group, C2 to C 10 Alkenyl group or C2 to C 10 An alkynyl group; most preferably, it may be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C2 to C5 alkynyl group substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, or halogen.

[0257]

[0258] The compound represented by the above chemical formula 2 may be selected from a compound represented by the following chemical formula 2-1 and a compound represented by the following chemical formula 2-2:

[0259] <Chemical Formula 2-1>

[0260]

[0261] <Chemical Formula 2-2>

[0262]

[0263]

[0264] The content of the compound represented by the above chemical formula 2 may be 10.00 to 20.00 parts by weight, preferably 10.00 to 17.00 parts by weight, and more preferably 10.00 to 15.00 parts by weight, based on 100 parts by weight of the sum of the polymer and the compound represented by the above chemical formula 2. When the above-described conditions are satisfied, a composition of an ion-conducting membrane having mechanically stable strength, flexibility, and excellent ion conductivity can be prepared. However, if the content of the compound represented by the above chemical formula 2 is less than the above-described conditions, the ion-conducting membrane does not have appropriate strength, is easily damaged, and is not capable of self-standing. If the content of the compound represented by the above chemical formula 2 is excessive than the above-described conditions, the molar ratio of *-(-CH2-CH2-O)-* and lithium ions deviates from the optimal value, so that the ion conductivity is significantly reduced.

[0265]

[0266] 3) Lithium salt compounds

[0267]

[0268] The lithium salt compound plays a role in improving the ionic conductivity of the composition of the ion conductive film.

[0269]

[0270] The lithium salt compound may include at least one selected from the group consisting of a compound represented by the following chemical formula 3, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium bis(oxalato)borate:

[0271] <Chemical Formula 3>

[0272]

[0273] In the above chemical formula 3,

[0274] R 31 and R 32 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

[0275]

[0276] The compound represented by the above chemical formula 3, unlike the compound represented by the above chemical formula 2, does not contain a crosslinkable functional group. Therefore, the anion in the compound represented by the above chemical formula 3 can be free compared to the anion represented by the above chemical formula 2. Therefore, when the compound represented by the above chemical formula 2 and the compound represented by the above chemical formula 3 are used together, the synergistic effect of these can improve the ion conductivity of the composition of the ion conductive membrane.

[0277]

[0278] In the above chemical formula 3, in order to increase the degree of dissociation of lithium ions, the R31 and R 32 are each independently, preferably hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 15 Alkyl group, C2 to C 15 Alkenyl group or C2 to C 15 Alkynyl group of; more preferably C1 to C substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, halogen 10 Alkyl group, C2 to C 10 Alkenyl group or C2 to C 10 An alkynyl group; most preferably, it may be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C2 to C5 alkynyl group substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, or halogen.

[0279]

[0280] The compound represented by the above chemical formula 3 may include at least one selected from the compound represented by the following chemical formula 3-1 or the compound represented by the following chemical formula 3-2:

[0281] <Chemical Formula 3-1>

[0282]

[0283] <Chemical Formula 3-2>

[0284]

[0285]

[0286] The content of the lithium salt compound may be 1.00 to 60.00 parts by weight, preferably 3.00 to 55.00 parts by weight, and more preferably 4.00 to 51.00 parts by weight, based on 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2. When the above-described conditions are satisfied, the compound represented by the chemical formula 2 can supplement the insufficient amount of alkali metal ions, specifically, the amount of lithium ions. In addition, the sum of the oxygen included in the polymer and the lithium ions included in the compound represented by the chemical formula 2 and the lithium salt compound can have an optimal molar ratio, thereby improving ionic conductivity.

[0287]

[0288] 4) Compound represented by chemical formula 4

[0289]

[0290] The compound represented by the above chemical formula 4 can play a role in further improving the transport rate of lithium ions by capturing the anion of the compound represented by the above chemical formula 3.

[0291]

[0292] In the above chemical formula 4, the L 41 and L 42 are each independently, preferably directly bonded, C1 to C 15 alkylene group, C2 to C 15 Alkenylene group or C2 to C 15 Alkynylene group of; more preferably direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group or C2 to C 10 Alkynylene group of; most preferably direct bond, C1 to C 10 alkylene group, C2 to C 10 Alkenylene group or C2 to C 10 It may be an alkynylene group.

[0293] The above R 41 Inland R 45are each independently, preferably hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 15 Alkyl group, C2 to C 15 Alkenyl group or C2 to C 15 Alkynyl group of; more preferably C1 to C substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, halogen 10 Alkyl group, C2 to C 10 Alkenyl group or C2 to C 10 An alkynyl group; most preferably, it may be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, or a C2 to C5 alkynyl group substituted or unsubstituted with hydrogen, halogen, *-CN, *-OH, or halogen.

[0294]

[0295] The compound represented by the above chemical formula 4 may be a compound represented by the following chemical formula 4-1:

[0296] <Chemical Formula 4-1>

[0297]

[0298] In the above chemical formula 4-1,

[0299] y' is chosen from 1.0 to 30.0.

[0300]

[0301] The above y' can be preferably selected from 1 to 23.0, more preferably from 1 to 16.0, and most preferably from 1 to 10.0. When the above conditions are satisfied, the transport rate of lithium ions can be increased while minimizing the decrease in the strength of the ion conductive film manufactured with the composition of the ion conductive film.

[0302]

[0303] The content of the compound represented by the above chemical formula 4 may be 1.00 to 35.00 parts by weight, preferably 3.00 to 30.00 parts by weight, and more preferably 5.00 to 25.00 parts by weight, of the compound represented by the above chemical formula 4, based on 100 parts by weight of the sum of the polymer and the compound represented by the above chemical formula 2. When the above-described conditions are satisfied, the transport rate of lithium ions can be further improved.

[0304]

[0305] 5) Cross-linking agent

[0306]

[0307] A crosslinking agent can serve to increase the mechanical strength of an ion conductive membrane manufactured from a composition of the ion conductive membrane through additional crosslinking.

[0308]

[0309] The crosslinking agent may include a crosslinking functional group, and the crosslinking functional group may be a (meth)acrylate group. In addition, the crosslinking agent may include *-(-CH2-CH2-O)-* as a repeating unit.

[0310]

[0311] The crosslinking agent may include at least one selected from poly(ethylene glycol) diacrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, or pentaerythritol tetraacrylate.

[0312]

[0313] The composition of the above ion conductive film may include the crosslinking agent in an amount of 0.50 to 50.00 parts by weight, preferably 0.50 to 40.00 parts by weight, and more preferably 0.5 to 30.00 parts by weight, based on 100 parts by weight of the sum of the polymer and the compound represented by the above chemical formula 2. If the above conditions are satisfied, an ion conductive film having improved mechanical properties while maintaining excellent ion conductivity can be manufactured.

[0314]

[0315] 6) Additives

[0316]

[0317] The additive can serve to increase the mechanical strength of an ion conductive membrane manufactured from the composition of the ion conductive membrane.

[0318]

[0319] The above additive may include at least one selected from inert inorganic particles or lithium-based solid electrolytes.

[0320] The above inert inorganic particles may include at least one selected from silicon dioxide, aluminum oxide, zirconium oxide, or titanium oxide.

[0321] The above lithium-based solid electrolyte may include at least one selected from lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxide, lithium lanthanum titanate, or lithium germanium phosphorus sulfide.

[0322]

[0323] The composition of the above ion-conducting membrane may contain the additive in an amount of 0.30 to 95.00 parts by weight, preferably 0.50 to 90.00 parts by weight, and more preferably 10.00 to 90.00 parts by weight, based on 100 parts by weight of the sum of the polymer and the compound represented by the above chemical formula 2. When the above-described conditions are satisfied, the mechanical strength of the ion-conducting membrane may be improved.

[0324]

[0325] 2. Battery

[0326]

[0327] A battery according to another embodiment of the present invention comprises an ion conductive membrane manufactured from a composition of an ion conductive membrane according to an embodiment of the present invention.

[0328] The battery may be an all-solid-state battery. The all-solid-state battery may include an anode, an anode (or anode-less), and an ion-conducting membrane positioned between the anode and the anode, the ion-conducting membrane being manufactured using a composition according to an embodiment of the present invention. The all-solid-state battery may have a small decrease in ion conductivity, and the electronic conductivity of the included ion-conducting membrane may be low, so that the initial efficiency, life characteristics, and output characteristics of the all-solid-state battery may be excellent.

[0329] The above-mentioned all-solid-state battery can be manufactured according to a conventional method known in the art. For example, it can be manufactured by laminating and pressurizing so that an ion-conducting film exists between the positive and negative electrodes.

[0330]

[0331] 1) Bipolar

[0332]

[0333] 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.

[0334] 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.

[0335]

[0336] 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 (where 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(Nip1 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, such that 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.

[0337] Among these, the lithium metal oxide is LiCoO2, LiMnO2, LiNiO2, lithium nickel manganese cobalt oxide (e.g., Li(Ni)) in that it 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.

[0338] 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.

[0339] 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.

[0340] Typically, the binder may be included in an amount of 1 to 20 wt%, preferably 1 to 15 wt%, and more preferably 1 to 10 wt%, based on the total weight of solids excluding the solvent in the positive electrode slurry.

[0341] The above-mentioned conductive agent is a component for further improving the conductivity of the positive electrode active material.

[0342] 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.

[0343] 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.

[0344] 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.

[0345]

[0346] 2) Cathode

[0347]

[0348] 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.

[0349] 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.

[0350] 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 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 including a silicon alloy or lithium metal 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.

[0351] In addition, in the case of the lithium metal, it may be a conventional one including lithium single 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.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] 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 lithium (Li), nickel (Ni), tin (Sn), copper (Cu), and indium (In), or an alloy of two metals.

[0360]

[0361] 3) Ion conductive membrane

[0362]

[0363] The ion-conducting membrane is manufactured using a composition of the ion-conducting membrane according to one embodiment of the present invention. Specifically, the ion-conducting membrane may be manufactured by cross-linking the composition of the ion-conducting membrane.

[0364] The thickness of the ion conductive film is not particularly limited, but may be 0.1 to 1,000.0 μm, preferably 0.1 to 500.0 μm, and more preferably 1.0 to 100.0 μm. If the above conditions are satisfied, the ion conductive film can realize excellent energy density.

[0365]

[0366] The above ion conductive film may include a support to improve mechanical strength.

[0367] The support may include at least one selected from polyethylene, polypropylene, polyimide, polybenzimidazole, non-woven fabric, cellulose, glass fiber, or porous silica.

[0368] The above support may be a porous membrane.

[0369]

[0370] An ion conductive membrane including the support can be manufactured by impregnating the support into a composition of an ion conductive membrane according to one embodiment of the present invention and then performing a crosslinking reaction.

[0371]

[0372] The present invention provides a battery module including the above-described all-solid-state battery as a unit cell and a battery pack including the same. The battery module and battery pack include a 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 among electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage systems.

[0373]

[0374] Hereinafter, the present invention will be described in detail with reference to examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art.

[0375]

[0376] Manufacturing Example 1

[0377] <Manufacture of poly(dichlorophosphazene)>

[0378] Into the first reactor were charged 12 g of hexachlorocyclotriphosphazene, 10 ml of 1,2,4-trichlorobenzene, 25.4 mg of sulfamic acid, and 22.5 mg of CaSO4·H2O, and the internal environment of the first reactor was changed to a nitrogen environment. Subsequently, the internal temperature of the reactor was increased to 210°C, and polymerization was performed for 3 hours. Thereafter, the obtained polymerization product was purified by precipitation in heptane to isolate poly(dichlorophosphazene).

[0379] <Manufacture of polymers>

[0380] A poly(dichlorophosphazene) solution was prepared by dissolving 4 g of the above poly(dichlorophosphazene) in 150 ml of anhydrous tetrahydrofuran.

[0381] Meanwhile, a NaH mixture was prepared by mixing 2.7613 g (0.069 mol) of NaH solution (NaH concentration: 60 wt%, dispersant: mineral oil) and 20 ml of tetrahydrofuran. An alcohol mixture was prepared by mixing 8.2 ml of a mixture containing allyl alcohol and diethylene glycol monoethyl ether in a molar ratio of 2:8 and 40 ml of tetrahydrofuran.

[0382] After the NaH mixture was introduced into the second reactor (internal temperature: 0°C), the alcohol mixture was introduced. Subsequently, the internal temperature of the second reactor was increased to 25°C, and the NaH mixture and the alcohol mixture were reacted for 12 hours to produce an activated substituent.

[0383] The poly(dichlorophosphazene) solution and the activated substituent were sequentially introduced into the third reactor. Subsequently, the internal temperature of the third reactor was raised to 70°C, and substitution was performed for 40 hours to produce a polymer (weight average molecular weight: 1,000,000 g / mol) comprising a structural unit represented by the following chemical formula 1-1-1.

[0384] <Chemical Formula 1-1-1>

[0385]

[0386]

[0387] Manufacturing Example 2

[0388] <Manufacture of poly(dichlorophosphazene)>

[0389] Poly(dichlorophosphazene) was manufactured using the same method as in Manufacturing Example 1.

[0390] <Manufacture of polymers>

[0391] A poly(dichlorophosphazene) solution was prepared by dissolving 4 g of the above poly(dichlorophosphazene) in 150 ml of anhydrous tetrahydrofuran.

[0392] Meanwhile, a NaH mixture was prepared by mixing 2.7613 g (0.069 mol) of NaH solution (NaH concentration: 60 wt%, dispersant: mineral oil) and 20 ml of tetrahydrofuran. An alcohol mixture was prepared by mixing 15.2 ml of a mixture containing allyl alcohol, diethylene glycol monoethyl ether, and methoxy polyethylene glycol 350 (weight average molecular weight: 350 g / mol) in a molar ratio of 2:4:4 and 40 ml of tetrahydrofuran.

[0393] After the NaH mixture was introduced into the second reactor (internal temperature: 0°C), the alcohol mixture was introduced. Subsequently, the internal temperature of the second reactor was increased to 25°C, and the NaH mixture and the alcohol mixture were reacted for 12 hours to produce an activated substituent.

[0394] The poly(dichlorophosphazene) solution and the activated substituent were sequentially introduced into the third reactor. Subsequently, the internal temperature of the third reactor was raised to 70°C, and substitution was performed for 40 hours to produce a polymer (weight average molecular weight: 300,000 g / mol) comprising a structural unit represented by the following chemical formula 1-2-1 and a structural unit represented by the following chemical formula 1-2-2.

[0395] <Chemical Formula 1-2-1>

[0396]

[0397] <Chemical Formula 1-2-2>

[0398]

[0399]

[0400] Manufacturing Example 3

[0401] <Preparation of a compound represented by Chemical Formula 2-1>

[0402] Step 1

[0403] Under an inert atmosphere, 15.0 g (0.061 mol) of potassium 3-(methacryloyloxy)propane-1-sulfonate was suspended in 25 ml of anhydrous tetrahydrofuran. At this time, 1.7 ml of dimethylformamide was injected as a catalyst via a syringe. The reaction flask was then cooled to 0°C, and 39.9 g (0.335 mol) of thionyl chloride was injected with stirring. The reaction was carried out at 0°C for 1 hour and then at 25°C for an additional 12 hours.

[0404] The reaction-completed suspension was slowly poured into 200 ml of ice water to remove the reactivity of thionyl chloride. The upper aqueous layer was decanted, and the lower organic oil layer was diluted with 80 ml of dichloromethane. This solution was then washed six times with 25 ml of water each time and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off, and the dichloromethane was evaporated under reduced pressure, followed by further vacuum drying to obtain trifluoromethanesulfonamide.

[0405] Step 2

[0406] 7.3 g (0.049 mol) of trifluoromethanesulfonamide was charged into a reactor, and after replacing the reactor with nitrogen conditions, 10.9 g (0.107 mol) of anhydrous triethylamine was added with stirring. This mixture was diluted with 40 ml of anhydrous tetrahydrofuran, and the diluted solution was cooled to 0 °C in an inert atmosphere. A mixed solution was prepared by dissolving 11.1 g (0.049 mol) of 3-(chlorosulfonyl)propyl methacrylate in 15 ml of anhydrous tetrahydrofuran. The mixed solution was injected into the diluted solution, and the reaction was carried out at 0 °C for 1 hour and then at 25 °C for an additional hour. After the reaction was completed, the formed precipitate was removed by filtration, and the filtrate was evaporated. The obtained pale yellow oil was redissolved in 90 ml of dichloromethane, washed four times with 35 ml of water each time, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered from the dried product, dichloromethane was evaporated under reduced pressure, and further dried under vacuum to obtain triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide.

[0407] Step 3

[0408] 20.0 g (45 mmol) of triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide was dissolved in 60 mL of anhydrous tetrahydrofuran while stirring at 25°C under a nitrogen atmosphere. 0.76 g (91 mmol) of LiH was added at once to the solution, and the resulting suspension was stirred at 30°C overnight. Subsequently, unreacted LiH was filtered off, and the solution was concentrated under reduced pressure to obtain a yellow viscous oil. The yellow viscous oil was washed three times with 40 mL of hexane each time, dried under reduced pressure, and then recrystallized from anhydrous dichloromethane in the form of a white crystalline powder. The powder was then collected by filtration and dried under vacuum to obtain the final product, a compound represented by the above chemical formula 2-1.

[0409]

[0410] Manufacturing Example 4

[0411] <Preparation of a compound represented by chemical formula 4-1-1>

[0412] 2,5-Dimethylhexane-2,5-diol (5.0 g, 0.034 mol) and trimethyl borate (3.8 mL, 0.034 mol) were dissolved in 50 mL of anhydrous acetonitrile, and the mixture was stirred at 65°C for 1 hour under N2 purge conditions. Subsequently, 12 g (0.034 mol) of poly(ethylene glycol) methacrylate (number-average molecular weight: 500 g / mol) was added to the solution, and the mixture was stirred for an additional 3 hours at 65°C. After the reaction was completed, the residual solvent was removed by evaporation under reduced pressure. The product was dissolved in toluene, and the insoluble portion was removed by filtration, and the toluene was removed under reduced pressure at 60°C. The mixture was dried under vacuum at 25°C for 24 hours to obtain PEGMA containing a boronic acid ester group (a compound represented by the following chemical formula 4-1-1). The obtained product was stored in a vacuum oven to prevent contact with moisture that could cause hydrolysis.

[0413] <Chemical Formula 4-1-1>

[0414]

[0415]

[0416] Examples and Comparative Examples

[0417] <Preparation of ion-conducting membrane composition>

[0418] A composition of an ion conductive membrane was prepared by mixing the polymer prepared in Manufacturing Example 1, the polymer prepared in Manufacturing Example 2, the compound represented by Chemical Formula 2-1 prepared in Manufacturing Example 3, the compound represented by Chemical Formula 3-2 (sold by TCI), the compound represented by Chemical Formula 4-1-1 prepared in Manufacturing Example 4, poly(ethylene glycol) dimethacrylate, and poly(ethylene glycol) methacrylate, according to the components and contents described in Tables 1 and 2 below.

[0419] <Manufacturing of ion-conducting membranes>

[0420] The composition of the above ion-conducting membrane was dissolved in ethylene glycol dimethyl ether at a concentration of 10 wt%. Then, 3.00 parts by weight of azobisisobutyronitrile was added to 100 parts by weight of the composition of the ion-conducting membrane contained in the solution to prepare a polymer solution. 1 ml of this polymer solution was solution-casted onto a glass substrate (2.5 cm × 2.5 cm). The solvent was removed by a room temperature vacuum drying method, and an ion-conducting membrane was prepared through a crosslinking reaction in a vacuum oven set to 70°C.

[0421] Meanwhile, the ion conductive film can be manufactured in the same manner even if the glass substrate is changed to a heterogeneous PET film.

[0422] <Battery Manufacturing>

[0423] After separating the ion-conducting film from the glass substrate, it was cut with a 19 mm puncher and dried in a vacuum oven set at 60°C for 2 days. The thickness of the ion-conducting film was 150 μm, and a coin cell was manufactured using this ion-conducting film according to the CR2032 standard.

[0424]

[0425] Experimental Example 1

[0426] <Manufacturing and Measurement of a Cell for Ionic Conductivity Measurement>

[0427] The ion-conducting membranes of the examples and comparative examples were placed between two stainless steel electrodes to prepare measurement samples. The ionic conductivity was measured by complex impedance spectroscopy in the range of 10 to 100 °C using a Zahner Electrik IM6 device at 25 °C, a voltage of 10 mV, and a frequency range of 0.1 Hz to 1.0 MHz. The ionic conductivity of the ion-conducting membrane was calculated by using the real part of the impedance at the minimum of the imaginary part as the resistance. The ionic conductivity (σ) was calculated by substituting the electrolyte resistance (R), the thickness of the ion-conducting membrane (d), and the area of ​​the electrode (A) obtained from the impedance spectrum into the equation below.

[0428] Ionic conductivity (σ) = (1 / R) × (d / A)

[0429] In the present invention, when the ionic conductivity is 1.0E-06 S / cm or more, the ionic conductivity is evaluated as excellent.

[0430]

[0431] Experimental Example 2

[0432] <Fabrication and Measurement of Cells for Measuring Lithium Ion Transport Rates>

[0433] A Li symmetric cell, which is a measurement sample, was prepared by positioning the ion-conducting membranes of the examples and comparative examples between two lithium electrodes. The lithium ion transport rate was measured by electrochemical impedance spectroscopy (EIS) and the Bruce-Vincent method using direct current polarization. The Li symmetric cell was polarized with a constant DC voltage of 10 mV, and the current until it reached a steady state was recorded. In addition, the impedance of the cell at the initial and steady states was measured by EIS, and the lithium cation transport rate was calculated using the following equation.

[0434]

[0435] Lithium ion transport rate (tLi + )= iss(V-i0R0) / i0(V-issRss)

[0436] V: Constant voltage applied to the cell

[0437] i0: current in the initial state

[0438] iss: current in steady state

[0439] R0: Interface resistance at initial state

[0440] Rss: interface resistance at steady state

[0441]

[0442] In the present invention, when the lithium ion transport rate is 0.4 or higher, the lithium ion transport rate is evaluated as excellent.

[0443]

[0444] Experimental Example 3

[0445] When the ion conductive films of the examples and comparative examples were separated from the glass substrate, whether self-standing was possible was evaluated, and the results are shown in Tables 1 and 2 below.

[0446] ×: The ion-conducting film cannot be separated from the glass substrate.

[0447] △: The ion conductive film can be separated from the glass substrate, but it is crumpled or torn.

[0448] ○: Not only can the ion-conducting film be separated from the glass substrate, but it is also relatively uniform and solid.

[0449]

[0450] Example 1 Example 2 Example 3 Example 4 Example 5 Composition of ion conductive film (weight parts) Polymer manufactured in Preparation Example 1 8 0.00 9 0.00 9 0.00 0.00 0.00 Polymer manufactured in Preparation Example 2 0.00 0.00 0.00 0.00 0.00 Compound represented by Chemical Formula 2-1 2 0.00 10.00 10.00 10.00 10.00 Compound represented by Chemical Formula 3-2 4 00 15.00 2 4.00 3 0.00 2 2.00 Compound represented by Chemical Formula 4-1-1 0.00 0.00 2 0.00 2 0.00 0.00 0.00 Poly(ethylene glycol) dimethacrylate 0.00 0.00 0.00 0.00 0.00 Ion conductivity (S / cm, 25 ℃)1.9E-061.8E-053.0E-052.0E-052.0E-05Lithium ion transport rate0.70.60.60.70.7Magnetic standing capability○○○○○

[0451] Comparison Example 1Comparative Example 2Comparative Example 3Comparative Example 4Composition of ion conductive film (weight parts)Polymer manufactured in Manufacturing Example 190.000.0075.0095.00Polymer manufactured in Manufacturing Example 20.0070.000.000.00Compound represented by Chemical Formula 2-110.0030.0025.005.00Compound represented by Chemical Formula 3-20.000.000.0020.11Compound represented by Chemical Formula 4-1-10.000.000.000.00Poly(ethylene glycol) dimethacrylate0.000.000.000.00Poly(ethylene glycol) methacrylate0.000.000.000.00Ion conductivity (S / cm, 25 ℃)5.9E-073.0E-081.3E-07-Lithium ion transport rate0.80.8--Self-standing capability△△○×

[0452] Referring to Tables 1 and 2, Examples 1 and 2 using compositions of ion-conducting membranes including a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, and a compound represented by Chemical Formula 3, had excellent ion conductivity and lithium ion transport rate, and were also capable of self-standing. In addition, Examples 3 and 4 using compositions of ion-conducting membranes including a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, and a compound represented by Chemical Formula 4 also had excellent ion conductivity and lithium ion transport rate, and were also capable of self-standing.

[0453] In addition, Example 5, which used a composition of an ion conductive film including a polymer including a structural unit represented by Chemical Formula 1, a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, and a crosslinker, also had excellent ion conductivity and lithium ion transport rate, and was also capable of self-standing.

[0454] However, Comparative Examples 1 and 2 using a composition of an ion-conducting membrane that does not include a compound represented by Chemical Formula 3 showed a significantly reduced ion conductivity.

[0455] Comparative Example 3, which used a composition of an ion-conducting membrane containing 75.00 parts by weight of a polymer including a structural unit represented by Chemical Formula 1, had significantly low ion conductivity.

[0456] However, Comparative Example 4 was unable to stand on its own. Furthermore, its mechanical properties were weak, making it impossible to measure ionic conductivity.

Claims

1. A polymer comprising a structural unit represented by the following chemical formula 1; A compound represented by the following chemical formula 2; and Contains a lithium salt compound, A composition of an ion conductive membrane comprising 80.00 to 90.00 parts by weight of the polymer, based on 100 parts by weight of the sum of the polymer and the compound represented by the chemical formula 2: <Chemical Formula 1> In the above chemical formula 1 R 11 and R 12 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group, C2 to C 20 alkynyl group of *-L 11 -X 11 -L 12 -(-L 13 -O-)n 11 -R 13 or *-(L 14 -X 12 -)n 12 -L 15 -CH=CH2, L 11 Inland L 15 are each independently bonded directly, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group, X 11 and X 12 are each independently a direct bond or *-O-*, R 13 is hydrogen or C1 to C 20 is an alkyl group, n 11 and n 12 are each independently selected from 1.0 to 30.0; <Chemical Formula 2> In the above chemical formula 2, M1 is an alkali metal, L 21 Silver direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group, C6 to C 20 Arylene group or *-L 22 -OC(=O)-*, L 22 is a direct bond, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group of C2 to C 20 Alkynylene group or C6 to C 20 is an arylene group, R 21 and R 22 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

2. In claim 1, The structural unit represented by the above chemical formula 1 is a composition of an ion conductive membrane including at least one structural unit selected from the structural unit represented by the following chemical formula 1-1 to the structural unit represented by the following chemical formula 1-8: <Chemical Formula 1-1> <Chemical Formula 1-2> In the above chemical formula 1-2, n 11-1 is selected from 1.0 to 30.0; <Chemical Formula 1-3> In the above chemical formula 1-3, n 12-1 is selected from 1.0 to 30.0; <Chemical Formula 1-4> In the above chemical formula 1-4, n 11-2 and n 11-3 are each independently selected from 1.0 to 30.0; <Chemical Formula 1-5> In the above chemical formula 1-5, n 11-4 and n 12-2 are each independently selected from 1.0 to 30.0; <Chemical Formula 1-6> In the above chemical formula 1-6, n 12-3 and n 12-4 are each independently selected from 1.0 to 30.0; <Chemical Formula 1-7> In the above chemical formula 1-7, n 11-5 , n 11-6 , n 12-5 and n 12-6 are each independently selected from 1.0 to 30.

0. <Chemical Formula 1-8> In the above chemical formula 1-8, n 11-7 , n 11-8 , n 11-9 , n 12-7 , n 12-8 and n 12-9 are each independently selected from 1.0 to 30.

0.

3. In claim 1, The above polymer is a composition of an ion-conducting membrane having a weight average molecular weight of 1,000 to 10,000,000 g / mol.

4. In claim 1, The compound represented by the above chemical formula 2 is a composition of an ion conductive film selected from among a compound represented by the following chemical formula 2-1 and a compound represented by the following chemical formula 2-2: <Chemical Formula 2-1> <Chemical Formula 2-2> 5. In claim 1, The lithium salt compound is a composition of an ion conductive film including at least one selected from the group consisting of a compound represented by the following chemical formula 3, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium bis(oxalato)borate. <Chemical Formula 3> In the above chemical formula 3, R 31 and R 32 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group.

6. In claim 5, The compound represented by the above chemical formula 3 is a composition of an ion conductive film including at least one selected from the compounds represented by the following chemical formula 3-1 or the compounds represented by the following chemical formula 3-2: <Chemical Formula 3-1> <Chemical Formula 3-2> 7. In claim 1, For 100 parts by weight of the sum of the above polymer and the compound represented by the above chemical formula 2, A composition of an ion conductive film comprising 1.00 to 60.00 parts by weight of the above lithium salt compound.

8. In claim 1, A composition of an ion conductive film comprising a compound represented by the following chemical formula 4: <Chemical Formula 4> In the above chemical formula 4, L 41 and L 42 are each independently, directly bonded, C1 to C 20 alkylene group, C2 to C 20 Alkenylene group or C2 to C 20 is an alkynylene group, R 41 Inland R 45 are each independently hydrogen, halogen, *-CN, *-OH, C1 to C substituted or unsubstituted with halogen 20 Alkyl group, C2 to C 20 Alkenyl group or C2 to C 20 is an alkynyl group, y is chosen from 1.0 to 30.

0.

9. In claim 8, The compound represented by the above chemical formula 4 is a composition of an ion conductive film represented by the following chemical formula 4-1: <Chemical Formula 4-1> In the above chemical formula 4-1, y' is chosen from 1.0 to 30.

0.

10. In claim 8, For 100 parts by weight of the sum of the above polymer and the compound represented by the above chemical formula 2, A composition of an ion conductive film comprising 1.00 to 35.00 parts by weight of a compound represented by the above chemical formula 4.

11. In claim 1, A composition of an ion conductive membrane comprising a crosslinking agent.

12. In claim 11, A composition of an ion conductive membrane, wherein the crosslinking agent comprises at least one selected from poly(ethylene glycol) diacrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, or pentaerythritol tetraacrylate.

13. In claim 11, For 100 parts by weight of the sum of the above polymer and the compound represented by the above chemical formula 2, A composition of an ion conductive film comprising 0.50 to 50.00 parts by weight of the above crosslinking agent.

14. A battery comprising an ion-conducting membrane manufactured from the composition of the ion-conducting membrane according to claim 1.

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