KR20160026648A - Composite electrolyte, and lithium battery comprising electrolyte - Google Patents

Abstract

The present invention relates to a complex electrolyte including a polymeric ionic liquid, inorganic particle, and organic electrolyte as well as a lithium battery including the same. The present invention can improve cycle properties of the lithium battery.

Description

[0001] The present invention relates to a composite electrolyte and a lithium battery including the composite electrolyte,

A composite electrolyte and a lithium battery including the composite electrolyte.

A representative example of the negative electrode active material for a lithium battery is a carbon-based material such as graphite. Graphite is excellent in capacity retention characteristics and dislocation characteristics. In addition, graphite does not change in volume when lithium is occluded / released, and thus the stability of the battery is high. The theoretical capacity of graphite is as low as 372 mAh / g.

Lithium metal may be used as a negative electrode active material for a lithium battery. Lithium metal has a very high electric capacity per unit mass. The lithium metal may form a dendritic structure on the surface of the lithium metal in the process of intercalating / deintercalating lithium ions, thereby causing a short circuit between the positive electrode and the negative electrode. Further, the lithium metal has high reactivity with the liquid electrolyte at the time of charging and discharging.

In order to suppress the high reactivity of the lithium metal, a solid electrolyte may be introduced onto the surface of the lithium metal. For example, lithium phosphorous oxynitride (LiPON), which is a kind of inorganic electrolyte, has a very low lithium ion conductivity of less than 2 × 10 ^-6 S / cm at room temperature and has a very high resistance at a thickness of 200 nm or more. For example, LATP, a type of glass-ceramic solid electrolyte, is fragile and the transition metal in the solid electrolyte can react with lithium.

Therefore, there is still a need for an electrolyte that is stable and flexible with respect to lithium metal and has high ion conductivity.

One aspect is to provide a composite electrolyte.

Another aspect is to provide a lithium battery including the composite electrolyte.

According to one aspect,

Ionic liquid polymeric;

Inorganic particles: and

There is provided a composite electrolyte comprising an organic electrolyte.

According to another aspect,

anode;

cathode; And

And an electrolyte layer disposed on at least a portion of the cathode,

There is provided a lithium battery in which the electrolyte layer comprises the composite electrolyte according to the above.

According to one aspect, the cycle characteristics of the lithium battery can be improved by introducing the composite electrolyte.

1 is a schematic view of a lithium battery according to one embodiment.
2 is a schematic diagram of a multi-layered electrolyte layer according to another embodiment.
3 is a schematic view of a lithium battery according to another embodiment.
4 is a schematic view of a lithium battery according to another embodiment.
5 is a schematic view of a lithium battery according to another embodiment.
6 is a schematic view of a lithium battery according to another embodiment.
7 is a schematic view of a lithium battery according to another embodiment.
8A and 8B are cyclic voltammetry measurement results of the lithium battery manufactured in Example 5. FIG.
9A is a Nyquist plot showing impedance measurement results with time for a lithium battery manufactured in Comparative Example 9. FIG.
9B is a Nyquist plot showing impedance measurement results with time for the lithium battery manufactured in Example 9. FIG.
10 is a graph showing the life characteristics of the lithium batteries prepared in Examples 13 to 16, Comparative Examples 13 to 14, and Reference Example 1. FIG.

Hereinafter, a composite electrolyte according to exemplary embodiments and a lithium battery including the composite electrolyte will be described in more detail.

The composite electrolyte according to one embodiment includes an ionic liquid polymer; An inorganic particle, and an organic electrolyte.

In the conventional electrolyte, when the mechanical strength is increased, the ionic conductivity is poor, and when the ionic conductivity is increased, the mechanical strength is poor. In addition, dendrites were easily formed due to irregularity of ion distribution at the interface between the electrolyte and the electrode. On the other hand, the composite electrolyte simultaneously provides both ionic conductivity and mechanical strength by simultaneously containing ionic liquid polymer, inorganic particles and organic electrolyte, while securing a uniform ion distribution at the electrode / electrolyte interface to suppress dendrite formation can do.

The composite electrolyte may also provide electrochemical stability.

The composite electrolyte may be electrochemically stable with respect to lithium in a voltage range of 0 to 5.5V. For example, the composite electrolyte may be electrochemically stable with respect to lithium in a voltage range of 0 to 5.0V. For example, the composite electrolyte may be electrochemically stable with respect to lithium in a voltage range of 0V to 4.2V. The composite electrolyte can be applied to an electrochemical device operated at a high voltage by having an electrochemically stable wide voltage window.

For example, the composite electrolyte may have a current density of 0.05 mA / cm ² or less due to side reactions other than insertion / extraction of lithium at about 0 V with respect to lithium. For example, the composite electrolyte may have a current density of 0.02 mA / cm ² or less due to side reactions other than insertion / extraction of lithium at about 0 V with respect to lithium. For example, the composite electrolyte may have a current density of 0.01 mA / cm ² or less due to side reactions other than insertion / extraction of lithium at about 0 V with respect to lithium.

For example, the complex electrolyte may have a current density of 0.05 mA / cm ² or less due to an oxidation reaction at about 5.0 V with respect to lithium. For example, the complex electrolyte may have a current density of 0.04 mA / cm ² or less due to an oxidation reaction at about 5.0 V with respect to lithium. For example, the composite electrolyte may have a current density of 0.02 mA / cm ² or less due to an oxidation reaction at about 5.0 V with respect to lithium.

The composite electrolyte may have an ion conductivity of 1 x 10 < ^-4 > S / cm or more at room temperature. For example, the composite electrolyte may have an ion conductivity of 5 × 10 ^-4 S / cm or more at room temperature. For example, the composite electrolyte may have an ionic conductivity of 1 x 10 ^-3 S / cm or more at room temperature. The composite electrolyte can provide a high ion conductivity by including an organic electrolyte.

The composite electrolyte may form a non self-standing film. The composite electrolyte forms a film of a flexible composition to easily accommodate a volume change of the cathode and may not easily crack. For example, when the content of the inorganic particles is high, the composite electrolyte is difficult to form a self-supporting film and can form a film or a layer in a form disposed on another substrate or a support. Thus, it can be distinguished from conventional inorganic and / or complex electrolytes which form a self-standing film that is not flexible and easily cracked.

By including the inorganic electrolyte in the composite electrolyte, the mechanical strength of the composite electrolyte can be improved and the conductivity can be improved.

The inorganic particles may include at least one selected from the group consisting of metal oxides, carbon oxides, carbon-based materials and organic-inorganic composites. However, the inorganic particles are not necessarily limited to them, and if they are capable of improving ionic conductivity and mechanical strength of the electrolyte in the art Everything is possible. For example, the inorganic particles may be selected from the group consisting of Al ₂ O ₃ , SiO ₂ , BaTiO ₃ , MOF (Metal Organic Framework), graphite oxide, graphene oxide, POS (Polyhedral Oligomeric Silsesquioxanes), Li 2 CO 3, Li 3 PO 4 , Li3N, Li3S4, Li2O, montmorillonite, and the like.

The particle size of the inorganic particles may be less than 100 nm. For example, the particle size of the inorganic particles may be from 1 nm to 100 nm. For example, the particle size of the inorganic particles may be from 5 nm to 100 nm. For example, the particle size of the inorganic particles may be from 5 nm to 70 nm. For example, the particle size of the inorganic particles may be from 5 nm to 50 nm. For example, the particle size of the inorganic particles may be from 5 nm to 30 nm. For example, the particle size of the inorganic particles may be 10 nm to 30 nm.

The content of the inorganic particles in the composite electrolyte may be 1 to 95% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be from 5% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 10% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 30% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be more than 30% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be from 35% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 40% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 45% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 50% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 55% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. For example, the content of the inorganic particles may be 60% by weight to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. When the content of the inorganic particles in the composite electrolyte is 95 wt% or more, the dispersion of the inorganic particles may not be uniform, and the composite electrolyte membrane may be broken by the impact.

The inorganic particles may be porous. For example, the inorganic particles may be mesoporous particles. For example, the inorganic particles may include a shape in which specific inorganic particles such as Al ₂ O ₃ and SiO ₂ described above are porous.

In the complex electrolyte, the ionic liquid polymer is obtained by polymerizing an ionic liquid monomer, is not soluble in water, and can be dissolved in an organic solvent. The ionic liquid polymer includes a polymer backbone and a counter ion. The counter ion is not an inorganic ion such as a halide ion such as Cl ^- , Br ^- , or I ^- And is distinguished from a conventional polyelectrolyte in that it is a polyelectrolyte. By including the ionic liquid polymer in the composite electrolyte, a more uniform distribution of ions in the composite electrolyte can be obtained.

In the composite electrolyte, the ionic liquid polymer may be at least one selected from a cationic polymeric liquid, an anionic polymeric ionic liquid, and a zwitterionic polymeric ionic liquid.

The cationic liquid polymer is an ionic liquid polymer containing cations in the backbone and counter ions in the anion. For example, the cationic liquid polymer may have the structure of the following 1 to 33.

The anionic liquid polymer is an ionic liquid polymer having anions in the backbone and counter ions in the cation. For example, the anionic liquid polymer may have the structure of 34 to 41 below.

The amphoteric liquid polymer is an ionic liquid polymer which contains both ions in the backbone and the counter ion is a cation and / or an anion. For example, the amphoteric liquid polymer may have the structure of the following 42 to 47.

For example, in the complex electrolyte, the ionic liquid polymer may be represented by the following Formula 1:

≪ Formula 1 >

는 하나 이상의 헤테로원자를 포함하는 C2-C30의 탄소를 함유하는 3원자 내지 31원자 고리이며, X는 -N(R₂)(R₃), -N(R₂), -P(R₂) 또는 -P(R₂)(R₃)이고, R₁ 내지 R₄는 서로 독립적으로 수소, 비치환된 또는 치환된 C1-C30 알킬기, 비치환된 또는 치환된 C1-C30 알콕시기, 비치환된 또는 치환된 C6-C30 아릴기, 비치환된 또는 치환된 C6-C30 아릴옥시기, 비치환된 또는 치환된 C3-C30 헤테로아릴기, 비치환된 또는 치환된 C3-C30 헤테로아릴옥시기, 비치환된 또는 치환된 C4-C30 사이클로알킬기, 비치환된 또는 치환된 C3-C30 헤테로사이클로알킬기, 또는 비치환된 또는 치환된 C2-C100 알킬렌옥사이드기이고, Y^-는 음이온이고, a 및 b는 서로 독립적으로 1 내지 5의 정수이고, n은 500 내지 2800의 정수이다.In Formula 1,

(R ₂ ) (R ₃ ), -N (R ₂ ), -P (R ₂ ), and -P (R ₂ ) Or -P (R ₂ ) (R ₃ ), R ₁ to R ₄ independently of one another are hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, Unsubstituted or substituted C6-C30 aryl groups, unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, An unsubstituted or substituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group, Y ^- is an anion, a and b are Independently of one another, an integer of 1 to 5, and n is an integer of 500 to 2800. [

The "3-to 31-membered ring containing C2-C30 carbon containing one or more heteroatoms" is an unsubstituted or substituted C2-C30 heterocycle or an unsubstituted or substituted C2-C30 heteroaryl ring , The heteroatom is one selected from nitrogen, oxygen, phosphorus and sulfur.

가 하기 화학식 2로 표시될 수 있다:In the composite electrolyte,

May be represented by the following formula (2): < EMI ID =

(2)

Wherein Z represents N, S or P, and R ₅ and R ₆ independently represent hydrogen, a C 1 -C 30 alkyl group, a C 1 -C 30 alkoxy group, a C 6 -C 30 aryl group, a C 6 -C 30 aryloxy group, a C 3 -C 30 aryl group, A C3-C30 heteroaryl group, a C3-C30 hetero aryloxy group, a C4-C30 cycloalkyl group, a C3-C30 heterocycloalkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group or a C2-C100 alkylene oxide group.

For example, in the composite electrolyte, the ionic liquid polymer represented by Chemical Formula 1 may be an ionic liquid polymer represented by Chemical Formula 3:

(3)

In Formula 3, R ₁ to R ₈ independently represent hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 alkoxy group, an unsubstituted or substituted C6-C30 aryl group , Unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, unsubstituted or substituted C4-C30 C 1-30 alkylcycloalkyl group, unsubstituted or substituted C 3 -C 30 heterocycloalkyl group, or unsubstituted or substituted C 2 -C 100 alkylene oxide group, Y ^- represents BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^{- _{, AlCl 4 -, HSO 4 -}} , ClO 4 -, CH 3 SO 3 -, CF 3 CO 2 -, (CF 3 SO 2) 2 N -, Cl -, Br -, I -, BF 4 -, SO 4 ^{_{-, PF 6 -, ClO 4}} -, CF 3 SO 3 -, CF 3 CO 2 -, (C 2 F 5 SO 2) 2 N -, (C 2 F 5 SO 2) (CF 3 SO 2) N - and _{(CF 3 SO 2) 2 n} - is at least one selected from the group consisting of, wherein a and b are independently an integer of 1 to 5 from each other, n Is an integer from 500 to 2800.

For example, in the above formula (3), R ₇ and R ₈ are a C 1 -C 10 alkyl group, R ₁ to R ₄ are hydrogen or a C 1 -C 10 alkyl group, a and b are 1, Y- is BF ₄ ^{- _{6 -, ClO 4 -, CH}} 3 SO 3 -, CF 3 CO 2 -, (CF 3 SO 2) 2 N -, CF 3 SO 3 -, (C 2 F 5 SO 2) 2 N - or (C ₂ F ₅ SO ₂ ) (CF ₃ SO ₂ ) N ^- .

For example, the ionic liquid polymer can be poly (diallyldimethylammonium) trifluoromethanesulfonylimide (poly (diallyldimethylammonium) TFSI).

In the composite electrolyte, the organic electrolytic solution may be at least one selected from an organic solvent and an ionic liquid.

For example, the organic solvent may be at least one selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinylethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, , Dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, gamma -butyrolactone, dioxolane, 4-methyldioxolane, dimethylacetamide, But is not limited to, one or more selected from the group consisting of dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, succinonitrile and dimethyl ether, Which can be used as an organic solvent in the field of lithium metal Anything stable is possible.

For example, the ionic liquid may be represented by the following formula 4 or 5:

≪ Formula 4 >

는 적어도 하나의 헤테로원자를 포함하는 C2-C30의 탄소를 함유하는 3원자 내지 31원자 고리를 의미하며, X는 -N(R₂)(R₃), -N(R₂), -P(R₂) 또는 -P(R₂)(R₃)이고, Y^-는 음이온이고,In Formula 4,

Refers to at least one of the 3 to 31 atoms comprising carbon atoms in the C2-C30 containing hetero ring atoms, and, X is _{-N (R 2) (R 3} ), -N (R 2), -P ( R ₂ ) or -P (R ₂ ) (R ₃ ), Y ^- is an anion,

≪ Formula 5 >

In Formula 5, X is _{-N (R 2) (R 3} ), -N (R 2), -P (R 2) or _{-P (R 2) (R 3} ), R 11 is an unsubstituted Or an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl group, an unsubstituted or substituted C 6 -C 30 aryloxy group, An unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C4-C30 cycloalkyl group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, Substituted or substituted C2-C100 alkylene oxide group, Y ^- is an anion,

Wherein R ₂ and R ₃ are independently of each other hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl Unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, unsubstituted or substituted C4- C30 cycloalkyl group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group.

는 하기 화학식 6으로 표시되며, 상기 화학식 5의

가 화학식 7로 표시되는 양이온일 수 있다:For example,

Is represented by the following formula (6), and the formula

May be a cation represented by the general formula (7): < EMI ID =

(6)

In Formula 6, Z represents N or P, and R ₁₂ to R ₁₈ independently represent hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 alkoxy group, Unsubstituted or substituted C6-C30 aryl groups, unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, An unsubstituted or substituted C2-C30 alkenyl group, an unsubstituted or substituted C2-C30 alkynyl group, or an unsubstituted or substituted C2-C30 alkynyl group, Substituted or substituted C2-C100 alkylene oxide group,

≪ Formula 7 >

In Formula 7, Z represents N or P, and R ₁₂ to R ₁₅ independently represent hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, Unsubstituted or substituted C6-C30 aryl groups, unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, An unsubstituted or substituted C2-C30 alkenyl group, an unsubstituted or substituted C2-C30 alkynyl group, or an unsubstituted or substituted C2-C30 alkynyl group, Substituted or substituted C2-C100 alkylene oxide group.

For example, the ionic liquid _{[emim] Cl / AlCl 3 (} emim = ethyl methyl imidazolium), [bmpyr] NTf2 (bppyr = butyl methyl pyridinium), [bpy] Br / AlCl 3 (bpy = 4, 4'- bipyridine, [choline] Cl / CrCl ₃ ㅇ 6H ₂ O, [Hpy (CH ₂ ) ₃ pyH] [NTf ₂ ] ₂ (NTf = trifluoromethanesulfonimide), [emim] OTf / [hmim] I (hmim = hexyl methyl imidazolium ), [choline] Cl / HOCH ₂ CH ₂ OH, [Et ₂ MeN (CH ₂ CH ₂ OMe)] BF ₄ (Et = ethyl, Me = octyl, Hex = hexyl), [ Bu 3 PCH 2 CH 2 C 8 F 17] OTf (OTf = trifluoromethane sulfonate), [bmim] PF 6 (bmim = butyl methyl imidazolium), [bmim] BF 4, [omim] PF _{6 (omim = octyl methyl imidazolium)} , [Oct 3 PC 18 H 37] I, [NC (CH 2) 3 mim] NTf 2 (mim = methyl imidazolium), [Pr 4 N] [B (CN) 4], [Me ₃ NCH (Me) CH (OH) Ph] NTf ₂ , [bmim] NTf ₂ , [bmim] Cl, [bmim] [Me (OCH ₂ CH ₂ ) ₂ OSO ₃ ], [PhCH ₂ mim] _{[pmim] [(HO) 2} PO 2] (pmim = propyl methyl imidazolium), [b (6-Me) quin] NTf 2 (bquin = butyl quinolinium, [bmim] [Cu 2 Cl 3], [C 18 H ₃₇ OCH ₂ mime] BF ₄ (mime = methy l imidazolium), [heim] PF 6 (heim = hexyl ethyl imidazolium), [mim (CH 2 CH 2 O) 2 CH 2 CH 2 mim] [NTf 2] 2 (mim = methyl imidazolium), [obim] PF 6 (obim = octyl butyl imidazolium), [oquin] NTf 2 (oquin = octyl quinolinium), [hmim] [PF 3 (C 2 F 5) 3], [C 14 H 29 mim] Br (mim = methyl imidazolium), _{[Me 2 N (C 12 H} 25) 2] NO 3, [emim] BF 4, [mm (3-NO 2) im] [dinitrotriazolate], [MeN (CH 2 CH 2 OH) 3], [MeOSO 3 ], [Hex ₃ PC ₁₄ H ₂₉ ] NTf ₂ , [emim] [EtOSO ₃ ], [choline] [ibuprofenate], [emim] NTf ₂ , [emim] [(EtO) ₂ PO ₂ ] / CrCl ₂ , [Hex ₃ PC ₁₄ H ₂₉ ] N (CN) ₂ , and the like, but it is not necessarily limited thereto and can be used as an ionic liquid in the related art.

The liquid electrolyte includes a medium containing an organic solvent and / or an ionic liquid and a lithium salt. The lithium salt is not particularly limited and can be used as long as it can be used as a lithium salt of a liquid electrolyte in the related art. For example, the lithium salt can be, for example, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiAlO ₂ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, LiI or mixtures thereof. For example, the lithium salt may be LiPF _6.

The concentration of the liquid electrolyte lithium salt may be 0.01 to 2.0 M, but it is not necessarily limited to this range, and an appropriate concentration may be used if necessary. Further improved battery characteristics within the above range of concentration can be obtained.

A lithium battery according to another embodiment includes a positive electrode; cathode; And an electrolyte layer disposed on at least a part of the cathode, wherein the electrolyte layer includes the composite electrolyte described above.

For example, as shown in FIG. 1, the lithium battery 1 includes an anode 11; A cathode 12; And an electrolyte layer 13 disposed on the cathode. An intermediate layer 14 may be disposed between the anode 11 and the electrolyte layer 13. [ The intermediate layer 14 may be an electrolyte layer having a composition different from that of the electrolyte layer 13, a separator, or the like.

The above-described composite electrolyte in the lithium battery is disposed on at least a portion of the cathode so that the surface of the cathode can be electrochemically and mechanically stabilized. Therefore, when the lithium battery is charged and discharged, the formation of dendrite on the surface of the negative electrode is suppressed, the stability of the interface between the negative electrode and the composite electrolyte is improved, and a uniform current distribution can be obtained on the surface of the negative electrode. As a result, the cycle characteristics of the lithium battery can be improved. In addition, the electrolyte layer may serve as a protective layer for protecting the surface of the negative electrode. For example, when the electrolyte layer completely covers the surface of the negative electrode, the negative electrode surface is in direct contact with an electrolyte having a different composition (that is, highly reactive with the negative electrode surface) disposed between the electrolyte layer including the composite electrolyte and the positive electrode . As a result, the stability of the negative electrode can be improved by protecting the negative electrode.

In the lithium battery, an electrolyte layer including a composite electrolyte may be coated on at least a portion of the cathode. That is, the electrolyte layer is not simply deposited on the cathode, but the electrolyte layer is formed by the coating, so that the surface of the anode and the electrolyte layer can be uniformly and closely contacted. For example, the electrolyte layer and the cathode may be integrally formed. The coating method is not particularly limited, and any method can be used as long as it can be used as a coating method of the electrolyte layer in the related art such as bar coating and spin coating. For example, a composition containing the composite electrolyte may be coated on the surface of a negative electrode and dried at room temperature to form an electrolyte layer.

In the lithium battery, the thickness of the electrolyte layer including the composite electrolyte may be 40 占 퐉 or less. For example, the thickness of the electrolyte layer including the composite electrolyte in the lithium battery may be 0.01 탆 to 40 탆. For example, in the lithium battery, the thickness of the electrolyte layer including the composite electrolyte may be 0.1 to 40 탆. For example, in the lithium battery, the thickness of the electrolyte layer including the composite electrolyte may be 1 to 40 탆. For example, in the lithium battery, the thickness of the electrolyte layer including the composite electrolyte may be 1 to 30 占 퐉. For example, in the lithium battery, the thickness of the electrolyte layer including the composite electrolyte may be 1 to 20 탆. For example, the thickness of the electrolyte layer including the composite electrolyte in the lithium battery may be 1 to 15 탆. If the thickness of the electrolyte layer is excessively large, the interfacial resistance may increase.

For example, in the lithium battery, the cathode may include lithium metal. Further, the negative electrode may further include an alloy of lithium and another metal. The other metal is not limited to Si or Sn but may be any metal that can form an alloy with lithium.

The thickness of the lithium metal in the lithium battery may be less than 100 mu m. For example, the lithium battery can obtain a stable cycle characteristic even for a lithium thin film having a thickness of less than 100 mu m. For example, the thickness of the lithium metal in the lithium battery may be 80 탆 or less. For example, the thickness of the lithium metal in the lithium battery may be 60 탆 or less. For example, the thickness of the lithium metal in the lithium battery may be 500 탆 or less. In a conventional lithium battery, when the thickness of the lithium thin film is reduced to less than 100 占 퐉, the thickness of lithium deteriorated due to side reaction, dendrite formation, or the like is increased and it is difficult to realize a lithium battery that provides stable cycle characteristics.

In the lithium battery, there is a resin having a multi-layer structure in which the electrolyte layer includes two or more layers. For example, the electrolyte layer 13 of FIG. 1 may have a multi-layer structure including a first layer 131, a second layer 132, and a third layer 133 as shown in FIG.

In addition, the two or more layers may have different compositions. For example, the first layer 131, the second layer 132, and the third layer 133 of FIG. 2 may have different compositions. For example, the two or more layers may independently include at least one selected from a liquid electrolyte, a gel electrolyte, and a solid electrolyte. For example, in the multilayer structure, the third layer 133 of FIG. 2 adjacent to the cathode 12 of FIG. 1 includes the composite electrolyte described above, the second layer 132 comprises a liquid electrolyte, Layer 131 may comprise a solid electrolyte.

For example, as shown in FIGS. 9A to 9B, the impedance (resistance) after a lapse of 96 hours at 25 DEG C of the lithium battery in which the electrolyte layer including the composite electrolyte is disposed on the negative electrode is less than the lithium battery To 10%. For example, the impedance after a lapse of 96 hours at 25 캜 of a symmetric cell including an electrode coated with a complex electrolyte on a lithium metal is 10% or more, as compared with a symmetric cell comprising an electrode made of lithium metal not coated with the complex electrolyte. ≪ / RTI > The surface of the negative electrode is stabilized by disposing the electrolyte layer including the composite electrolyte on the negative electrode, and the increase of the interface resistance of the negative electrode over time can be remarkably reduced.

The lithium battery may further include a separator disposed between the anode and the cathode. As shown in FIG. 3, the lithium battery includes an anode 11; A cathode 12; An electrolyte layer (13) comprising a composite electrolyte disposed on the cathode; And a separator 141 disposed between the anode 11 and the electrolyte layer 13. The composition and the like of the separator 141 will be described more specifically in the following section of the battery manufacturing method. The separator 141 may be used in a state impregnated with a liquid electrolyte.

The lithium battery may further include a liquid electrolyte adjacent to the anode. As shown in FIG. 4, the lithium battery includes an anode 11; A cathode 12; An electrolyte layer (13) comprising a composite electrolyte disposed on the cathode; And a liquid electrolyte 142 disposed between the anode 11 and the electrolyte layer 13. The liquid electrolyte 142 may be the same or different in composition from the liquid electrolyte contained in the composite electrolyte of the electrolyte layer 13. The composition and the like of the liquid electrolyte 142 are as described above.

In the lithium battery, the anode may be a porous anode impregnated with a liquid electrolyte. As shown in FIG. 5, the lithium battery includes a porous anode 111; A cathode 12; An electrolyte layer (13) comprising a composite electrolyte disposed on the cathode; And a liquid electrolyte 142 disposed between the anode 11 and the electrolyte layer 13. In this specification, the porous anode 111 includes not only an anode in which pores are intentionally formed but also an anode in which the liquid electrolyte can be permeated into the anode by capillary phenomenon without intentionally excluding the formation of pores. That is, the porous anode 111 includes an anode including pores formed in the manufacturing process. For example, the porous anode 111 includes a cathode obtained by coating and drying a cathode active material composition including a cathode active material, a conductive material, a binder, a solvent, and the like. The porous anode 111 obtained from the cathode active material composition may include pores existing between the cathode active material particles. The porous anode 111 may be impregnated into the liquid electrolyte 142. As the porous anode 111 is impregnated into the liquid electrolyte 142, the contact between the cathode active material and the electrolyte increases, thereby reducing the internal resistance of the lithium battery.

In the lithium battery, the anode may include at least one selected from a liquid electrolyte, a gel electrolyte, and a solid electrolyte. The positive electrode may include a liquid electrolyte, a gel electrolyte, a solid electrolyte, and the like in the positive electrode to improve the conductivity of the lithium ion. The liquid electrolyte, the gel electrolyte, and the solid electrolyte can be used as an electrolyte of a lithium battery in the related art, as long as they do not deteriorate the cathode active material by reacting with the cathode active material during charging and discharging. The liquid electrolyte may be the same as the liquid electrolyte impregnated into the porous anode 111 in FIG. The gel electrolyte may be a polymer gel electrolyte. The solid electrolyte may be a solid polymer electrolyte, a solid inorganic ion conductor, or the like.

The lithium battery includes a positive electrode; cathode; And a composite electrolyte layer adjacent to the anode, and a solid electrolyte layer disposed on at least a portion of the cathode. 6, the lithium battery includes a positive electrode 11, a negative electrode 12, a composite electrolyte layer 13 adjacent to the positive electrode 11, and a negative electrode 12 between the composite electrolyte layer 13 and the negative electrode 12, And a solid electrolyte layer 143 disposed on the solid electrolyte layer. The composite electrolyte layer 13 may have a multilayer structure as shown in FIG. For example, the composite electrolyte layer 13 in which the composite electrolyte is contained in at least one of the first layer 131, the second layer 132, and the third layer 133 of the multilayer structure shown in FIG. 2, (Not shown).

The solid electrolyte layer 143 may be formed of one selected from the group consisting of an ionically conducting polymer, an ionic liquid polymer (PIL), an inorganic electrolyte, a polymer matrix, and an electronically conducting polymer But are not limited thereto and can be used as solid electrolytes in the art. The polymer matrix may not have ionic conductivity or electron conductivity.

For example, the solid electrolyte layer 143 can be formed of a polymer selected from the group consisting of polyethylene oxide (PEO), a solid graft copolymer including a polymer block having a low Tg of 2 or more, poly (diallyldimethylammonium) methane sulfonyl imide (poly (diallyldimethylammonium) TFSI), Cu 3 N, Li 3 N, LiPON, Li 3 PO 4 .Li 2 S.SiS 2, Li 2 S.GeS 2 .Ga 2 S 3, Li 2 O _{.11Al 2 O 3, Na 2 O.11Al} 2 O 3, (Na, Li) 1 + x Ti 2-x Al x (PO 4) 3 (0.1-x-0.9), Li 1 + x Hf 2-x _{Al x (PO 4) 3 (} 0.1-x-0.9), Na 3 Zr 2 Si 2 PO 12, Li 3 Zr 2 Si 2 PO 12, Na 5 ZrP 3 O 12, Na 5 TiP 3 O 12, Na 3 Fe ₂ P ₃ O ₁₂ , Na ₄ NbP ₃ O ₁₂ , Na-Silicates, Li _0.3 La _0.5 TiO ₃ , Na ₅ MSi ₄ O ₁₂ (M is rare earth element such as Nd, Gd and Dy) Li ₅ ZrP ₃ O ₁₂ , _{Li 5 TiP 3 O 12, Li} 3 Fe 2 P 3 O 12, Li 4 NbP 3 O 12, Li 1 + x (M, Al, Ga) x (Ge 1-y Ti y) 2-x (PO 4) _{3 (x-0.8, 0-} y-1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , or _{Yb), Li 1 + x +} y Q x Ti 2-x Si y P _3-y O ₁₂ (0 < x-0.4, 0 < y-0.6, Q is Al or G _{a), Li 6 BaLa 2 Ta} 2 O 12, Li 7 La 3 Zr 2 O 12, Li 5 La 3 Nb 2 O 12, Li 5 La 3 M 2 O 12 (M is _{Nb, Ta), Li 7 +} x A _x La _3-x Zr ₂ O ₁₂ (0 <x <3, A is Zn).

For example, the solid electrolyte layer 143 may include at least one ion conductive repeating unit selected from ether-based monomers, acrylic monomers, methacrylic monomers, and siloxane monomers as the ion conductive polymer .

For example, the ion conductive polymer may be at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polymethylmethacrylate, polyethylmethacrylate, polydimethylsiloxane, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, Polyhexyl methacrylate, poly 2-ethylhexyl acrylate, polybutyl methacrylate, poly 2-ethylhexyl methacrylate, polydesyl acrylate, and polyethylene vinyl acetate.

For example, the ion conductive polymer may be a copolymer including an ion conductive repeating unit and a structural repeating unit.

For example, the ionic conductive repeating unit may be selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, butyl methacrylate, Methacrylate, decyl acrylate, ethylene vinyl acetate, ethylene oxide, propylene oxide, and the structural repeating unit is at least one monomer selected from the group consisting of styrene, 4-bromostyrene, tert-butylstyrene, divinylbenzene, methyl Acrylates such as methacrylate, isobutyl methacrylate, butadiene, ethylene, propylene, dimethylsiloxane, isobutylene, N-isopropylacrylamide, vinylidene fluoride, acrylonitrile, , Ethylene terephthalate, and vinyl pyridine. Lt; / RTI &gt;

For example, the ion conductive polymer may be a block copolymer including an ion conductive phase and a structural phase. Block copolymers comprising the ionic conducting and structural phases are described, for example, in USP 8,269,197; USP 8,563,168; US 2011/0206994.

The lithium battery including the composite electrolyte can be made as follows. For example, the anode 11 shown in Fig. 4; A cathode 12; An electrolyte layer (13) comprising a composite electrolyte disposed on the cathode; And a liquid electrolyte 142 disposed between the anode 11 and the electrolyte layer 13 can be manufactured as follows. Further, a separator may be additionally disposed between the anode 11 and the electrolyte layer 13.

First, a cathode is prepared.

The lithium metal thin film can be used as the negative electrode as it is. Alternatively, the negative electrode may include a current collector and a negative electrode active material layer disposed on the current collector. For example, the cathode can be used as a counter electrode disposed on a conductive substrate where a lithium metal thin film is a current collector. The lithium metal thin film can form an integrated body with the current collector.

In the cathode, the current collector may be any one selected from the group consisting of stainless steel, copper, nickel, iron, and cobalt, but is not necessarily limited thereto, and any metallic substrate having excellent conductivity that can be used in the technical field is available. For example, the current collector may be a conductive oxide substrate, a conductive polymer substrate, or the like. The current collector may have various structures such as a structure in which the entire substrate is made of a conductive material, a form in which a conductive metal, a conductive metal oxide, and a conductive polymer are coated on one surface of an insulating substrate. The current collector may be a flexible substrate. Therefore, the current collector can be easily bent. Further, after bending, the current collector may be easily restored to its original shape.

The negative electrode may further include a negative electrode active material in addition to lithium metal. The negative electrode may be an alloy of a lithium metal and another negative active material, a composite of a lithium metal and another negative active material, or a mixture of a lithium metal and another negative active material.

Other negative electrode active materials that may be added to the negative electrode may include, for example, at least one selected from the group consisting of lithium-alloyable metals, transition metal oxides, non-transition metal oxides, and carbon-based materials.

For example, the metal that can be alloyed with lithium is at least one element selected from the group consisting of Si, Sn, Al, Ge, Pb, Bi, Sb Si-Y alloys (Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, (Wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination element thereof, and not a Sn element) ) And the like. The element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, or a combination thereof.

For example, the transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like.

For example, the non-transition metal oxide may be SnO ₂ , SiO _x (0 <x <2), or the like.

The carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake, spherical or fibrous shape, and the amorphous carbon may be soft carbon or hard carbon carbon, mesophase pitch carbide, calcined coke, and the like.

Alternatively, the cathode may comprise another anode active material instead of lithium metal. The negative electrode may be prepared by using a negative electrode active material composition containing a conventional negative electrode active material, a conductive agent, a binder and a solvent in place of the lithium metal.

For example, after a conventional general negative electrode active material composition is produced, a negative electrode plate is coated directly on the current collector, or a negative electrode active material film that is cast on a separate support and peeled from the support is laminated on the current collector, Can be obtained. The cathode is not limited to those listed above, but may be any other form that can be used in the art. For example, the negative electrode may be manufactured by printing a negative electrode active material ink including a conventional negative electrode active material, an electrolyte, and the like on the current collector, using an ink jet method or the like.

The conventional negative electrode active material may be in powder form. The powdery negative electrode active material may be applied to the negative electrode active material composition or the negative electrode active material ink.

As the conductive agent, carbon black, graphite fine particles, and the like may be used, but not limited thereto, and any conductive agent may be used as long as it can be used in the art.

Examples of the binder include vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and mixtures thereof, and styrene butadiene rubber-based polymers May be used, but not limited to, and may be used as long as they can be used as binders in the art.

As the solvent, N-methylpyrrolidone, acetone, water, or the like may be used, but not limited thereto, and any solvent that can be used in the technical field can be used.

The content of the conventional negative electrode active material, the conductive agent, the binder, and the solvent is generally used in a lithium battery. Depending on the use and configuration of the lithium battery, one or more of the conductive agent, the binder and the solvent may be omitted.

Next, a composite electrolyte composition is prepared.

The composite electrolyte composition may be prepared by adding inorganic particles and a liquid electrolyte to a solution containing an ionic liquid polymer and mixing them. The ionic liquid polymer, inorganic particles, and liquid electrolyte that can be used in the preparation of the composite electrolyte composition are as described above. For example, the composite electrolyte composition may be prepared by adding poly (diallyldimethylammonium) TFSI, alumina (Al ₂ O ₃ ), and ethylene carbonate (DMF) to a dimethylformamide (DMF) EC), diethyl carbonate (DEC), and fluoroethylene carbonate (FEC) in a volume ratio of 2: 6: 2 by volume of a liquid electrolyte containing 1.3M LiPF6 dissolved therein.

The composite electrolyte composition prepared above was coated on a negative electrode and dried at room temperature to remove the solvent (DMF) to obtain a composite electrolyte layer coated on the negative electrode.

Next, the anode can be manufactured as follows.

The anode may be manufactured in the same manner as the anode active material composition except that the anode is used as a cathode active material instead of the anode active material.

As the conductive agent, the binder and the solvent in the positive electrode active material composition, the same materials as those of the negative electrode active material composition may be used. A cathode active material composition, a conductive agent, a binder and a solvent are mixed to prepare a cathode active material composition. The positive electrode active material composition is directly coated on the aluminum current collector and dried to produce a positive electrode plate having a positive electrode active material layer. Alternatively, the cathode active material composition may be cast on a separate support, and then a film obtained by peeling the support from the support may be laminated on the aluminum current collector to produce a cathode plate having a cathode active material layer.

The cathode active material is a lithium-containing metal oxide, and any of those conventionally used in the art can be used without limitation. For example, at least one of complex oxides of metal and lithium selected from cobalt, manganese, nickel, and combinations thereof may be used. Specific examples thereof include Li _a A _1-b B _b D ₂ In the formula, 0.90? A? 1.8, and 0? B? 0.5); Li _a E _1-b B _b O _{2 -c} D _c wherein, in the formula, 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05; LiE (in the above formula, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05) 2-b B b O 4-c D c; Li _a Ni _{1 -bc} Co _b B _c D _? Wherein, in the formula, 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05, 0 <? Li _a Ni _{1- b c} Co _b B _c O _{2 -?} F _? Wherein? 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05, 0 <? Li _a Ni _{1- b c} Co _b B _c O _2-α F ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 <α <2; Li _a Ni _1-bc Mn _b B _c D _? Wherein, in the formula, 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05, 0 <? Li _a Ni _1-bc Mn _b B _c O _2-α F _α wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 <α <2; Li _a Ni _1-bc Mn _b B _c O _2-α F ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 <α <2; Li _a Ni _b E _c G _d O ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, and 0.001 ≤ d ≤ 0.1; Li _a Ni _b Co _c Mn _d GeO ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5, and 0.001 ≤ e ≤ 0.1; Li _a NiG _b O ₂ (in the above formula, 0.90? A? 1.8, and 0.001? B? 0.1); Li _a CoG _b O ₂ wherein, in the above formula, 0.90? A? 1.8, and 0.001? B? 0.1; Li _a MnG _b O ₂ (in the above formula, 0.90? A? 1.8, 0.001? B? 0.1); Li _a Mn ₂ G _b O ₄ wherein, in the above formula, 0.90? A? 1.8, and 0.001? B? 0.1; QO _2; QS ₂ ; LiQS ₂ ; V ₂ O ₅ ; LiV ₂ O ₅ ; LiIO ₂ ; LiNiVO _4; Li _(3-f) J ₂ (PO ₄ ) ₃ (0? F? 2); Li _(3-f) Fe ₂ (PO ₄ ) ₃ (0? F? 2); In the formula of LiFePO ₄ may be used a compound represented by any one:

In the above formula, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; F is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or combinations thereof; Q is Ti, Mo, Mn, or a combination thereof; I is Cr, V, Fe, Sc, Y, or a combination thereof; J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

For example, LiCoO ₂ , LiMn _x O ₂ x (x = 1, 2), LiNi _1-x Mn _x O _2x (0 <x <1), Ni _1-xy Co _x Mn _y O ₂ ? 0.5, 0? Y? 0.5), LiFePO _4, or the like can be used.

Of course, a compound having a coating layer on the surface of the compound may be used, or a compound having a coating layer may be mixed with the compound. The coating layer may comprise an oxide, a hydroxide of the coating element, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, or a coating element compound of the hydroxycarbonate of the coating element. The compound constituting these coating layers may be amorphous or crystalline. The coating layer may contain Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or a mixture thereof. The coating layer forming step may be any coating method as long as it can coat the above compound by a method which does not adversely affect the physical properties of the cathode active material (for example, spray coating, dipping, etc.) by using these elements, It will be understood by those skilled in the art that a detailed description will be omitted.

The content of the cathode active material, the conductive agent, the binder and the solvent is a level commonly used in a lithium battery.

Next, a separator to be inserted between the positive electrode and the negative electrode is prepared.

The separator can be used as long as it is commonly used in a lithium battery. A material having low resistance against the ion movement of the electrolyte and excellent in the ability to impregnate the electrolyte may be used. For example, selected from glass fibers, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or a combination thereof, in the form of a nonwoven fabric or a woven fabric. For example, a rewindable separator such as polyethylene, polypropylene or the like may be used for the lithium ion battery. For example, a separator having excellent ability to impregnate an organic electrolyte can be used for a lithium ion polymer battery. A separator having an excellent ability to impregnate an organic electrolyte can be produced by the following method.

A polymer resin, a filler and a solvent are mixed to prepare a separator composition. The separator composition may be coated directly on the electrode and dried to form a separator. Alternatively, after the separator composition is cast and dried on a support, a separator film peeled from the support may be laminated on the electrode to form a separator.

The polymer resin that can be used in the production of the separator is not particularly limited, and any material used for the binder of the electrode plate may be used. For example, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, or a mixture thereof may be used.

Next, a liquid electrolyte is prepared.

For example, an organic electrolytic solution is prepared. The organic electrolytic solution can be prepared by dissolving a lithium salt in an organic solvent.

The organic solvent may be any organic solvent which can be used in the art. Examples of the solvent include propylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinylethylene carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, But are not limited to, furan, gamma -butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, Examples of the solvent include ethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl isopropyl carbonate, succinonitrile, diethyl glycol dimethyl ether, tetraethylene glycol dimethyl ether, triethyl glycol dimethyl ether, polyethyl glycol dimethyl ether, ethyl propyl carbonate, Propyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether or the like A mixture thereof.

The lithium salt may also be used as long as it can be used in the art as a lithium salt. For example, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiAlO ₂ , LiAlCl ₄ , _x F _{2x + 1} SO 2) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, LiI, or a mixture thereof.

7, the lithium battery 1 includes a positive electrode 3, a negative electrode 2, and a separator 4. The positive electrode 3, the negative electrode 2, The anode 3, the cathode 2 and the separator 4 described above are wound or folded and housed in the battery case 5. Then, an organic electrolytic solution is injected into the battery case 5 and is sealed with a cap assembly 6 to complete the lithium battery 1. Although not shown in the drawing, an electrolyte layer including a composite electrolyte is formed on the cathode 2. The battery case may have a cylindrical shape, a rectangular shape, a thin film shape, or the like. For example, the lithium battery may be a thin film battery. The lithium battery may be a lithium ion battery.

Alternatively, a separator may be disposed between the anode and the cathode to form a battery structure. The cell structure is laminated in a bi-cell structure, then impregnated with an organic electrolyte solution, and the obtained result is received in a pouch and sealed to complete a lithium ion polymer battery.

In addition, a plurality of battery assemblies may be stacked to form a battery pack, and such battery pack may be used for all devices requiring high capacity and high output. For example, a notebook, a smart phone, an electric vehicle (EV), and the like.

The lithium battery is not limited to a lithium ion battery or a lithium polymer battery, and may include a lithium air battery, a lithium total solid battery, or the like.

The present invention will be described in more detail by way of the following examples and comparative examples. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

 (Preparation of composite electrolyte)

Preparation Example 1: Preparation of ionic liquid polymer

(Diallyldimethylammonium) chloride (# 409022 Aldrich, weight (weight)) represented by the following general formula (11) was obtained by dissolving 8.52 g of lithium bis (trifluoromethanesulfonyl) imide: LiTFSi in 10 ml of distilled water, Average molecular weight: 200,000 ~ 350,000, 20% by weight in water) in 100 ml of distilled water was put in a 250 ml spherical flask. When the reaction mixture was stirred at room temperature (20 ° C) for 1 hour, a precipitate, white crystal, was formed. The obtained white crystals were filtered and dried in a vacuum oven at 105 ° C. to obtain poly (diallyldimethylammonium) TFSI represented by the following formula (12). The recovery of poly (diallyldimethylammonium) TFSI was about 93.5% by weight.

[Chemical Formula 12]

In the above formula (11), n was about 2,500.

(11)

In the above formula (12), n is about 2500

Example 1: Preparation of composite electrolyte and negative electrode

Poly (diallyldimethylammonium) TFSI of Formula 12 prepared in Preparation Example 1, alumina (Al ₂ O ₃ ) particles (Nanoamor, 10 nm, 99% purity, 160 m ² / g, Lot # 1041-070510) , An electrolytic solution in which 1.3 M of LiPF ₆ was dissolved in a liquid electrolyte (EC (ethylene carbonate): DEC (diethyl carbonate): FEC (fluoroethylene carbonate) mixed solvent of 2: 6: 2 by volume ratio) (Diallyldimethylammonium) TFSI solution was obtained in dimethylformamide (DMF) at a weight ratio of 1: 1, and the mixture was stirred at room temperature (20 DEG C) for 1 hour to prepare a composite electrolyte-forming composition. The composition was coated on a lithium metal thin film having a thickness of 40 탆 formed on a copper current collector with a doctor blade and dried at a high temperature (40 캜), followed by vacuum drying (20 캜, 12 hr) A negative electrode having a structure in which a composite electrolyte layer having a thickness of 15 mu m was coated was prepared. The content of alumina in the composite electrolyte layer was 60% by weight based on the total weight of the alumina and the ionic liquid polymer.

Example 2

A negative electrode was prepared in the same manner as in Example 1, except that the composite electrolyte composition was changed so that the alumina content was 30% by weight based on the total weight of the alumina and the ionic liquid polymer in the composite electrolyte layer.

Example 3

A negative electrode was prepared in the same manner as in Example 1, except that the composition of the composite electrolyte-forming composition was changed so that the content of alumina was 90% by weight based on the total weight of the alumina and the ionic liquid polymer in the composite electrolyte layer.

Example 4

Silica (SiO ₂ ) particles (Dittotechnology, DT- ₁ ) having an average particle diameter of 30 nm were used instead of alumina (Al ₂ O ₃ ) particles having an average particle diameter of 10 nm (Nanoamor, 10 nm, 99% purity, 160 m ² / g, Lot # 1041-070510) SIO-N50S) is used,

A negative electrode was prepared in the same manner as in Example 1, except that the composition of the composite electrolyte-forming composition was changed so that the content of silica in the composite electrolyte layer was 40% by weight based on the total weight of the silica and the ionic liquid polymer.

Comparative Example 1: Inorganic particles were not added

A negative electrode was prepared in the same manner as in Example 1, except that the inorganic particles (Al ₂ O ₃ ) were not added.

Specifically, poly (diallyldimethylammonium) TFSI of Formula 12 prepared in Preparation Example 1, 2: 6: 2 of liquid electrolyte (EC (ethylene carbonate): DEC (diethyl carbonate): FEC (fluoroethylene carbonate) (Electrolytic solution in which 1.3 M of LiPF ₆ was dissolved in a mixed solvent at a volume ratio of 2: 3) was added to obtain a 10 wt% poly (diallyldimethylammonium) TFSI solution in dimethylformamide (DMF) at a weight ratio of 2: 3 A negative electrode was prepared in the same manner as in Example 1.

Comparative Example 2: Addition of organic solvent and inorganic particles

A negative electrode was prepared in the same manner as in Example 1 except that only the lithium salt was added instead of the liquid electrolyte without adding the inorganic particles (Al ₂ O ₃ ).

Specifically, poly (diallyldimethylammonium) TFSI of Formula 12 prepared in Preparation Example 1, monomer (repeating unit) and lithium salt (LiPF ₆ ) were dissolved in dimethylformamide (DMF) in a molar ratio of 18: Except that a 10 wt% poly (diallyldimethylammonium) TFSI solution was obtained in the same manner as in Example 1.

Comparative Example 3: Ionic liquid polymer not added

The negative electrode was prepared in the same manner as in Example 1 except that the ionic liquid polymer was not added, but the electrolyte layer was not formed on the lithium metal thin film.

Comparative Example 4: Use of Conventional Ionic Conducting Polymer

A negative electrode was prepared in the same manner as in Example 1, except that polyethylene oxide (PEO) was used instead of the ionic liquid polymer.

(Manufacture of half cell)

Example 5

The composition prepared in Example 1 was coated on a copper current collector and a SUS current collector with a Doctor blade and dried at a high temperature (40 ° C), followed by vacuum drying at room temperature (25 ° C, 12 hours) An electrode having a structure in which a composite electrolyte layer was coated was prepared. The content of alumina in the composite electrolyte layer was 60% by weight based on the total weight of the alumina and the ionic liquid polymer.

The prepared electrode was used as a working electrode and a lithium metal thin film coated on the copper current collector and the SUS current collector was used as a counter electrode and a polypropylene separator (Celgard 3501) was used as a separator And a solution in which 1.3 M LiPF ₆ was dissolved in EC (ethylene carbonate) + DEC (diethylene carbonate) + FEC (fluoroethylene carbonate) (2: 6: 2 by volume) was used as an electrolyte to prepare a coin cell.

Examples 6 to 8

A lithium battery was prepared in the same manner as in Example 5, except that the compositions prepared in Examples 2 to 4 were used in place of the compositions prepared in Example 1, respectively.

Comparative Examples 5 to 8

A lithium battery was prepared in the same manner as in Example 5, except that the composition prepared in Comparative Examples 1 to 4 was used instead of the composition prepared in Example 1 above.

(Manufactured by symmetry cell)

Example 9

The electrode prepared in Example 1 was used as a working electrode and a polypropylene separator (Celgard ^® 3501) was used as a separator. 1.3M LiPF ₆ was added to a mixture of EC (ethylene carbonate) + DEC Coin cell (symmetric cell) was prepared by using a solution in which the electrolyte solution was dissolved in an electrolyte (ethylene carbonate) + FEC (fluoroethylene carbonate) (2: 6: 2 by volume) as an electrolyte.

Examples 10 to 12

A symmetric cell was fabricated in the same manner as in Example 9, except that the electrodes prepared in Examples 2 to 4 were used in place of the electrodes prepared in Example 1, respectively.

Comparative Examples 9 to 12

A symmetric cell was fabricated in the same manner as in Example 9, except that the electrodes prepared in Comparative Examples 1 to 4 were used in place of the electrodes prepared in Example 1 above.

(Full cell manufacture)

Example 13

A polypropylene separator (Celgard ^® 3501) was used as the anode, LiCoO ₂ as the positive electrode active material, and a separator (separator, Celgard ^® 3501), and 1.3M LiPF ₆ was mixed with EC (ethylene carbonate) + DEC Carbonate) + FEC (fluoroethylene carbonate) (2: 6: 2 by volume) was used as an electrolyte to prepare a coin cell.

The positive electrode was prepared as follows.

LiCoO ₂ powder and a Super-P (Timcal Ltd.) were uniformly mixed at a weight ratio of 90: 5, and then a PVDF (polyvinylidene fluoride) binder solution was added to prepare an active material: Lt; RTI ID = 0.0 &gt; wt / 5 &lt; / RTI &gt;

The cathode active material slurry was coated on an aluminum foil having a thickness of 15 탆 and dried to prepare a cathode.

Examples 14 to 16

A lithium battery was prepared in the same manner as in Example 13 except that the negative electrodes prepared in Examples 2 to 4 were used in place of the negative electrodes prepared in Example 1, respectively.

Comparative Examples 13 to 16

A lithium battery was prepared in the same manner as in Example 13, except that the negative electrode prepared in Comparative Examples 1 to 4 was used in place of the negative electrode prepared in Example 1 above.

In the lithium battery of Comparative Example 16, the electrolyte layer was swelled while the composite electrolyte layer on the lithium metal thin film was in contact with the liquid electrolyte in the negative electrode manufactured in Comparative Example 4. [

Evaluation Example 1: Evaluation of electrochemical stability

Lithium batteries prepared in Examples 5 to 8 and Comparative Examples 5 to 8 were subjected to a cyclic voltametry at a scan rate of 1 mV / sec for a voltage range of 0 to 6 V (vs. Li) The electrochemical stability of the coated electrolyte layer was evaluated, and the results for Example 5 are shown in FIGS. 8A and 8B.

Electrodes (working electrode and counter electrode) employing a copper current collector were used at about 0 to 1.5 V with respect to lithium, and an experiment using a SUS current collector at a voltage of 3 to 6 V for lithium was carried out. Respectively.

As shown in FIG. 8A, other side reactions did not occur without decomposition of the composite electrolyte layer except for the insertion / extraction of lithium at around 0V.

As shown in FIG. 8B, the current due to side reactions such as oxidation up to about 5.0 V was as small as 0.02 mA / cm ² .

Thus, it has been shown that the composite electrolyte is electrochemically stable in the range of 0 to 5V.

Evaluation example 2: Impedance measurement

The resistance of the membrane electrode assembly was measured by a two-probe method using an impedance analyzer (Solartron 1260A Impedance / Gain-Phase Analyzer) for the symmetric cells prepared in Examples 9 to 12 and Comparative Examples 9 to 12 . The current density was 0.4 A / cm ² , the amplitude was ± 10 mV, and the frequency range was 0.1 Hz to 1 MHz.

9a and 9b show Nyguist plots of impedance measurement results according to time after fabrication of the symmetric cells of Comparative Examples 9 and 9, respectively. The interface resistance of the electrodes in Figures 9A and 9B is related to the position and size of the semicircle. The difference between the left x-axis section and the right x-axis section of the semicircle represents the resistance (R _ovr , overall resistance) at the electrode. The results of analysis of the graphs of FIGS. 9A and 9B are shown in Table 1 below.

The resistance (R _ovr ) [ohm-cm ² ] Elapsed time 12hr 72hr 96hr Comparative Example 9 498 1648 2098 Example 9 128 145 162

As shown in Table 1 and FIGS. 9A and 9B, the symmetric cell of Example 9 had a resistance after 96 hours as compared with the symmetric cell of Comparative Example 9 in which the lithium metal was used as it was by introducing the composite electrolyte coating layer, Respectively.

That is, in the symmetric cell of Example 9, the surface of the lithium metal was stabilized by the composite electrolyte, and the increase of the interfacial resistance with time was remarkably decreased.

Evaluation Example 3: Charge-discharge experiment

The lithium batteries prepared in Examples 13 to 16 and Comparative Examples 13 to 16 were charged and discharged 100 times at a constant current of 1.9 mA / cm ² at a room temperature (25 ° C) in a voltage range of 3.0 to 4.4 V versus lithium metal. Part of the charge-discharge test results in the first cycle are shown in FIG. 10 and Table 2 below.

Reference Example 1 in FIG. 10 is the same lithium battery as Example 13, except that lithium metal itself not coated with a composite electrolyte was used as a negative electrode.

Table 2 shows initial discharge capacity, initial charge / discharge efficiency, and capacity retention rate. The initial discharge capacity in Table 1 is the discharge capacity in the first cycle. In Table 1, the initial coulombic efficiency is the ratio of the charge capacity to the discharge capacity in the first cycle. The capacity retention rate is calculated from the following equation (3).

&Quot; (3) &quot;

Capacity retention rate (%) = [100th cycle discharge capacity / 1st cycle discharge capacity] × 100

Early
Discharge capacity
[mAh / g] Early
Charge / discharge efficiency
[%] 100th cycle
Capacity retention rate
[%] Example 13 176.46 97.53 87.9 Example 14 177.04 97.7 58.1 Example 15 175.96 96.63 90.5 Example 16 174.323 97.7 60.3 Comparative Example 13 174.46 97.45 64.4 Comparative Example 14 168.77 95.62 48.9 Comparative Example 15 - - -

As shown in Table 2 and FIG. 10, the life characteristics of the lithium batteries of Examples 13 and 15 including the anode coated with the composite electrolyte layer were significantly improved as compared with the lithium batteries of Comparative Examples 13 and 14. The lithium battery of Comparative Example 15 was incapable of producing a negative electrode, and thus the battery characteristic measurement was impossible. In addition, the lithium batteries of Examples 13 to 16 improved the initial discharge capacity as compared with the lithium batteries of Comparative Examples 13 to 14. [

1: Lithium battery 2: cathode
3: anode 4: separator
5: Battery case 6: Cap assembly
11: anode 111: porous anode
12: cathode 13: electrolyte layer
14: intermediate layer 141: separator
142: Liquid electrolyte 143: Solid electrolyte
20: Groundwork

Claims (35)

Ionic liquid polymeric;
Inorganic particles: and
An organic electrolyte. The composite electrolyte according to claim 1, wherein the inorganic particles comprise at least one selected from a metal oxide, a carbon oxide, a carbon-based material, and an organic-inorganic hybrid material. The method of claim 1, wherein the inorganic particles are selected from the group consisting of Al ₂ O ₃ , SiO ₂ , BaTiO ₃ , graphite oxide, graphene oxide, MOF (Metal Organic Framework), POS (Polyhedral Oligomeric Silsesquioxanes) A composite electrolyte comprising at least one selected from Li ₂ CO ₃ , Li ₃ PO ₄ , Li ₃ N, Li ₃ S ₄ , Li ₂ O, and montmorillonite. The composite electrolyte according to claim 1, wherein a particle diameter of the inorganic particles is less than 100 nm. The composite electrolyte according to claim 1, wherein the content of the inorganic particles is 1 to 95% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. The composite electrolyte according to claim 1, wherein the content of the inorganic particles is in a range of 30 to 90% by weight based on the total weight of the inorganic particles and the ionic liquid polymer. The composite electrolyte according to claim 1, wherein the ionic liquid polymer is at least one selected from a cationic liquid polymer, an anionic liquid polymer, and a zwitterionic liquid polymer. 2. The composite electrolyte according to claim 1, wherein the ionic liquid polymer is represented by the following formula (1): < EMI ID =
&Lt; Formula 1 &gt;

In Formula 1,

Quot; is a 3 to 31 membered ring containing a C2-C30 carbon containing at least one heteroatom,
X is a _{-N (R 2) (R 3} ), -N (R 2), -P (R 2) or _{-P (R 2) (R 3} ),
R ₁ to R ₄ independently of one another are hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl group, An unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C4-C30 cycloalkyl group, an unsubstituted or substituted C3- A substituted or unsubstituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group,
Y ^- is an anion,
a and b are each independently an integer of 1 to 5,
and n is an integer of 500 to 2800. [ A compound according to claim 8,

Is a complex electrolyte represented by the following general formula (2): < EMI ID =
(2)

Z in formula (2) represents N, S or P,
R ₅ and R ₆ independently represent hydrogen, a C 1 -C 30 alkyl group, a C 1 -C 30 alkoxy group, a C 6 -C 30 aryl group, a C 6 -C 30 aryloxy group, a C 3 -C 30 heteroaryl group, a C 3 -C 30 heteroaryloxy group, C4-C30 cycloalkyl group, a C3-C30 heterocycloalkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group or a C2-C100 alkylene oxide group. The composite electrolyte according to claim 1, wherein the ionic liquid polymer represented by Formula 1 is an ionic liquid polymer represented by Formula 3:
(3)

In Formula 3, R ₁ to R ₈ independently represent hydrogen, an unsubstituted or substituted C1-C30 alkyl group, an unsubstituted or substituted C1-C30 alkoxy group, an unsubstituted or substituted C6-C30 aryl group , Unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, unsubstituted or substituted C4-C30 A cycloalkyl group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group,
Y ^- is ^{_{BF 4 -, PF 6 -,}} AsF 6 -, SbF 6 -, AlCl 4 -, HSO 4 -, ClO 4 -, CH 3 SO 3 -, CF 3 CO 2 -, (CF 3 SO 2) 2 ^{N -, Cl -, Br -} , I -, BF 4 -, SO 4 -, PF 6 -, ClO 4 -, CF 3 SO 3 -, CF 3 CO 2 -, (C 2 F 5 SO 2) 2 N ^- , (C ₂ F ₅ SO ₂ ) (CF ₃ SO ₂ ) N ^- and (CF ₃ SO ₂ ) ₂ N ^-
a and b are each independently an integer of 1 to 5,
and n is an integer of 500 to 2800. [ The composite electrolyte according to claim 1, wherein the organic electrolyte comprises at least one selected from an organic solvent and an ionic liquid. 12. The method according to claim 11, wherein the organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinylethylene carbonate butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, The organic solvent is preferably selected from the group consisting of a carbonate, a dipropyl carbonate, a dibutyl carbonate, a benzonitrile, an acetonitrile, a tetrahydrofuran, a 2-methyltetrahydrofuran, a -butyrolactone, a dioxolane, A complex electrolyte comprising at least one selected from the group consisting of lithium, sodium, sodium, potassium, sodium, sodium, potassium, sodium, 12. The composite electrolyte according to claim 11, wherein the ionic liquid is represented by the following formula (4) or (5):
&Lt; Formula 4 >

In Formula 4,

Quot; means a 3- to 31-membered ring containing a C2-C30 carbon containing at least one heteroatom,
X is a _{-N (R 2) (R 3} ), -N (R 2), -P (R 2) or _{-P (R 2) (R 3} ),
Y ^- is an anion,
&Lt; Formula 5 >

In Formula 5,
X is a _{-N (R 2) (R 3} ), -N (R 2), -P (R 2) or _{-P (R 2) (R 3} ),
R ₁₁ is an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl group, an unsubstituted or substituted C 6 -C 30 aryloxy group , An unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C4-C30 cycloalkyl group, an unsubstituted or substituted C3-C30 hetero A cycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group,
Y ^- is an anion,
Wherein R ₂ and R ₃ are independently of each other hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl Unsubstituted or substituted C6-C30 aryloxy groups, unsubstituted or substituted C3-C30 heteroaryl groups, unsubstituted or substituted C3-C30 heteroaryloxy groups, unsubstituted or substituted C4- C30 cycloalkyl group, an unsubstituted or substituted C3-C30 heterocycloalkyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group. 14. The method according to claim 13,

Is represented by the following formula (6), and the formula

Is a cation represented by the general formula (7): < EMI ID =
(6)

In Formula 6,
Z represents N or P,
R ₁₂ to R ₁₈ independently represent hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl group, An unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C4-C30 cycloalkyl group, an unsubstituted or substituted C3- An unsubstituted or substituted C3-C30 heterocycloalkyl group, an unsubstituted or substituted C2-C30 alkenyl group, an unsubstituted or substituted C2-C30 alkynyl group or an unsubstituted or substituted C2-C100 alkylene oxide group,
&Lt; Formula 7 &gt;

In Formula 7,
Z represents N or P,
R ₁₂ to R ₁₅ independently represent hydrogen, an unsubstituted or substituted C 1 -C 30 alkyl group, an unsubstituted or substituted C 1 -C 30 alkoxy group, an unsubstituted or substituted C 6 -C 30 aryl group, An unsubstituted or substituted C3-C30 heteroaryl group, an unsubstituted or substituted C3-C30 heteroaryloxy group, an unsubstituted or substituted C4-C30 cycloalkyl group, an unsubstituted or substituted C3- An unsubstituted or substituted C3-C30 heterocycloalkyl group, an unsubstituted or substituted C2-C30 alkenyl group, an unsubstituted or substituted C2-C30 alkynyl group, or an unsubstituted or substituted C2-C100 alkylene oxide group. anode;
cathode; And
And an electrolyte layer disposed on at least a portion of the cathode,
Wherein the electrolyte layer comprises the composite electrolyte according to claim 1. 16. The lithium battery according to claim 15, wherein the electrolyte layer is coated on at least a part of the negative electrode. The lithium battery according to claim 15, wherein the thickness of the electrolyte layer is 40 占 퐉 or less. 16. The lithium battery according to claim 15, wherein the negative electrode comprises lithium metal. 19. The lithium battery according to claim 18, wherein the thickness of the lithium metal is less than 100 mu m. 16. The lithium battery according to claim 15, wherein the electrolyte layer has at least two layers. The lithium battery according to claim 20, wherein the two or more layers have different compositions. The lithium battery according to claim 20, wherein the two or more layers independently comprise at least one selected from a liquid electrolyte, a gel electrolyte and a solid electrolyte. The lithium battery according to claim 15, wherein the impedance of the lithium battery after lapse of 96 hours at 25 캜 is 10% or less as compared to a free lithium battery. 16. The lithium battery according to claim 15, further comprising a separator disposed between the anode and the cathode. 16. The lithium battery according to claim 15, further comprising a liquid electrolyte adjacent to the anode. The lithium battery according to claim 25, wherein the anode is a porous anode impregnated with a liquid electrolyte. 16. The lithium battery according to claim 15, wherein the anode comprises at least one selected from a liquid electrolyte, a gel electrolyte and a solid electrolyte. anode; cathode; And
And a composite electrolyte layer according to claim 1 adjacent to said anode,
And a solid electrolyte layer disposed between the composite electrolyte layer and the cathode. The method of claim 28, wherein the solid electrolyte layer comprises an ionically conducting polymer, a polymeric ionic liquid (PIL), an inorganic electrolyte, a polymer matrix, an electronically conducting polymer, &Lt; / RTI &gt; lithium battery. The method of claim 29, wherein the solid electrolyte layer is selected from the group consisting of polyethylene oxide (PEO), solid graft copolymer comprising a polymer block having a low Tg of at least 2, poly (diallyl dimethyl ammonium) trifluoromethane sulfonyl imide (poly (diallyldimethylammonium) TFSI), Cu 3 N, Li 3 N, LiPON, Li 3 PO 4 .Li 2 S.SiS 2, Li 2 S.GeS 2 .Ga 2 S 3, Li 2 O. _{11Al 2 O 3, Na 2 O.11Al} 2 O 3, (Na, Li) 1 + x Ti 2-x Al x (PO 4) 3 (0.1-x-0.9), Li 1 + x Hf 2-x Al _x (PO ₄ ) ₃ (0.1-x-0.9), Na ₃ Zr ₂ Si ₂ PO ₁₂ , Li ₃ Zr ₂ Si ₂ PO ₁₂ , Na ₅ ZrP ₃ O ₁₂ , Na ₅ TiP ₃ O ₁₂ , Na ₃ Fe ₂ P ₃ O ₁₂ , Na ₄ NbP ₃ O ₁₂ , Na-Silicates, Li _0.3 La _0.5 TiO ₃ , Na ₅ MSi ₄ O ₁₂ (M is a rare earth element selected from Nd, Gd and Dy) Li ₅ ZrP ₃ O ₁₂ , _{Li 5 TiP 3 O 12, Li} 3 Fe 2 P 3 O 12, Li 4 NbP 3 O 12, Li 1 + x (M, Al, Ga) x (Ge 1-y Ti y) 2-x (PO 4) _{3 (x-0.8, 0-} y-1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , or _{Yb), Li 1 + x +} y Q x Ti 2-x Si y P _3-y O ₁₂ (0 < x-0.4, 0 < y- 0.6, Q is Al or Ga), Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ M ₂ O ₁₂ (M is Nb or Ta ), Li _{7 + x} A _x La _3-x Zr ₂ O ₁₂ (0 <x <3, A is Zn). The lithium battery according to claim 29, wherein the ion conductive polymer comprises at least one ion conductive repeating unit selected from an ether monomer, an acrylic monomer, a methacryl monomer, and a siloxane monomer. 32. The method of claim 31, wherein the ion conductive polymer is selected from the group consisting of polyethylene oxide, polypropylene oxide, polymethylmethacrylate, polyethylmethacrylate, polydimethylsiloxane, polyacrylic acid, polymethacrylic acid, polymethyl acrylate, At least one selected from the group consisting of poly (2-ethylhexyl acrylate), poly (2-ethylhexyl acrylate), polybutyl methacrylate, poly (2-ethylhexyl methacrylate), poly (decyl acrylate) and polyethylene vinyl acetate. The lithium battery according to claim 29, wherein the ion conductive polymer comprises an ion conductive repeating unit and a structural repeating unit. 34. The method of claim 33, wherein the ionic conductive repeating unit is selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, butyl methacrylate, 2- Ethylhexyl acrylate, ethylhexyl methacrylate, decyl acrylate, ethylene vinyl acetate, ethylene oxide, propylene oxide,
Wherein said structural repeating units are selected from the group consisting of styrene, 4-bromostyrene, terbutylstyrene, divinylbenzene, methylmethacrylate, isobutylmethacrylate, butadiene, ethylene, propylene, dimethylsiloxane, isobutylene, Amide, vinylidene fluoride, acrylonitrile, 4-methylpentene-1, butylene terephthalate, ethylene terephthalate and vinyl pyridine. 30. The lithium battery according to claim 29, wherein the ion conductive polymer comprises an ion conductive phase and a structural phase.

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