KR101475705B1 - anion receptors, electrolyte containing anion receptors, lithium ion battery and lithium ion capacitor using the same - Google Patents

Abstract

The present invention provides an electrolyte containing an anion receptor compound, and the electrolyte according to the present invention has high ionic conductivity and high electrochemical stability, so that the electrochemical cell and lithium ion capacitor employing the electrolyte according to the present invention have high efficiency and stability .

Description

The present invention relates to an anion receptor, an electrolyte containing the same, and a lithium ion battery and a lithium ion capacitor using the same, and more particularly, to an anion receptor, an electrolyte containing anion receptors,

The present invention relates to a novel anion receptor, an electrolyte comprising the same, and a battery and a lithium ion capacitor manufactured using such an electrolyte. More particularly, the present invention relates to an amine group substituted with an electron withdrawing group, An anion receptor into which a nitrogen atom is introduced, an electrolyte added with the anion receptor, and a battery and a lithium ion capacitor manufactured using such an electrolyte.

Recently, in order to meet the demand as a power source for information communication equipment and electronic products which are combined with various applications such as development of environmentally friendly electric vehicles and smart phones due to global warming and depletion of fossil fuels, Development is required.

Lithium ion capacitors have been studied as a new concept electrochemical capacitor having high energy density and output characteristics by combining a lithium secondary battery and an electric double layer capacitor as the power source.

On the other hand, among the component materials that determine the performance of these power sources, the electrolyte greatly affects the performance of the electrode as well as itself. When the electrolyte used in the conventional secondary battery is used as it is, deterioration of the electrode and the electrolyte There is a problem in that the electrochemical stability by the electrolyte solution is drastically deteriorated.

In order to overcome the problems of these electrolytes, anion receptors are being studied, and anion receptors improve the stability of anions by the interaction of Lewis acid and salts. Anion receptors are compounds with atoms lacking electrons (N, B). By coordinating the anion rich in electrons with the surrounding atoms, it prevents the binding of anions and lithium cations to ion pairs, facilitating migration of lithium cations. The first compound known as an anion receptor is to make the nitrogen atom of the amine group substituted by the perfluoroalkylsulfonyl substituent a state of deficient electron so that it can interact properly with the electron rich anion through the Coulomb attraction (J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9) which consists of cyclic or linear amides.

However, these aza-ethers exhibit limited solubility for polar solvents employed as typical non-aqueous electrolytes, and the electrochemical stability window of the electrolyte to which the LiCl salt is added meets the required 4.0 V for the commercially available cathode material but not only was not found to be unstable in the _{LiPF 6 (J. Electrochem. Solid-} State Lett., 5 (2002) A248). In other words, LiPF ₆ is chemically and thermally unstable and equilibrates with solid LiF at room temperature and PF ₅ , which is gas. The generation of PF ₅ , the gas product, further tilts the equilibrium toward the generation of PF ₅ .

In non-aqueous solvents, PF ₅ tends to initiate a series of reactions, such as ring-opening polymerization or breaking of ether bonds composed of atoms with non-covalent electron pairs, such as oxygen or nitrogen. Strong Lewis acid, PF ₅ , attacks the electron pair, which causes an immediate attack of PF ₅ due to its high electron density (J. Power Sources, 104 (2002) 260).

Therefore, studies have been proposed in Korean Patent Laid-Open Publication No. 2008-0023294 to overcome the above-mentioned problems, but there is still a research on new chemical substances that can eliminate the chemical instability of the battery, the instability of the lithium salt, .

Korean Patent Publication No. 2008-0023294

J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9 J. Electrochem. Solid-State Lett., 5 (2002) A 248 J. Power Sources, 104 (2002) 260

The present invention provides an anion receptor into which an amine group or a nitrogen atom in a ring is substituted with an electron-withdrawing functional group, and an electrolyte comprising the anion receptor.

 The present invention also provides a battery and a lithium ion capacitor manufactured using an electrolyte including an anion receptor according to the present invention.

The present invention provides a novel anion receptor and an electrolyte comprising a novel anion receptor for improving ionic conductivity and cation transport rate.

The anion receptor of the present invention includes a compound represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

R ₁ and R ₂ is independently H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ or -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

이거나, R₁ 또는 R₂와 (C₂-C₂₀)알킬렌 또는 (C₂-C₂₀)알케닐렌으로 연결되어 고리를 형성할 수 있으며, 상기 형성된 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있으며, 상기 R₁₁은 (C₂-C₂₀)알케닐 또는 (C₂-C₂₀)알키닐이며;A is (C ₁ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkyl substituted at the end by (C ₃ -C ₂₀ ) heterocycloalkyl,

, Or R ₁ or R ₂ may be linked with (C ₂ -C ₂₀ ) alkylene or (C ₂ -C ₂₀ ) alkenylene to form a ring, and the carbon atoms of the formed ring may be replaced by nitrogen, oxygen and sulfur Optionally substituted with one or more heteroatoms, wherein R ₁₁ is (C ₂ -C ₂₀ ) alkenyl or (C ₂ -C ₂₀ ) alkynyl;

로 더 치환될 수 있으며, R₂₂는 (C₁-C₂₀)알킬이다.]Alkenyl of A of cycloalkyl, alkyl, heterocycloalkyl, and alicyclic ring and R ₁₁ Al or alkynyl are halogen, (C ₁ -C ₂₀₎ alkyl or

And R ₂₂ is (C ₁ -C ₂₀ ) alkyl.

The formula 1 according to an embodiment of the present invention may be represented by the following formulas 2 to 7.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[In the above Chemical Formulas 2 to 7,

R ₁ and R ₂ is independently H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ or -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

R ₃ and R ₄ independently of one another are hydrogen, halogen or (C ₁ -C ₂₀ ) alkyl,

R ₂₂ is (C ₁ -C ₂₀ ) alkyl;

n is an integer from 1 to 10;

o is an integer from 1 to 4;

p is an integer determined according to an integer of n and is an integer of 4 to 9.]

Specifically, Formula 2 according to an embodiment of the present invention is represented by Formula 8 or 9, Formula 3 is represented by Formula 10, Formula 6 is represented by Formula 11, (12).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[In the above formulas (8) to (12)

R ₁ and R ₂ is independently H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ or -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

R ₃ and R ₄ independently of one another are hydrogen, halogen or (C ₁ -C ₂₀ ) alkyl,

R ₂₂ is (C ₁ -C ₂₀ ) alkyl.

More specifically, Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

The electrolyte according to an embodiment of the present invention may include the compound of Formula 1 in an amount of 0.01 to 40% by weight based on 100% by weight of the electrolyte.

The present invention also provides an electrolyte including an anion receptor according to the present invention, a polymer electrolyte thin film, a battery, and a lithium ion capacitor manufactured using such an electrolyte.

The battery or the lithium ion capacitor according to the present invention has high electrochemical stability and high electrode life characteristics due to charge and discharge.

The electrolyte of the present invention includes an amine group substituted with an electron-withdrawing functional group or an anion receptor into which a nitrogen atom in a ring is introduced, and thus ionic conductivity and cation transport rate are very high.

Also, the electrolyte of the present invention includes an anion receptor having a double bond hydrocarbon such as acryl or vinylene incorporated therein to form a SEI (Solid Electrode Interface) film on the surface of the electrode, so that damage to the electrode surface due to deterioration of the electrolyte The electrode life is increased.

In addition, the electrolyte of the present invention includes an amine group substituted with an electron-withdrawing functional group or an anion receptor into which a nitrogen atom in a ring is introduced, thereby suppressing generation of strong acid such as HF by decomposition of a lithium salt contained in the electrolyte depending on use of the electrolyte This increases the lifetime of the battery and the rechargeable capacitor due to charging and discharging.

1 is a graph showing the lithium cycling performance of lithium ion batteries of Example 25 (with Acryl-TFSI) and Comparative Example 3 (No Addition) of the present invention

The present invention provides an anion receptor having an amine group or a nitrogen atom in a ring substituted with an electron-withdrawing functional group and an electrolyte added with such anion receptor, wherein the anion receptor of the present invention includes a compound represented by the following formula .

[Chemical Formula 1]

[In the above formula (1)

R ₁ And R ₂ is independently from each other H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ Or is -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

이거나, R₁ 또는 R₂와 (C₂-C₂₀)알킬렌 또는 (C₂-C₂₀)알케닐렌으로 연결되어 고리를 형성할 수 있으며, 상기 형성된 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있으며, 상기 R₁₁은 (C₂-C₂₀)알케닐 또는 (C₂-C₂₀)알키닐이며;A is (C ₁ -C ₂₀ ) cycloalkyl, (C ₁ -C ₂₀ ) alkyl substituted at the end by (C ₃ -C ₂₀ ) heterocycloalkyl,

, Or R ₁ or R ₂ may be linked with (C ₂ -C ₂₀ ) alkylene or (C ₂ -C ₂₀ ) alkenylene to form a ring, and the carbon atoms of the formed ring may be replaced by nitrogen, oxygen and sulfur Optionally substituted with one or more heteroatoms, wherein R ₁₁ is (C ₂ -C ₂₀ ) alkenyl or (C ₂ -C ₂₀ ) alkynyl;

로 더 치환될 수 있으며, R₂₂는 (C₁-C₂₀)알킬이다.]Alkenyl of A of cycloalkyl, alkyl, heterocycloalkyl, and alicyclic ring and R ₁₁ Al or alkynyl are halogen, (C ₁ -C ₂₀₎ alkyl or

And R ₂₂ is (C ₁ -C ₂₀ ) alkyl.

The anion receptor according to the present invention is a compound substituted with an amine group or a functional group which attracts electrons to a nitrogen atom in a ring. The anion receptor of the present invention is contained in an electrolyte and has a nitrogen atom which is an atom lacking electrons, It is possible to increase the ionic conductivity by facilitating the movement of the lithium cation by preventing the anion and the lithium cation from being bonded to the ion pair and by substituting the functional group for attracting electrons to the nitrogen atom to facilitate the migration of the cation, When employed in a battery or a lithium ion battery, the electrochemical stability can be improved and the lifetime characteristics of the electrode can be enhanced.

More specifically, an amine group substituted with an electron-withdrawing functional group or a nitrogen atom in a ring is used to enhance dissociation of an alkali metal salt to enhance electronegativity and cation mobility. That is, the amine group or the nitrogen in the ring is deficient in electrons due to the electron-withdrawing functional group such as -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ and -SO ₂ CN, To form an electrically neutral complex with the anionic species of the alkali metal salt to promote dissociation of the alkali metal salt. In addition, the electrochemical instability caused by the presence of a nitrogen atom susceptible to attack in the middle of the bond by allowing the nitrogen atom of the amine group substituted with the electron-withdrawing functional group and the nitrogen atom in the ring to be located only at the end of the hydrocarbon chain, the lithium salt (particularly LiPF ₆ ) And high ionic conductivity can be obtained by increasing dissociation of lithium salt and increasing cation mobility since the center of nitrogen is more exposed and bulky anions are easily accessible.

The term " alkyl " or other substituents comprising the " alkyl " moiety of the present invention encompass both linear and branched forms, and " cycloalkyl " refers to a single ring system as well as substituted or unsubstituted adamantyl, But also include various cyclic hydrocarbons such as (C ₇ -C ₂₀ ) bicycloalkyl.

In the anion receptor of the present invention, when A is connected to R ₁ or R ₂ through (C ₂ -C ₂₀ ) alkylene or (C ₂ -C ₂₀ ) alkenylene to form a ring, the ring is a central element N, and the carbon atom of the heterocycle may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur.

The formula 1 according to an embodiment of the present invention may be represented by the following formulas 2 to 7.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[In the above Chemical Formulas 2 to 7,

R ₁ and R ₂ is independently H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ or -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

R ₃ and R ₄ independently of one another are hydrogen, halogen or (C ₁ -C ₂₀ ) alkyl,

R ₂₂ is (C ₁ -C ₂₀ ) alkyl;

n is an integer from 1 to 10;

o is an integer from 1 to 4;

p is an integer determined according to an integer of n and is an integer of 4 to 9.]

Specifically, Formula 2 according to an embodiment of the present invention is represented by Formula 8 or 9, Formula 3 is represented by Formula 10, Formula 6 is represented by Formula 11, (12).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[In the above formulas (8) to (12)

R ₁ and R ₂ is independently H, -SO ₂ CF ₃ , -CN, -F, -Cl, -COCF ₃ or -SO ₂ CN, R ₁ and R ₂ is not simultaneously hydrogen;

R ₃ and R ₄ independently of one another are hydrogen, halogen or (C ₁ -C ₂₀ ) alkyl,

R ₂₂ is (C ₁ -C ₂₀ ) alkyl.

More specifically, Formula 1 according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

The electrolyte according to an embodiment of the present invention comprises 0.01 to 40% by weight of the compound of Formula 1 based on 100% by weight of the electrolyte. If the content is less than 0.01% by weight, the ionic conductivity can not be improved. If the content is more than 40% by weight, the ionic conductivity of the electrolyte is lowered. Therefore, it is more preferable to increase the ionic conductivity by 0.1 to 20% by weight.

The formula 1 of the present invention can be synthesized by a known method. For example, the formula 1 can be illustrated by the following reaction formula 1, but it is not limited thereto.

[Reaction Scheme 1]

[Wherein R ₁ , R ₂ and A are the same as defined in the above formula (1)).

The present invention provides an electrolyte comprising an anion receptor represented by Formula 1, wherein the electrolyte of the present invention can be used for a battery or a lithium ion capacitor, but is preferably used as a non-aqueous liquid electrolyte, a gel-type polymer electrolyte and a solid polymer electrolyte .

Specifically, in one embodiment of the electrolyte of the present invention,

(I) an anion receptor of Formula 1;

(Ii) non-aqueous solvent; And

(Iii) a non-aqueous liquid electrolyte comprising an alkali metal ion-containing material. In another embodiment of the present invention,

(I) an anion receptor of Formula 1;

(Ii) a polymeric support;

(Iii) non-aqueous solvent; And

(Iv) a gel-type polymer electrolyte comprising an alkali metal ion-containing substance.

According to another embodiment of the present invention,

(i) an anion receptor of Formula 1;

(Ii) a polymer compound or a crosslinkable polymer compound selected from reticular, comb and branched polymer compounds; And

(Iii) a solid polymer electrolyte composed of an alkali metal ion-containing substance.

The solid polymer electrolyte according to an embodiment of the present invention may further include one or more compounds selected from polyalkylene glycol dialkyl ether and non-aqueous solvent.

The nonaqueous solvent used in the electrolyte may be at least one selected from the group consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, But are not limited to, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxyethane, dimethoxymethane, Methylol formate, sulfolane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2-pyrrolidinone or a mixture thereof may be used;

Wherein the alkali metal ion-containing material is selected from the group consisting of LiSO ₃ CF ₃ , LiCOOC ₂ F ₅ , LiN (SO ₂ CF ₃ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiPF ₆ , LiSbF ₆ , LiI, LiBr, LiCl, or a mixture thereof.

The polymer scaffold used in the gel-type polymer electrolyte is not particularly limited, but a polyacrylonitrile (PAN) -based polymer or a polyvinylidene fluoride (PVDF) -hexafluoropropylene-based polymer may be used.

Also, the network, comb or branched polymer compound used for the solid polymer electrolyte is not particularly limited, but a flexible inorganic polymer or a linear polyether can be used. As the crosslinkable polymer compound, a flexible inorganic polymer or Those having a linear polyether main chain as a basic skeleton and having functional groups such as acrylic, epoxy, trimethylsilyl, silanol, vinylmethyl or divinylmonomethyl introduced at their terminals can be used.

The flexible inorganic polymer is preferably polysiloxane or polyphosphazene, and the linear polyether is preferably polyalkylene oxide.

Examples of the crosslinkable polymer compound include bisphenol A ethoxylated dimethacrylate represented by the following formula (11) or TA-10 represented by the following formula (12): < EMI ID =

(11)

[Chemical Formula 12]

The polyalkylene glycol dialkyl ether or nonaqueous solvent which may be contained in the solid polymer electrolyte acts as a plasticizer like the anion receptor of the present invention,

Examples of polyalkylene glycol dialkyl ethers include polyethylene glycol dimethyl ether (PEGDME), polyethylene glycol diethyl ether, polyethylene glycol dipropyl ether, polyethylene glycol dibutyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dimethyl ether, Polypropylene glycol diglycidyl ether, dibutyl ether terminal polypropylene glycol / polyethylene glycol copolymer, or dibutyl ether terminal polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymer.

In addition, when the solid polymer electrolyte includes a crosslinkable polymer compound, it further includes a curing initiator.

The curing initiator may be a photocurable initiator, a thermosetting initiator, or a mixture thereof.

The photocurable initiator may be selected from the group consisting of dimethylphenylacetophenone (DMPA), t-butylperoxypivalate, ethylbenzoin ether, isopropylbenzoin ether,? -Methylbenzoin ethyl ether, benzoinphenyl ether,? -Acyloxime ester , α, α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, Benzyl benzoate, benzoyl benzoate, Michler's ketone, or a mixture thereof, may be used as the solvent, for example,

The thermosetting initiator may be an azoisobutylonitrile compound, a peroxide compound, or a mixture thereof.

In the electrolyte of the present invention, the anion receptor is contained in an amount of 0.01 to 40% by weight of the total composition, and the alkali metal ion-containing substance is contained in an amount of 3 to 60% by weight.

In the gel-type polymer electrolyte of the present invention, the polymer scaffold is preferably contained in an amount of 5 to 40% by weight.

In the solid polymer electrolyte of the present invention, 10 to 95% by weight of the polymer compound or crosslinkable polymer compound selected from the reticular, comb and branched polymer compounds is contained, and 0.5 to 5% by weight of the curing initiator is contained desirable.

The polyalkylene glycol dialkyl ether contained in the solid polymer electrolyte, and the non-aqueous solvent may be contained in an amount of 10 to 50% by weight.

Also, the present invention provides an alkali metal battery containing the anion receptor, wherein the alkali metal battery using the liquid or gel polymer electrolyte of the present invention comprises a negative electrode, a positive electrode, and a separator, and uses the solid polymer electrolyte of the present invention The battery includes a cathode and an anode.

The negative electrode and the positive electrode used in the alkali metal battery of the present invention can be used according to the manufacturing method of the negative electrode and the positive electrode used in a conventional battery. The assembly of the alkali metal battery can also be carried out by assembling the conventional negative electrode, positive electrode and electrolyte Method. ≪ / RTI >

The cathode is lithium; Lithium alloys such as Li-Al, Li-Si, or Li-Cd; Lithium-carbon intercalation compounds; Lithium-graphite intercalation compounds; Intercalation compounds of lithium metal oxides such as Li _x WO ₂ or LiMoO ₂ ; Lithium metal sulfide intercalation compounds such as LiTiS ₂ ; A mixture thereof or a mixture of these and an alkali metal.

The anode comprises a transition metal oxide, a transition metal chalcogenide, a poly (carbon disulfide) polymer, an organo-disulfide redox polymer, a polyaniline, an organic-disulfide / polyaniline complex or a mixture thereof with oxychloride.

Hereinafter, structural examples of the alkali metal battery of the present invention will be described.

The primary battery comprising the non-aqueous liquid electrolyte containing the anion receptor of the present invention,

(I) an anode containing lithium, a lithium alloy, a lithium-carbon intercalation compound, a lithium-graphite intercalation compound, a lithium metal oxide intercalation compound, a mixture containing them, or an alkali metal;

(Ⅱ) transition metal oxides, transition metal chalcogenide, a poly (carbon disulfide) polymer, an organic-disulfide redox polymer, a polyaniline, organic-for disulfide / polyaniline composite and a positive electrode containing oxychloride, for example, SO _2, CuO , CuS, Ag ₂ CrO ₄ , I ₂ , PbI ₂ , PbS, SOCl ₂ , V ₂ O ₅ , MoO ₃ , MnO ₂ or polycarbon monofluoride (CF 3) _n ;

(Iii) the non-aqueous liquid electrolyte of the present invention described above; And

(iv) a separator,

Manufacture of the anode and cathode and assembly of the battery can be made by known methods.

Further, in the secondary battery comprising the non-aqueous liquid electrolyte containing the anion receptor of the present invention,

(I) lithium; Lithium alloys such as Li-Al, Li-Si and Li-Cd; Lithium-carbon intercalation compounds, lithium-graphite intercalation compounds; Lithium metal oxide intercalation compounds such as Li _x WO ₂ or LiMoO ₂ ; Or a lithium metal sulfide intercalation compound such as LiTiS ₂ , or the like; a negative electrode containing a substance capable of reversibly acting as a lithium metal or a lithium metal;

_{(Ⅱ) Li 2.5 V 6 O} 13, Li 1.2 V 2 O 5, LiCoO 2, LiNiO 2, LiNi 1-x M x O 2 ( where M is Co, Mg, Al or Ti), LiMn ₂ O ₄ or LiMnO A transition metal oxide capable of intercalating lithium such as lithium ( _II ); Transition metal halide; Or a chalcogenide such as LiNbSe ₃ , LiTiS ₂ or LiMoS ₂ ;

(Iii) the non-aqueous liquid electrolyte of the present invention described above; And

(iv) a separator, and the production of the positive electrode and the negative electrode and the assembly of the battery can be performed by a known method.

The secondary battery composed of the gel type polymer electrolyte containing the anion receptor of the present invention is composed of the gel type polymer electrolyte of the present invention together with the negative electrode, the positive electrode and the separator used in the secondary battery comprising the nonaqueous liquid electrolyte.

The secondary battery composed of the solid polymer electrolyte containing the anion receptor compound of the present invention may be composed of the solid polymer electrolyte of the present invention together with the cathode and the anode used in the secondary battery comprising the nonaqueous liquid electrolyte.

In addition, the present invention provides a polymer electrolyte thin film using the electrolyte of the present invention.

Hereinafter, a method of preparing a gel or solid polymer electrolyte thin film containing the components of the present invention will be described in detail.

First, in case of a gel type polymer electrolyte, a nonaqueous solvent, an anion receptor compound of formula (1) and an alkali metal ion-containing substance are put into a vessel at an appropriate mixing ratio, and the mixture is stirred with a stirrer to prepare a solution. do. When the polymer scaffold is mixed, a predetermined amount of heat is applied to dissolve the polymer scaffold, if necessary, to prepare a composition solution for preparing the gel-type polymer electrolyte thin film of the present invention. The prepared solution is coated on a support substrate made of glass or polyethylene having an appropriate thickness, or a commercial Mylar film. Then, the coated substrate is dried or exposed to an electron beam, ultraviolet ray or gamma ray, or heated to cause a curing reaction to form a thin film.

Next, in the case of a solid polymer electrolyte, first, an anion receptor or a polyalkylene glycol dialkyl ether or a non-aqueous solvent and an alkali metal ion-containing substance are put into a container at an appropriate mixing ratio, the mixture is stirred with a stirrer to prepare a solution, Type, branched or comb-like polymer compound or a crosslinkable polymer compound is added and mixed with each other. When mixing the polymer compound of the reticular, branched or comb type, it is melted by applying a predetermined heat, if necessary. When a crosslinkable macromolecule compound is added to this mixed solution, a curing initiator is added and stirred to prepare a composition liquid mixture for preparing the solid polymer electrolyte of the present invention. The prepared solution is coated on a support substrate made of glass or polyethylene having an appropriate thickness, or a commercial Mylar film. Then, the coated substrate is dried or exposed to an electron beam, ultraviolet ray or gamma ray, or heated to cause a curing reaction to form a thin film.

Another method for producing a thin film is as follows. After a spacer for thickness control is fixed on both ends of the support substrate, another support substrate is covered thereon, and the curing reaction is performed using the curing light source or heat source to form a gel or solid To produce a polymer electrolyte thin film.

The present invention also provides a polymer electrolyte thin film, an electrochemical cell, and a lithium ion capacitor using an electrolyte containing an anion receptor according to the present invention.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

[Example 1]

To a mixture of 9.92 g of cyclohexylamine and 24.3 g of triethylamine in 100 ml of chloroform at -25 캜, 62.1 g of triflic anhydride was added dropwise in a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, poured into distilled water, and the organic layer was separated and washed three times with distilled water. The organic extracts were then dried over anhydrous magnesium sulfate (anhydrous) and filtered. The chloroform was removed under vacuum to obtain the product cyclohexyl- (bis-trifluoromethane sulfonyl) imide: Cyclohexyl-TFSI].

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.21-1.29 (m, 6H), 1.48-1.51 (m, 4H), 2.54-2.61

[Example 2]

To a mixture of 1.74 g of cyclohexylamine and 2.0 g of triethylamine in 40 ml of dichloromethane at -40 캜, 5.0 g of triflic anhydride was added dropwise in a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours and then volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 4 moles of sodium hydroxide and then washed three times with 25 ml of dichloromethane. The aqueous phase was then neutralized with hydrochloric acid and extracted three times with 30 ml of dichloromethane. The organic extract was dried over anhydrous magnesium sulfate (anhydrous) and the dichloromethane was removed under vacuum to obtain the product cyclohexyl-trifluoromethanesulfonamide (Cyclohexyl-TFSA).

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 1.21-1.29 (m, 6H), 1.48-1.51 (m, 4H), 2.54-2.61 (m, 1H), 5.9 (m, 1H)

IR: υN-H 3315 cm ^-1

[Example 3]

19.8 g of cyclohexylamine, 24.3 g of triethylamine and 46.9 g of trifluoroacetic anhydride were reacted with 100 ml of chloroform in the same manner as in Reaction Scheme 5 of Example 2 to obtain the product cyclohexyl-trifluoroacetamide [ Cyclohexyl-trifluoroacetamide: Cyclohexyl-TFAc].

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 1.19-1.25 (m, 6H), 1.43-1.50 (m, 4H), 2.52-2.58 (m, 1H), 5.75 (m, 1H)

IR: υN-H 3315 cm ^-1

[Example 4]

Trifluoroacetic anhydride of 14.22 g of pyrrolidine and 24.3 g of triethylamine and 46.9 g of trifluoroacetic anhydride was synthesized in 100 ml of chloroform in the same manner as in the reaction scheme 5 of Example 2 to obtain the product pyrrolidine-trifluoroacetate Amide [Pyrrolidine-trifluoroacetamide: Pyrrolidine-TFAc].

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.58-1.61 (m, 4H), 2.76-2.81 (m, 4H)

[Example 5]

14.82 kg of Pyrrolidine-TFSI was placed in an 8 L recovery vessel and heated and circulated to a light irradiation reactor equipped with a 150 W UV high pressure mercury lamp (Heraeus TQ150). The reaction temperature in the light irradiation reactor was maintained in the range of 40 to 45 캜. Chlorine gas was continuously supplied from the bottom of the light irradiation reactor at a rate of about 200 L per hour. Nitrogen gas was supplied to the top of the light irradiation reactor at a rate of 800 L per hour. A second flow nitrogen gas was also fed into the liquid phase at the bottom of the recovery vessel at a rate of 800 L / hr. The liquid reactant was circulated at a rate of 2 to 3 L per minute. After 4.6 Kg of chlorine was introduced, the reaction was terminated. The reaction product was transferred to a vacuum distillation apparatus and distilled under reduced pressure while raising the temperature at 3 torr. As a result of distilling the material at a temperature of 70 to 80 캜, a chloropyrrolidine-trifluoromethanesulfonylimide having a purity of 99% was obtained. Chloropyrrolidine-TFSI].

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.78-1.81 (m, 2H), 2.76-2.81 (m, 4H), 3.5-3.8

[Example 6]

1 Kg of Hyflo Super Cell, a diatomaceous earth filter aid, was suspended in 115 L of butyl methyl ether and 64 L of triethylamine was added. The mixture was heated in a stirred reactor equipped with a reflux condenser. When the solvent began to reflux, a mixture containing 115 Kg of chloropyrrolidine-trifluoromethanesulfonylimide prepared above was added to the reactor for 45 minutes. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and water was added to 80 L of butyl methyl ether. The organic layer was separated and washed three times with water. The organic extracts were then dried over anhydrous magnesium sulfate (anhydrous) and filtered. The product t-butyl methyl ether was removed under vacuum to obtain the product vinylene-trifluoromethane sulfonylimide (Vinylene-TFSI).

¹ H NMR (300 MHz, CDCl ₃ ): ppm 3.18-3.31 (m, 4H), 5.76-5.81 (m, 2H)

[Example 7]

2437 g of pyrrolidine-TFSI and 600 g of potassium fluoride (KF) were put into a 2 L reactor equipped with a stirrer and a condenser and purged with nitrogen at 80 캜 for about 30 minutes. 1145 ml of sulfuryl chloride (SO 2 Cl 2) was added to the dropping funnel provided in the reactor head, and the mixture was added dropwise with stirring for 1 hour. Then, 719 mg of 2,2'-Azoisobutironitrile (AIBN) was dissolved in 20 ml of dichloromethane, The solution was added dropwise 4 times. The HCl gas generated in the reaction was neutralized in a base trap containing a saturated aqueous sodium hydroxide solution connected to a condenser. After the dropwise addition, the reaction mixture was stirred for 10 hours at a reaction temperature of 100 ° C. The reaction product was distilled under a condition of 80 ° C. and 30 torr to remove salts through a filter paper to obtain a product having a purity of 90.3% Vacuum distillation was carried out. Fluoropyrrolidine-trifluoromethane sulfonylimide (Fluoro-pyrrolidine-TFSI) was condensed and purified in a top-stage condenser with 20 stages using NMR, MASS and gas chromatograph (gas chromatograph, Agilent Technologies, 6890N, column: J & W Scientific HP-5). NMR and MASS. As a result, it was confirmed that mono-substituted fluoroethylene carbonate was mono-substituted. In addition, as a result of the peak area% on a gas chromatograph detector (FID), a fluoropyrrolidine-TFSI having a purity of 98.51% was obtained. This was recrystallized at 14 占 폚 to obtain fluoropyrrolidine-TFSI having a purity of 99.9%.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.78-1.81 (m, 2H), 2.76-2.81 (m, 4H), 3.5-3.8

[Example 8]

 12.23 kg of pyrrolidine-TFAc was placed in a 8 L recovery vessel and heated and circulated to a light irradiation reactor equipped with a 150 W UV high pressure mercury lamp (Heraeus TQ150). The reaction temperature in the light irradiation reactor was maintained in the range of 40 to 45 캜. Chlorine gas was continuously supplied from the bottom of the light irradiation reactor at a rate of about 200 L per hour. Nitrogen gas was supplied to the top of the light irradiation reactor at a rate of 800 L per hour. A second flow nitrogen gas was also fed into the liquid phase at the bottom of the recovery vessel at a rate of 800 L / hr. The liquid reactant was circulated at a rate of 2 to 3 L per minute. After 4.6 Kg of chlorine was introduced, the reaction was terminated. The reaction product was transferred to a vacuum distillation apparatus and distilled under reduced pressure while raising the temperature at 3 torr. As a result of distilling the material at a temperature of 70 to 80 캜, chloropyrrolidine-trifluoroacetamide (Chloropyrrolidine-TFAc) with a purity of 99% was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.74 - 1.80 (m, 2H), 2.74 - 2.83 (m, 4H), 3.3 - 3.9

[Example 9]

1 Kg of Hyflo Super Cell, a diatomaceous earth filter aid, was suspended in 115 L of butyl methyl ether and 64 L of triethylamine was added. The mixture was heated in a stirred reactor equipped with a reflux condenser. When the solvent began to reflux, a mixture containing 97.5 Kg of chloropyrrolidine-trifluoroacetamide prepared above was added to the reactor for 45 minutes. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and water was added to 80 L of butyl methyl ether. The organic layer was separated and washed three times with water. The organic extracts were then dried over anhydrous magnesium sulfate (anhydrous) and filtered. The product vinylene-trifluoroacetamide (Vinylene-TFAc) was obtained by removing t-butyl methyl ether under vacuum.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 3.18-3.31 (m, 4H), 5.76-5.81 (m, 2H)

[Example 10]

In a 2 L reactor equipped with a stirrer and a condenser, 1943 g of pyrrolidine-TFAc and 600 g of potassium fluoride (KF) were purged with nitrogen at 80 캜 for about 30 minutes. 1145 ml of sulfuryl chloride (SO 2 Cl 2) was added to the dropping funnel provided in the reactor head, and the mixture was added dropwise with stirring for 1 hour. Then, 719 mg of 2,2'-Azoisobutironitrile (AIBN) was dissolved in 20 ml of dichloromethane, The solution was added dropwise 4 times. The HCl gas generated in the reaction was neutralized in a base trap containing a saturated aqueous sodium hydroxide solution connected to a condenser. After the dropwise addition, the reaction mixture was stirred for 10 hours at a reaction temperature of 100 ° C. The reaction product was distilled under a condition of 80 ° C. and 30 torr to remove salts through a filter paper to obtain a product having a purity of 90.3% Vacuum distillation was carried out. The number of stages used was 20 stages and the purified fluoropyrrolidine-TFAc was condensed and purified in a tower top condenser and analyzed by NMR, MASS and gas chromatograph (Agilent Technologies, 6890N, column: J & W Scienctific HP-5) Respectively. NMR and MASS. As a result, it was confirmed that the compound was a mono-substituted fluoropyrrolidine-trifluoroacetamide (Fluoropyrrolidine-TFAc). Further, as a result of a peak area% on a gas chromatograph detector (FID), a fluoropyrrolidine-TFAc having a purity of 98.51% was obtained. This was recrystallized at 14 占 폚 to obtain fluoropyrrolidine-TFAc having a purity of 99.9%.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.74 - 1.80 (m, 2H), 2.74 - 2.83 (m, 4H), 3.3 - 3.9

[Example 11]

Cyanogen chloride (86 g, 1.4 mol) was dissolved in 150 ml of anhydrous ether cooled to -10 ° C. A solution of cyclohexylamine (127.23 g, 1.0 mol) dissolved in 200 ml of anhydrous ether was added thereto at a temperature of -5 ° C or lower for 2 hours. The reaction mixture was kept at room temperature for 12 hours, the resulting white precipitate was filtered, washed once with 100 ml of anhydrous ether and twice with 75 m of anhydrous ether. A solution of cyanogen chloride (30.7 g, 0.5 mol) dissolved in 150 ml of anhydrous ether cooled to -15 ° C was added dropwise to the filtrate while stirring. At the same time, triethylamine (50.6 g, 0.5 mol) dissolved in 150 ml of anhydrous ether was added thereto at -10 캜. After the addition was complete, stirring and cooling were continued for 15 minutes and then the temperature of the reaction mixture was raised to + 10 ° C. The resulting precipitate was filtered and washed twice with 100 ml of anhydrous ether once with 75 ml of anhydrous ether. The ether solution was evaporated, and the residue was fractionally distilled under a reduced pressure in a nitrogen gas atmosphere with a 15-cm Vigreux column. To obtain dicyanamide whose diethyl cyanamide had been removed, the product was further distilled with a Vigreux column to obtain a product, Cyclooctyldicyanamide (Cyclooctyl-DCN).

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.29 (m, 10H), 1.51 (m, 4H), 2.63

[Example 12]

Cyclooctyl iodide (21.0 g, 100 mmol) and 35 ml of tetrachloroethane were placed in a 100 ml round flask connected to a glass manifold system equipped with an expansion valve, and the entire system was subjected to freeze-thawing three times under vacuum to remove air Respectively. Tetrafluorohydrazine (6.70 g, 64 mmol) was charged to the system and the mixture was heated to 60 C for 2 hours. During this process the pressure dropped from a minimum of 525 mm to 368 mm. The excess gas fraction by mass spectroscopy was tested and it was found that 5.63 g (54 mmol) of tetrafluorohydrazine was consumed. The resulting dark solution was treated with mercury to remove dissolved iodine to obtain a solution close to transparency. The solution was distilled to obtain a product, Cyclooctyldifluoroamine (Cyclooctyl-DFA).

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.29 (m, 10H), 1.51 (m, 4H), 2.63

_{^{19 FNMR (CDCl 3): ppm}} -53.7 (s)

[Example 13]

N-chlorosuccinimide (40 g, 0.3 mol), a chlorinating agent mixed with 106 g of chromatographic alumina, was charged to a reactor tube (60 cm x 40 cm). The chlorinating agent was distributed horizontally between two pieces of quartz wool at a distance of 50 cm. Cyclooctylamine (12.7 g, 0.1 mol) pre-cooled to -30 占 폚 was slowly introduced into the system for 1 hour. The vapor phase was condensed in a liquid nitrogen trap to give the product, N, N-dichlorocyclobutylamine (Cyclooctyl-DCA).

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.29 (m, 10H), 1.51 (m, 4H), 2.63

[Example 14]

Di-tert-butyl-4-methyl-pyridine (0.637 g, 3.11 mmol) dissolved in trifluoroacetic anhydride (0.49 mL, 3.2 mmol) and 3 mL of carbon tetrachloride (0.206 g, 2.08 mmol) mmol) was reacted for 4 hours and pyridinium triflate was filtered off to obtain the product N-cyclohexyl-2,2,2-trifluoro-N- (2,2,2, -trifluoroacetyl) Amide (N-Cyclohexyl-2,2,2-trifluoro-N- (2,2,2-trifluoro-acetyl) -acetamide, Cyclohexyl-di-TFAC).

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.29 (m, 6H), 1.51 (m, 4H), 3.58

[Example 15]

To a mixture of 14.42 g of 3-morpholinopropylamine and 24.3 g of triethylamine in 100 ml of chloroform at -25 캜, 62.1 g of triflic anhydride was added dropwise in a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, poured into distilled water, and the organic layer was separated and washed three times with distilled water. The organic extracts were then dried over anhydrous MgSO ₄ and filtered. Morpholinopropyl- (bis-trifluoromethane sulfonyl) imide: 3-Morpholino-propyl-TFSI] was obtained by removing chloroform under vacuum.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.65 (m, 2H), 2.36 (m, 6H), 2.65 (m, 2H), 3.67

[Example 16]

62.1 g of triflic anhydride was added to a mixture of 11.92 g of 4,4'-methylenebis (2-methylcyclohexylamine) and 24.3 g of triethylamine in 100 ml of chloroform at -25 ° C in a nitrogen atmosphere . The solution was stirred at room temperature for 1 hour, poured into distilled water, and the organic layer was separated and washed three times with distilled water. The organic extracts were then dried over anhydrous MgSO ₄ and filtered. The chloroform was removed under vacuum to obtain the product 4,4'-methylene bis (2-methylcyclohexyl- (bis-trifluoromethanesulfonyl) imide) [4,4'-Methylenebis (2-methylcyclohexyl- -

sulfonylimide): 4,4'-Methylenebis (2-methylcyclohexyl-TFSI)] () g.

¹ H NMR (300 MHz, CDCl ₃ ): ppm 1.06 (m, 6H), 1.21-1.25 (m, 10H), 1.47 (m, 2H) m, 2H)

[Example 17]

62.1 g of triflic anhydride was added dropwise to a mixture of 21.04 g of 4,4'-trimethylene dipiperidine and 24.3 g of triethylamine in 100 ml of chloroform at -25 캜 in a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, poured into distilled water, and the organic layer was separated and washed three times with distilled water. The organic extracts were then dried over anhydrous MgSO ₄ and filtered. The chloroform was removed under vacuum to obtain the product 4,4'-trimethylenedipiperidine trifluoromethanesulfonylamide [4,4'-Trimethylenedipiperidinetrifluoromethanesulfonylamide: 4,4'-Trimethylenedipiperidine-TFSA].

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 1.25 (m, 4H), 1.29 (m, 2H), 1.46 (m, 4H), 1.49 (m, 2H), 2.7 (m, 8H)

[Example 18]

62.1 g of triflic anhydride was added dropwise to a mixture of 2.55 g of acrylamide and 24.3 g of triethylamine in 100 ml of chloroform at -25 캜 in a nitrogen atmosphere. The solution was stirred at room temperature for 1 hour, poured into distilled water, and the organic layer was separated and washed three times with distilled water. The organic extracts were then dried over anhydrous magnesium sulfate (anhydrous) and filtered. The chloroform was removed under vacuum to obtain the product acrylic- (bis-trifluoromethane sulfonyl) imide: Acryl-TFSI.

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 5.71 (m, 1H), 6.17 (m, 1H), 6.48 (m, 1H)

 [Example 19]

To a mixture of 1.25 g of acrylamide and 2.0 g of triethylamine in 40 ml of dichloromethane at -40 캜, 5.0 g of triflic anhydride was added dropwise in a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours and then volatiles were removed under reduced pressure. The remaining viscous liquid was dissolved in 4 moles of sodium hydroxide and then washed three times with 25 ml of dichloromethane. The aqueous phase was then neutralized with hydrochloric acid and extracted three times with 30 ml of dichloromethane. The organic extract was dried over anhydrous magnesium sulfate and the dichloromethane was removed under vacuum to obtain the product acrylamide-trifluoromethanesulfonamide (Acrylamide-TFSA).

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 4.9 (s, 1H), 5.71 (m, 1H), 6.17 (m, 1H), 6.48 (m, 1H)

IR: υN-H 3315 cm ^-1

[Example 20]

To 40 ml of dichloromethane was added 1.25 g of acrylamide, 2.0 g of triethylamine and 3.72 g of trifluoroacetic anhydride as in Scheme 22 of Example 19 to give the product acrylamide-trifluoroacetamide [ Acrylamide-trifluoroactamide: Acrylamide-TFAC] was obtained.

_{^{1 H NMR (300MHz, CDCl 3}} ): ppm 4.9 (s, 1H), 5.71 (m, 1H), 6.17 (m, 1H), 6.48 (m, 1H)

IR: υN-H 3315 cm ^-1

[Example 21] Preparation of ion conductive thin film

Acrylamide-trifluoromethanesulfonamide (0.25 g), an anion receptor compound prepared in Example 19, was dissolved in a mixture of bisphenol A ethoxylate dimethacrylate (obtained from Aldrich, Mw = 1,700, " BIS-15m ", 0.25 g) , poly (ethylene glycol) dimethyl ether (Mw = 350," PEGDME 300 ", 0.5 g) and methane sulfonic acid imide lithium trifluoroacetate _{(Li (CF 3 SO 2)} 2 N, 0.3943 g). The composition of this mixture is shown in Table 1 below. Dimethylphenylacetophenone (DMPA, 0.0075 g) was added to the mixture, the mixture solution was applied to a conductive glass substrate, and exposed to ultraviolet light of 350 nm wavelength for 30 minutes under a nitrogen atmosphere. A solid polymer thin film was prepared by this irradiation.

[Comparative Example 1] Production of a thin film containing no anion receptor

The composition of the compound used is shown in Table 1 below, and a solid polymer thin film was prepared in the same manner as in Example 21.

Cross-linking agent Anion receptor compound Plasticizer Lithium salt Initiator usage usage usage usage usage Example 21 Bis-15m Example 19 PEGDME _{Li (CF 3 SO 2) 2} N DMPA 0.25 g 0.25 g 0.50 g 0.3943 g 0.0075 g Comparative Example 1 Bis-15m - - _{Li (CF 3 SO 2) 2} N DMPA 0.250 - - 0.1270 g 0.0075 g

[Example 22] Ionic conductivity experiment

The thin film of the solid polymer electrolyte thin film prepared in Example 21 and the thin film prepared in Comparative Example 1 using the anion receptor acrylamide-trifluoromethane sulfonamide synthesized in Example 19 according to the present invention and the ion of the thin film prepared in Comparative Example 1 Conductivity was measured. The ionic conductivity was measured by the following method.

The solid polymer electrolyte composition was coated on a band-type conductive glass substrate or a lithium-copper foil, then photocured and sufficiently dried. Then, AC impedance between the band-type or sandwich-type electrodes was measured in a nitrogen atmosphere, And analyzed by a response analyzer to determine the complex impedance.

Band-type electrodes were prepared by attaching masking tapes with a width of 0.5-2 mm to the center of conductive glass (ITO) at intervals of 0.5-2 mm in length, etching them by etching solution, washing and drying. The ionic conductivity was measured using the solid polymer electrolyte membrane of Example 22 prepared as shown in Table 1 above. The results of measurement of the ionic conductivity at 30 ° C are shown in Table 2 below.

Ion conductivity σ (S / cm) Example 22 1.68 x 10 ^-5 Comparative Example 1 4.62 × 10 ^-6

As shown in Table 2, it can be seen that the solid polymer electrolyte thin film prepared using the anion receptor according to the present invention has significantly higher ion conductivity than the solid polymer electrolyte thin film prepared without the anion receptor, The electrochemical cell and the lithium ion capacitor employing the solid polymer electrolyte thin film according to the present invention can have high efficiency.

 [Example 23] Manufacture of lithium ion polymer cell using gel type polymer electrolyte including anion receptor

Acrylamide-trifluoromethanesulfonamide (0.2 g), an anion receptor prepared in Example 19, was dissolved in a mixture of bisphenol A ethoxylate diacrylate (obtained from Aldrich, Mw = 688, "BIS- (LUPEROX 11M70, 0.004 g), organic solvent EC / DMC / DEC (1: 1: 1, 1M LiPF ₆ ) (0.667 g) and t-butylperoxy pivalate A lithium ion polymer battery in which a polyethylene separator impregnated with lithium and nickel metal impregnated with the above mixture solution was sandwiched therebetween was placed in an oven at 80 캜 for 2 hours to thermally cure it. A typical 2-electrode electrochemical cell was prepared. Nickel metal was used as working electrode and lithium metal was used as reference electrode and counter electrode. The cell was assembled in a glove box and was fabricated by vacuum sealing using a metal-lined polyether bag.

[Comparative Example 2] Production of lithium ion polymer cell using gel polymer electrolyte without anion receptor

A lithium ion polymer battery was prepared in the same manner as in Example 22, except that acrylamide-trifluoromethane sulfonamide as an anion receptor prepared in Example 19 was not used.

[Example 24] Electrochemical stability experiment

The electrochemical stability of the lithium ion polymer batteries prepared in Example 23 and Comparative Example 2 was evaluated using a cyclic voltammetry and a linear sweep method using Potentiostat (EG & G, Model 270A) Voltammography). CV was measured at a temperature of 30 캜 in a range of -0.5 V to 6.0 V at a speed of a potential scanning speed of 5 mV / sec. The lithium ion polymer battery manufactured using the electrolyte containing no anion receptor is deteriorated at a potential near 4.0 V. In comparison with the lithium ion polymer battery produced using an electrolyte including anion receptor, And showed reversible redox reaction of lithium to the working electrode.

[Example 25] Production of lithium ion battery using liquid electrolyte containing anion receptor

Acrylamide-trifluoromethanesulfonamide (0.01 g), an anion receptor prepared in Example 19, was mixed with 1.0 g of organic solvent EC / DMC / EMC (1: 1: 1, 1 M LiPF ₆ ). A polypropylene separator impregnated with the above mixture solution was sandwiched between the LiCoO ₂ positive electrode and the graphite carbon negative electrode in a dry room (humidity: within 3%) to assemble the lithium ion battery. The LiCoO ₂ anode was 94 wt. % LiCoO ₂ (Nippon Chemical Industries), 3 wt% acetylene black, 3 wt. % Polyvinylidene fluoride (PVDF) on an aluminum foil.

 [Comparative Example 3] Production of a lithium ion battery using a liquid electrolyte containing no anion receptor

 A lithium ion battery was prepared in the same manner as in Example 24, except that acrylamide-trifluoromethane sulfonamide as an anion receptor prepared in Example 19 was not used.

 [Example 26] Lithium cycling performance and efficiency test of a lithium ion battery

Lithium cycling performance and efficiency of the lithium ion batteries prepared in Example 25 and Comparative Example 3 of the present invention were measured at room temperature using a charge-discharge experiment apparatus (Maccor 4000). Charging and discharging were performed at 0.2, 0.5, and 1 C, respectively. The lithium ion battery was charged and discharged between 3.0 V and 4.2 V at a constant current density of 0.6 mA / cm ² (charge) and 1.5 mA / cm ² (discharge) against the LiCoO ₂ counter electrode.

A comparison of the discharge capacity with respect to the cycling number of a lithium ion battery cell manufactured using an electrolyte solution containing an anion receptor acrylamide-trifluoromethane sulfonamide of the present invention and an electrolyte solution containing no additive compound is shown in FIG. Except for the first few cycles, a higher capacity than that of a lithium ion battery using an electrolyte containing no lithium ion battery using an electrolyte including acrylamide-trifluoromethane sulfonamide as an anion receptor of the present invention was exhibited. Also, the discharge capacity of the battery containing the anion receptor increased until it reached 20 cycles and then gradually decreased. However, the capacity of cells without anion receptor tended to decrease significantly as the cycle progressed. These results show that the performance of the lithium ion battery is improved by the addition of the anion receptor.

[Example 27] Manufacture of lithium ion capacitor cell using electrolytic solution containing additive compound

Acrylamide-trifluoromethanesulfonamide (0.007 g), an anion receptor prepared in Example 19, was mixed with 1.0 g of organic solvent EC / DMC / EMC (1: 1: 1, 1 M LiPF ₆ ) . The Li ₄ Ti ₅ O ₁₂ anode had 82.5 wt. % Of Li ₄ Ti ₅ O ₁₂ , 10 wt.% Of carbon black (DB-100) and 7.5 wt.% Of polyvinylidene fluoride (PVDF) on aluminum foil. The negative electrode was prepared by coating an aluminum foil with a mixture of 85 wt.% Activated carbon, 10 wt.% Carbon black (DB-100), and 10 wt.% Polyvinylidene fluoride (PVDF). A polypropylene separator impregnated with the above mixture solution was sandwiched between the Li ₄ Ti ₅ O ₁₂ anode and the activated carbon cathode in a drier (humidity: 3% or less) and assembled by vacuum sealing.

[Comparative Example 4] Production of lithium ion capacitor cell using an electrolyte solution containing no additive compound

 A lithium ion capacitor cell was prepared in the same manner as in Example 26 except that acrylamide-trifluoromethanesulfonamide, which is an anion receptor prepared in Example 19, was not used.

[Example 28] Lithium cycling performance and efficiency test of lithium ion capacitor cell

Lithium cycling performance and efficiency of the lithium ion capacitor cell prepared in Example 27 and Comparative Example 4 of the present invention were measured at room temperature using a charge and discharge test apparatus (Maccor 4000). Charging and discharging were performed at 0.2, 0.5, and 1 C, respectively. The battery was charged and discharged between 1.5 V and 3.5 V at a constant current density of 0.6 mA / cm ² (charge) and 1.5 mA / cm ² (discharge) against the Li ₄ Ti ₅ O ₁₂ counter electrode.

Ionic capacitor cell using an electrolyte containing no lithium ion capacitor cell using an electrolyte containing acrylamide-trifluoromethanesulfonamide, which is an anion receptor of the present invention, and exhibits remarkably excellent stability.

Claims (8)

(4) or (10).
[Chemical Formula 4]

[Chemical formula 10]

[In the formulas (4) and (10)
R ₁ is -SO ₂ CF ₃ , or -SO ₂ CN;
R ₃ is halogen or (C ₁ -C ₂₀ ) alkyl;
R ₄ is independently from each other hydrogen, halogen or (C ₁ -C ₂₀ ) alkyl;
and o is an integer of 1 to 4.] delete The method according to claim 1,
(4) or (10) is selected from the following compounds.

An electrolyte comprising a compound according to any one of claims 1 and 3. 5. The method of claim 4,
Wherein the electrolyte comprises 0.01 to 40% by weight of the compound of Formula 4 or Formula 10 based on 100% by weight of the total electrolyte. The polymer electrolyte thin film produced by using the electrolyte of claim 4.  A battery fabricated using the electrolyte of claim 4.  A lithium ion capacitor produced using the electrolyte of claim 4.

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