WO2007091817A1

WO2007091817A1 - Anion receptor, and electrolyte using the same

Info

Publication number: WO2007091817A1
Application number: PCT/KR2007/000625
Authority: WO
Inventors: Hee Jung Kim; Won Sil Lee; Ki Beom Park
Original assignee: Individual
Current assignee: Individual
Priority date: 2006-02-06
Filing date: 2007-02-06
Publication date: 2007-08-16
Anticipated expiration: 2008-08-06

Abstract

Disclosed is a novel anion receptor and electrolytes containing the same. A novel anion receptor is a linear hydrocarbon compound having an amine substituted with electron withdrawing groups as (a) terminal group(s). When the anion receptor is added to the electrolyte, ionic conductivity and cation transference number of electrolytes are enhanced, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes.

Description

ANION RECEPTOR, AND ELECTROLYTE USING THE SAME

Field of the Invention

The present invention relates to a novel anion receptor, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel anion receptor, which is a linear hydrocarbon compound having an amine substituted with electron withdrawing groups as (a) terminal group(s) and which is added to enhance ionic conductivity and cation transference number of electrolytes, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the anion receptors.

Description of the Related Art

Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base. These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li⁺) by coordinating electron- rich anions around to interfere with forming ion pairs between the anions and the lithium cations. The first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 146 (2000) 9). However, these aza- ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of cathode materials. In addition, it has been discovered that aza-ethers are unstable to LiPF₆

(J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, chemically and thermally unstable LiPF₆ is in equilibrium with solid LiF and PF₅ gas even at room temperature, and production of PF₅ gas makes the equilibrium moved towards generating PF₅ gas.

LiPF₆ (S) .^=- LiF (s) + PF₅ (g)

In a nonaqueous solvent, PF₅ has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electron, e.g., oxygen or nitrogen. Meanwhile, PF₅, a relatively strong Lewis acid, is known to attack electron pairs. Due to high electron density, aza-ethers are promptly attached by PF₅ (J. Power Sources, 104 (2002) 260). This is a major drawback to commercialize aza-ether compounds. To resolve this problem, McBreen et al. synthesized an anion receptor comprising boron as an electron deficient atom substituted by an electron withdrawing group using the same means (J. Electrochem. Soc, 145 (1998) 2813, 149 (2002) A1460). On the other hand, solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances. In 1975, a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M. Aπnand in 1978. Typically, a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor. One of the most well- known solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes

thereof. Because these have ionic conductivity as low as l O^"8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature.

A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted. In order to increase mobility of molecular chains, the crystalline area existing in the polymer structure should be minimized while the amorphous area therein should be expanded. A research to achieve such has been and is under way by using a siloxane having a flexible molecular chain (Marcromol. Chem. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6845) as a main chain, or by introducing PAO having a relatively short molecular length as a side branch (Electrochem. Acta, 34 (1989) 635). According to another research in progress, net-shaped solid polymer electrolytes are prepared by introducing at least one crosslinkable functional group to the PAO as a terminal group. Unfortunately however, ionic conductivity of such electrolytes at room temperature is as low as 10^"5~10^"4 S/cm which is not suitable for use in lithium batteries operating at room temperature conditions, so continuous researches have been made to improve the ionic conductivity. This problem was resolved by Abraham et al. who introduced polyethylene oxide with low molecular weight into a vinylidenhexafluoride - hexafluoropropene copolymer to enhance ionic conductivity (Chem. Mater., 9 (1997) 1978). In addition, by adding lower molecular weight PEGDME (polyethyleneglycol dimethylether) to a photocuring type crosslinking agent having a siloxane based main chain and a PEO side branch, the ionic conductivity was increased to

8^χ 10^" S/cm at room temperature under film forming conditions (J. Power Sources 119- 121 (2003) 448). However, cycling efficiency on a Ni electrode was about 53% at most mainly because the newly deposited lithium surface rapidly eroded, thereby passivating the electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). That is, according to Vincent, lithium metal reacts with a lithium salt as follows (Solid State Chem. 17 (1987) 145):

LiSO₃CF₃ + Li (s) → 2Li⁺ + SO₃ ^2" + CF₃-

The CF₃ radical would extract a hydrogen atom from the PEO polymer chain forming HCF₃ and may cause the breaking of the polymer chain. That is, the =C-O-C- group may be caused by this abstraction of hydrogen and main chain of the polymer breaks. At this time, CH₃ produced by chain scission together with the CF₃ radical attack the chain or break a C-O bond. A Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated.

Therefore, in order to solve the above-described problems, there is a need to develop a novel substance capable of resolving the electrochemical instability and the instability towards lithium salts and offering enhanced ionic conductivity by designing a compound which does not have an easily attackable nitrogen atom in the middle of a compound as in aza-ether compounds, or by replacing the PAO type plasticizer.

Detailed Description of the Invention Technical Subject

It is, therefore, an object of the present invention to provide a novel anion receptor, which is a linear hydrocarbon compound having an amine substituted with electron λvithdrawing groups as (a) terminal group(s) and which enhances ionic conductivity and cation transference number of electrolytes containing it, thereby increasing the

electrochemical stability of alkali metal batteries using the electrolytes.

It is another object of the present invention to provide a nonaqueous liquid

electrolyte and a gel or solid polymer electrolyte containing at least one of the novel anion

receptors.

It is still another object of the present invention to provide an electrochemical cell

which uses an electrolyte containing the novel anion receptors.

Technical Solution To achieve the above objects and advantages, there is provided an anion receptor

for use in a polymer electrolyte represented by the following Formula 1, which is

composed of a linear hydrocarbon compound having an amine substituted with electron

withdrawing groups as (a) terminal group(s):

[Formula 1]

wherein Ri and R₂ each independently represents a hydrogen atom, or an electron

withdrawing functional group selected from the group consisting Of -SO₂CF₃, -CN, -F, -Cl,

-COCF₃, - BF₃ and -SO₂CN, but do not both simultaneously represent a hydrogen atom;

R₃ represents a hydrogen atom or a methyl group;

H / ' X is a hydrogen atom, a methyl group, ^CH2 or ^R2 ;

R₃ and X do not simultaneously represent a hydrogen atom; n is an integer from O to 20.

The compound of the Formula 1 functions as an anion receptor in an electrolyte and preferred examples of the compound include; N-Allyltrifluoromethanesulfonamide, N,N-

Dicyanoallylamine, N,N-Difluoroallylamine, N,N-Dichloroallylamine, N-allyl-2,2,2- trifluoro-N-trifluoroacetyl-acetamide, N,N,N,N-Tetra(trifluoromethanesulfonyl)-ρropane- 1 ,3-diamine, N,N,N,N-Tetracyano-propane-l ,3 -diamine, N,N,N,N-Tetrafluoro-propane- 1 ,3-diamine, N,N,N,N-Tetrachloro-propane-l ,3-diamine, N-{3-[Bis-(2,2,2-trifluoro- acetyl)-amino]-propyl}-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide, N,N-

Di(trifluoromethanesulfonyl)butylamine, N,N-Dicyanobutylamine, N,N- Difluorobutylamine, N,N-Dichlorobutylamine, N-Butyl-2,2,2-trifluoro-N-(2,2,2-trifluoro- acetyl)-acetamide, N,N-Di(trifluoromethanesulfonyl)octylamine, N,N-Dicyanooctylamine, N,N-Difluorooctylamine, N,N-Dichlorooctylamine, N-Octyl-2,2,2-trifluoro-N-(2,2,2- trifluoro-acetyl)-acetamide, N,N,N,N-Tetra(trifluoromethanesulfonyl)-octane- 1 ,8-diamine, N,N,N,N-Tetracyano-octane-l,8-diamine, N,N,N,N-Tetrafluoro-octane-l,8-diamine, N,N,N,N-Tetrachloro-octane-l ,8-diamine, N-{8-[Bis-(2,2,2-trifIuoro-acetyl)-amino]- octyl} -2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide, N₅N-

Di(trifluoromethanesulfonyl)hexadecylamine, N,N-Dicyanohexadecylamine, N,N- Difluorohexadecylamine, N,N-Dichlorohexadecylamine, or N-Hexadecyl-2,2,2-trifluoro- N-(2,2,2-trifluoro-acetyl)-acetamide. The nonaqueous liquid electrolyte and a gel or solid polymer electrolyte of the present invention comprises at least one of. the novel anion receptors represented by the Formula 1, which is composed of a linear hydrocarbon compound having an amine substituted with electron withdrawing groups as (a) terminal group(s).

Among the functional groups introduced as a side branch, the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number. In detail, nitrogen in the amine becomes electron deficient by electron withdrawing groups, such as -SO₂CF₃, - CN, -F, -Cl, -COCF₃, -BF₃ and -SO₂CN, and forms electrically neutral complexes with anions of alkali metal salts. In this manner, the dissociation of alkali metal salts into ions is promoted. A family of aza-ether based compounds is disclosed in U.S. Pat. Nos. 5,705,689 and 6,120,941 , in which an easily attackable nitrogen atom existing in the middle of the compound causes electrochemical instability, instability to lithium salts (especially, LiPF₆) and steric hindrance. On the contrary, in the present invention, a nitrogen of the amine group atom, where one of the hydrogen atoms is substituted with electron withdrawing groups, exists in terminal position of the hydrocarbon chain, and

therefore more portion of the center of the nitrogen atom is exposed, easily attracting bulky anions thereto. As a result, dissociation of lithium salt is enhanced, cation transference number is increased and thus, high ionic conductivity can be achieved. The anionic receptor represented by the Formula 1 can be synthesized by any known method.

For example, the compound of the Formula Ia can be synthesized by substitution reaction of an amine terminal group of linear hydrocarbon compound represented by the following Formula 2a with electron withdrawing groups, such as -SO₂CF₃, -CN, -F, -Cl, - COCF₃, -BF₃ and -SO₂CN (see Reaction Scheme 1). [Reaction Scheme 1]

2a 1 a wherein, Ri, R₂, R₃ and n are defined as in the compound of the Formula 1, and X of Formula 1 is methyl group.

For another example, the compound of the Formula Ib can be synthesized by substitution reaction of an amine terminal group of linear hydrocarbon compound represented by the following Formula 2b with electron withdrawing groups, such as - SO₂CF₃, -CN, -F, -Cl, -COCF₃, -BF₃ and -SO₂CN (see Reaction Scheme 2). [Reaction Scheme 2]

wherein, Ri, R₂, R₃ and n are defined as in the compound of the Formula 1 , and X

^, of Formula 1 is CH₂

For another example, the compound of the Formula Ic can be synthesized by substitution reaction of two amine terminal groups of linear hydrocarbon compound represented by the following Formula 2c with electron withdrawing groups, such as - SO₂CF₃, -CN, -F, -Cl, -COCF₃, -BF₃ and -SO₂CN (see Reaction Scheme 3). [Reaction Scheme 3]

2c wherein, Ri, R₂, R₃ and n are defined as in the compound of the Formula 1, and X

A of Formula 1 is ^R2.

The present invention provides electrolytes containing the anion receptor represented by the compound of the Formula 1 , and the electrolytes comprise nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.

In detail, the nonaqueous liquid electrolyte of the present invention comprises (i) an anion receptor of the Formula 1 ; (ii) a nonaqueous solvent; and (iii) an alkali metal ion containing substance.

In addition, the present invention provides a gel polymer electrolyte, which comprises (i) an anion receptor of the Formula 1; (ii) a polymer support; (iii) a nonaqueous solvent; and (iv) an alkali metal ion containing substance.

Moreover, the present invention provides a solid polymer electrolyte, which comprises (i) an anion receptor of the Formula 1; (ii) a polymer selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.

The solid polymer electrolyte may further include one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof. The nonaqueous solvent used for the electrolyte includes ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2- methyltetrahydrofuran, 4-methyl-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,

dimethoxymethane, γ-butyrolactone, methyl formate, sulforane, acetonitrile, 3-methyl-2-

oxazolidinone, N-methyl-2-pyrrolidinone or mixtures thereof.

The alkali metal ion containing substance includes LiSO₃CF₃, LiCOOC₂F₅, LiN(SO₂CF₃)₂, LiC(SO₂CF₃)₃, LiClO₄, LiAsF₆, LiBF₄, LiPF₆, LiSbF₆, LiI, LiBr, LiCl or a mixture thereof. Although there is no limitation on the polymer support for use in the gel polymer electrolyte, preferred examples include polyacrylonitrile (PAN) type polymers or polyvinylidenfluoride (PVDF)-hexafluoropropylene type polymers.

Also, there is no limitation on the net-shaped, comb-shaped or branched polymer compounds used in the solid polymer electrolyte, but flexible inorganic polymers or linear polyethers are preferred examples. As for the crosslinkable polymer compound, a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl is used.

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

Examples of the crosslinkable polymer compound include bisphenol A ethoxylate dimethacrylate represented by the following Formula 3 or TA-IO represented by the following Formula 4 disclosed in Korean Patent Registration No. 10-0419864:

[Formula 3]

Bis- 15m

[Formula 4]

TA-I O

Similar to the anion receptor of the present invention, polyalkyleneglycol dialkylether or a nonaqueous solvent contained in the solid polymer electrolyte is used as a plasticizer.

Examples of the polyalkyleneglycol dialkylether include polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether.

When the solid polymer electrolyte contains a crosslinkable polymer compound, it further comprises a curing initiator.

As for the curing initiator, a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used. Preferred examples of the photocuring initiator is selected from the group

consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl

benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl ether, benzoin phenyl ether,

α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-

methyl- 1-phenylpropane-l -on, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p- chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone and a mixture thereof.

Examples of the heat-curing initiator include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.

More particularly, the electrolyte of the present invention preferably contains 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.

The gel polymer electrolyte of the present invention preferably contains 5 - 40 parts by weight of the polymer support.

The solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of a polymer compound selected from the net-shaped, comb-shaped and branched polymer compounds, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator. The solid polymer electrolyte of the present invention preferably contains 10 - 50 parts by weight of one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkyl ether, a nonaqueous solvent and a mixture thereof.

In addition, the present invention provides an electrochemical cell containing the above anion receptor. Particularly, a cell using the liquid or gel polymer electrolyte of the present invention is composed of a cathode, an anode, and a separator, while a cell using the solid polymer electrolyte is composed of a cathode and an anode.

Here, an anode and a cathode used in the electrochemical cell of the present

invention are manufactured by any known method of manufacturing anodes and cathodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.

The anode is made of a material selected from the group that consists of lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as Li_xWO₂ or LiMoO₂; lithium metal sulfide intercalation compounds, such as

LiTiS₂; mixtures thereof; and mixtures of these and alkali metals.

The cathode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfϊde)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.

The following now describes constitutional embodiments of the electrochemical cell of the present invention.

A primary cell composed of a nonaqueous liquid electrolyte containing the anion receptor of the present invention is composed of: (i) an anode made of a material selected from the group consisting of lithium, lithium alloys, lithium-carbon intercalation compounds, lithium-graphite intercalation compounds, lithium metal oxide intercalation compounds, mixtures thereof, and alkali metals;

(ii) a cathode made of a material selected from the group consisting of transition metal oxides, transition metal chalcogenides, poly(carbondisulfϊde)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and oxychlorides, such as, SO₂, CuO, CuS, Ag₂CrO₄, 1₂, PbI₂, PbS, SOCl₂, V₂O₅, MoO₃, MnO₂ and polycarbon mono fluoride (CF)_n; (iii) a nonaqueous liquid electrolyte described above; and

(iv) a separator.

Manufacture of an anode and a cathode, and assembly of a cell can be achieved by well-known methods.

In addition, a secondary cell composed of a nonaqueous liquid electrolyte containing the anion receptor of the present invention is composed of:

(i) an anode containing lithium metals or materials capable of reversibly reacting with lithium metal, including: lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as Li_xWO₂ or LiMoO₂; and lithium metal sulfide intercalation compounds, such as LiTiS₂;

(ii) a cathode containing transition metal oxides capable of intercalating lithium, such as, Li₂.₅V₆Oi₃, Li] ₂V₂O₅, LiCoO₂, LiNiO₂, LiNi i_-xM_xO₂ (wherein M is Co, Mg, Al or Ti), LiMn₂O₄ or LiMnO₂ and the like; transition metal halides; or chalcogenides, such as, LiNbSe₃, LiTiS₂, LiMoS₂ and the like; (iii) a nonaqueous liquid electrolyte described above; and

(iv) a separator.

The secondary cell composed of a gel polymer electrolyte containing the anion receptor of the present invention comprises a gel polymer electrolyte of the present

invention in addition to an anode, a cathode, and a separator used in a secondary cell composed of the above nonaqueous liquid electrolyte.

The secondary cell composed of a solid polymer electrolyte containing the anion receptor of the present invention comprises a solid polymer electrolyte of the present invention in addition to an anode and a cathode used in a secondary cell composed of the above nonaqueous liquid electrolyte.

Moreover, the present invention provides a polymer electrolyte film (membrane) using an electrolyte of the present invention. A preparation method of a gel or solid polymer electrolyte film (membrane) containing the components of the present invention is as follows:

First, in case of a gel polymer electrolyte, a nonaqueous solvent, an anion receptor of the Formula 1 and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. A polymer support is then added to the solution and mixed together. If necessary, heat can be applied to completely dissolve the polymer support in the solution. In this manner, a composite mixture for preparing a gel polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron beams, UV rays

or γ-rays, or heated to cause the hardening reaction, and a desired film is obtained.

In case of a solid polymer electrolyte, on the other hand, an anion receptor or polyalkyleneglycol dialkylether or a nonaqueous solvent and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.

Then, a net-shaped, branched or comb-shaped polymer compound or a crosslinkable polymer compound is added to the solution and is mixed together. If necessary, heat can be applied to completely dissolve the net-shaped, branched or comb-shaped polymer compound in the solution. Meanwhile, a curing initiator can be added to the solution when

the crosslinkable polymer is used. In this manner, a composite mixture for preparing a solid polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron beams, UV

rays or γ-rays, or heated to cause the hardening reaction, and a desired film is obtained.

Another example of the preparation method for a film is as follows. After the support substrate is coated with the composite mixture, a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a gel or solid polymer electrolyte film.

Brief Description of the Drawings

FIG. 1 is a graph showing ionic conductivities in solid polymer electrolytes of the present invention (Experimental example 1);

FIG. 2 is a graph showing ionic conductivities in solid polymer electrolytes of the present invention (Experimental example 2); FIG. 3 is a graph showing electrochemical stabilities in solid polymer electrolytes of the present invention (Experimental example 3); and

FIG. 4 is a graph showing cycling performance of cells including anion receptor as an additive of the present invention (Experimental example 4). Preferred Embodiments

A preferred embodiment of the present invention will be described herein below. It is also to be understood that examples herein are for the purpose of describing the present

invention only, and are not intended to be limiting. Example 1. Preparation of an anion receptor (1)

[Reaction Scheme 4]

AIIyI-TFSA

1.Og of allylamine (17.5mmol) and 2.Og of triethylamine (20mmol) were mixed with 40ml of chloroform at -4O⁰C, and 5.0g of triflic anhydride (18mmol) was added dropwise to the mixture under nitrogen atmosphere. The solution was stirred at room

temperature for four hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30ml of 4M NaOH, washed three times with 25ml of chloroform, and water soluble component was neutralized with HCl, followed by washing three times with 30ml of chloroform. Then, an organic extract was dried over anhydrous MgSO₄ and filtered. The chloroform was removed under vacuum to yield N-Allyltrifluoromethanesulfonamide (Allyl-TFSA) (see the Reaction Scheme 2).

¹H NMR (300MHz, CDCl₃): ppm 3.9 (m, 2H), 4.9 (s-broad, IH), 5.35 (m, 2H), 5.9

(m, IH); ¹⁹F NMR (CDCl₃): ppm -77.9 (s); IR: υ_N._H 3315 cm^"1

Example 2. Preparation of an anion receptor (2) [Reaction Scheme 5] C,H₅),N

,NH-, CICN ClCN, (

ΓH ΓHΓH NH Π -(C₂H₅J₃NHCl

-C H₂CHC H₂NH₂C, _{A1Iyl-cyanamlde} N,N-D,cvanoal_ly.a_m,ne

86g of cyanogen chloride (1.4mol) was dissolved in 150ml of cold anhydrous ether (-1O⁰C). A mixed solution of 57.1g of allylamine and 200ml of anhydrous ether was added thereto over 2 hours while keeping the temperature below -5⁰C. The reaction mixture was set aside until room temperature for 12 hours. A white precipitate thusly produced was collected and washed once with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. Then, a mixed solution of 30.7g of cyanogen chloride (0.5mol) and 150ml of cold anhydrous ether (-15⁰C) was added dropwise to the filtrate while stirring. At the same time, another mixed solution of 50.6g of triethylamine (0.5mol) and 150ml of anhydrous ether was added dropwise to the filtrate while keeping the temperature below - 1O⁰C. Stirring and cooling was continued for an additional 15 minutes and the temperature of the reaction mixture was raised to +1O⁰C. A precipitate was filtered and washed once

with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. The ether solution was evaporated and the residue was fractionally distilled over a 15cm Vigreux column under nitrogen atmosphere. To obtain dicyanamide free of diethyl cyanamide, the crude product was distilled once more over the Vigreux column to yield N₅N- dicyanoallylamine (Allyl-DCN) (see the Reaction Scheme 5).

¹H NMR (300MHz, CDCl₃): ppm 4.02 (m, 2H), 5.25 (m, 2H), 6.63 (m, IH); ¹³C NMR (CDCl₃): ppm 45.4, 1 16.3, 119.2, 136.2. Example 3. Preparation of an anion receptor (3) [Reaction Scheme 6]

N,N-Difluoroallylamine

16.8g of allyl iodide (lOOmmol) and 35ml of tetrachloroethane were placed in a

100ml round flask connected to a glass manifold system having an expansion valve, and the entire system went through 3 freezing - defreezing cycles under vacuum to remove air therein. The system was then filled with 6.7Og of tetrafluorohydrazine (64mmol), and the mixture was heated at 6O⁰C for 2 hours. During the heating process, the pressure was dropped from the lowest 525mmHg to 368mmHg. When excess gas fraction was analyzed by mass spectroscopy, it was discovered that 5.63g of tetrafluorohydrazine (54mmol) was

consumed. Obtained dark colored solution was treated with mercury to remove iodine therein. A substantially transparent solution thusly obtained was then distilled to yield

N,N-difluoroallylamine (allyl-DFA) (see the Reaction Scheme 6).

¹H NMR (300MHz, CDCl₃): ppm 4.26 (m, 2H), 5.37 (m, 2H), 5.97 (m, IH); ¹⁹F NMR (CDCl₃): ppm -53.7 (s). Example 4. Preparation of an anion receptor (4) [Reaction Scheme 7]

N.N-Dichloroallylamine

A mixture of 106g of chromatographic alumina and 4Og of N-chlorosuccinimide, a chlorinating agent (0.3mol) was packed into a reactor tube (60cm x 40cm). Then, the chlorinating agent was horizontally split between two pieces of quartz wool being 50cm apart from each other. 5.7g of allylamine which was precooled to -3O⁰C was slowly introduced into the system over 1 hour. Later, vapor was condensed in liquid nitrogen trap to yield N, N-dichloroallylamine (Allyl-DCA) (see the Reaction Scheme 7).

¹H NMR (300MHz, CDCl₃): ppm 5.2 (m, 2H), 5.4 (m, 2H), 5.95 (m, IH); ¹³C NMR (CDCl₃): ppm 62.7, 116.3, 135.2.

Example 5. Preparation of an anion receptor (5) [Reaction Scheme 8]

N-allyl-ljl.l-tπfluoro-N-trifluoroacctyl-acetamide

0.119g of allylamine (2.09mmol) and 0.49g of anhydrous trifluoro acetic acid

(3.2mmol) were reacted with a mixed solution of 3ml of carbon tetrachloride and 0.637g of 2,6-di-tertiary-butyl-4-methyl-pyridine (3.11mmol) for four hours. Pyridinium triflate was filtered and removed to yield N-allyl-2,2,2-trifluoro-N-trifluoroacetyl-acetamide (Allyl-

TFAC) (see the Reaction Scheme 8).

¹H NMR (300MHz, CDCl₃): ppm 4.37 (m, 2H), 5.07-5.26 (m, 2H), 5.80 (m, IH); ¹³C NMR (CDCl₃): ppm 43.0, 116.9, 122.9, 132.3. 167.2; ¹⁹F NMR (CDCl₃): ppm -71.3 (s). Example 6. Preparation of an anion receptor (6) [Reaction Scheme 9]

1,3-Diaminopropane N,N,N,N-Tetra(trinuoromcthanesulfonyl)-propane-l,3-tliamine

3.7g of 1,3-diaminopropane and 24.3g of triethylamine were mixed with 100ml of chloroform at -25⁰C, and 62.1g of triflic anhydride was added dropwise to the mixture under nitrogen atmosphere. The solution was stirred at room temperature for one hour and

added to distilled water. An organic layer was separated and washed three times with distilled water. Then, an organic extract was dried over anhydrous MgSO₄ and filtered. The chloroform was removed under vacuum to yield N,N,N,N- Tetra(trifluoromethanesulfonyl)-propane-l,3-diamine (1,3-propane-di-TFSI) (see the Reaction Scheme 9). It was confirmed that quantitative substitution reaction was processed in view of disappearing N-H stretch absorption band at 3, 300-3, 500cm^"1 in IR spectrum.

¹H NMR (300MHz, CDCl₃): ppm 2.26-2.32 (m, 2H), 3.98-4.00 (m, 4H); ¹⁹F NMR (CDCl₃): ppm -72.6 (s).

Example 7. Preparation of an anion receptor (7) [Reaction Scheme 10]

ClCN H H ClCN, (C,H<),N ^NC\ /^CN

-CH₂CHCH₂NH₂Cl -(C₂H_S)₃NHC1 ^{Nc CN}

N,N-Dicyano-propane-l ,3-diamide N,N.N,N-Tetracya«o-propa,,e-l .3-diamine

As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 37.06g of 1,3-diaminopropane (0.5mol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain

N,N,N,N-Tetracyano-propane-l , 3-diamine (1,3-propane-di-DCN) (see Reaction Scheme

10).

¹H NMR (300MHz, CDCl₃): ppm 1.78 (m, 2H), 2.55 (m, 4H); ¹³C NMR (CDCl₃): ppm 25.1, 38.4, 116.7.

Example 8. Preparation of an anion receptor (8) [Reaction Scheme 1 1]

N,N,N,N-Tetrafluoro-propane-l ,3-diamine

14.8g of 1,3-propane-di-iodide (50mmol) and 6.7Og of tetrafluorohydrazine (64mmol) were reacted as Example 3 to obtain N,N,N,N-Tetrafluoro-propane-l,3-diamine (1 ,3-propane-di-DFA) (see Reaction Scheme 1 1).

¹H NMR (300MHz, CDCl₃): ppm 1.90 (m, 2H), 3.31 (m, 4H); ¹³C NMR (CDCl₃): ppm 12.5, 53.7; ¹⁹F NMR (CDCl₃): ppm -53.5 (s). Example 9. Preparation of an anion receptor (9) [Reaction Scheme 12]

N,N,N ^-Tetrachloro-propane- 1 ,3-diamine

40g of N-chlorosuccinimide (0.3mol) and 3.7g of 1,3-diaminopropane (0.05mol) were reacted as Example 4 to obtain N,N,N,N-Tetrachloro-propane- 1,3 -diamine (1,3- propane-di-DCA) (see Reaction Scheme 12).

^]R NMR (300MHz, CDCl₃): ppm 1.73 (m, 2H), 3.33 (m, 4H); ¹³C NMR (CDCl₃): ppm 10.9, 51.3 Example 10. Preparation of an anion receptor (10)

[Reaction Scheme 13]

.V- { 3-[Bis-(2.2,2-tπ fluoro-acetyl )-amino]-propyl [ - 2.2.2-trifluoiO-W-(2.2.2-lrifluoiO-acetyl)-acetamide

0.154g of 1,3-diaminopropane (2.08mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.1 lmmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-{3-[Bis-(2,2,2- trifluoro-acetyl)-amino]-propyl}-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (1 ,3-

propane-di-DTFAC) (see Reaction Scheme 13).

¹H NMR (300MHz, CDCl₃): ppm 1.40-1.59 (m, 2H), 3.33(m, 4H); ¹³C NMR

(CDCl₃): ppm 25.9, 36.3, 127.3, 165.4. Example 11. Preparation of an anion receptor (11)

[Reaction Scheme 14]

N,N-Di(trifluoromethanesulfonyl)butylamine

7.3g of butylamine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted under the same condition of Example 6 to obtain N,N- Di(trifluoromethanesulfonyl)butylamine (butyl-TFSI) (see Reaction Scheme 14). It was confirmed that quantitative substitution reaction was processed in view of disappearing N- H stretch absorption band at 3,300-3,50OCm^"1 in IR spectrum. ¹H NMR (300MHz, CDCl₃): 0.73 (t, 3H), 1.00-1.20 (m, 2H), 1.50-1.60 (m, 2H),

3.70 (t, 2H); ¹³C NMR (300MHz, CDCl₃): 13.7, 20.2, 29.4, 36.5, 145.8 ; ¹⁹F NMR (300MHz, CDCl₃): ppm - 73.68 (s). Example 12. Preparation of an anion receptor (12) [Reaction Scheme 15]

Butyl-cyanamide N,N-Dicyanobutylamine

As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 73.14g of butylamine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N,N- Dicyanobutylamine (butyl-DCN) (see Reaction Scheme 15).

¹H NMR (300MHz, CDCl₃): ppm 0.96 (t, 3H), 1.13-1.33 (m, 2H), 1.50-1.60 (m, 2H), 2.65 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.5, 19.8, 32.1, 45.2, 116.7.

Example 13. Preparation of an anion receptor (13) [Reaction Scheme 16]

N,N-Difluorobutylamine

18.4g of butyl iodide (lOOmmol) and 6.7Og of tetrafluorohydrazine (64mmol) were reacted as Example 3 to obtain N,N-Difluorobutylamine (butyl-DFA) (see Reaction Scheme 16).

¹H NMR (300MHz, CDCl₃): ppm 0.86 (t, 3H), 1.03-1.23 (m, 2H), 1.40-1.50 (m, 2H), 2.55 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.6, 21.3, 24.3, 56.2; ¹⁹F NMR (CDCl₃): ppm - 53.8 (s). Example 14. Preparation of an anion receptor (14) [Reaction Scheme 17]

N,N-Dichlorobutylamine

4Og of N-chlorosuccinimide (0.3mol) and 7.3g of butylamine (O.lmol) were reacted as Example 4 to obtain N,N-Dichlorobutylamine (butyl-DCA) (see Reaction Scheme 17). ¹H NMR (300MHz, CDCl₃): ppm 0.54 (t, 3H), 0.71 -0.91 (m, 2H), 1.08-1.18 (m,

2H), 2.23 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.3, 18.3, 25.8, 57.6 Example 15. Preparation of an anion receptor (15)

[Reaction Scheme 18]

Λ'-Buty)-2,2,2-trifluoro-Λ'-(2.2,2-tπfluoiO-acetyl)-acetam>de

0.3Og of butylamine (4.16mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2, 6-di-tert-butyl-4-methyl -pyridine (3.1 lmmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-Butyl-2,2,2-trifluoro-N- (2,2,2-trifluoro-acetyl)-acetamide (butyl-DTFAC) (see Reaction Scheme 18).

¹H NMR (300MHz, CDCl₃): ppm 0.35 (t, 3H), 0.723 (m, 2H), 0.94 (m, 2H), 2.87 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.7, 20.2, 31.2, 40.5, 122.6, 168.9. Example 16. Preparation of an anion receptor (16) [Reaction Scheme 19]

3

N,N-Di(trifluoromethanesulfonyl)octylamine

12.9g of octylamine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted under the same condition of Example 6 to obtain N,N- Di(trifluoromethanesulfonyl)octylamine (Octyl-TFSI) (see Reaction Scheme 19).

¹H NMR (300MHz, CDCl₃): 0.85-0.88 (t, 3H), 1.26-1.29 (m, 10H), 1.78 (m, 2H), 3.89(t, 2H); ¹⁹F NMR (300MHz, CDCl₃): ppm - 72.43 (s). Example 17. Preparation of an anion receptor (17) [Reaction Scheme 20]

Octyl-cyanamide N ,N-Dιcyanooctvlamine

As the same method of Example 2, the first reaction was performed by using 86g of

cyanogen chloride (1.4mol) and 129g of octylamine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N₅N-

Dicyanooctylamine (octyl-DCN) (see Reaction Scheme 20).

¹H NMR (300MHz, CDCl₃): ppm 0.95 (t, 3H), 1.28-1.31 (m, 10H), 1.57 (m, 2H), 2.68 (t, 2H); ¹³C NMR (CDCl₃): ppm 14.0, 23.1, 27.8, 30.0, 32.7, 44.6, 1 17.8. Example 18. Preparation of an anion receptor (18) [Reaction Scheme 21]

J Q N,N-Difluorooctylamine

24.1g of hexadecyl iodide (lOOmmol) and 6.7Og of tetrafluorohydrazine (64mmol) were reacted as Example 3 to obtain N,N-Difluorooctylamine (octyl-DFA) (see Reaction Scheme 21).

¹H NMR (300MHz, CDCl₃): ppm 0.84 (t, 3H), 1.29-1.31 (m, 8H), 1.33 (m, 2H), 15 1.55 (m, 2H), 2.65 (t, 2H); ¹⁹F NMR (CDCl₃): ppm -53.4 (s). Example 19. Preparation of an anion receptor (19) [Reaction Scheme 22]

N.N-Dichlorooctylamme

4Og of N-chlorosuccinimide (0.3mol) and 12.9g of octylamine (O.lmol) were reacted as Example 4 to obtain N,N-Dichlorooctylamine (octyl-DCA) (see Reaction

Scheme 22).

¹H NMR (300MHz, CDCl₃): ppm 0.58 (t, 3H), 0.92-0.98 (m, 8H), 1.03 (m, 2H), 1.26 (m, 2H), 2.48 (t, 2H); ¹³C NMR (CDCl₃): ppm 14.2, 24.1, 24.5, 26.8, 30.3, 30.5, 32.8, 60.2.

Example 20. Preparation of an anion receptor (20) [Reaction Scheme 23]

/V-Octyl-2,2,2-trifluoro-Λ'-(2,2,2-trifluoro-acetyl)-acetamide

0.54g of octylamine (4.16mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.1 lmmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-Octyl-2,2,2-trifluoro-N-

(2,2,2-trifluoro-acetyl)-acetamide (octyl-DTFAC) (see Reaction Scheme 23).

¹H NMR (300MHz, CDCl₃): ppm 0.48 (t, 3H), 0.82-0.88 (m, 8H), 0.97(m, 2H), 1.06 (m, 2H), 2.29 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.7, 22.1 , 26.4, 28.4, 29.8, 30.1 , 39.8, 120.6, 167.9

Example 21. Preparation of an anion receptor (21) [Reaction Scheme 24]

H₂N

1 ,8-Diaminooctane N,N,N,N-Tetra(trifluoromethanesulfonyl)-octane-l ,8-diamine

14.4g of 1 ,8-diaminooctane, 24.3g of tri ethyl amine and 62.1 g of triflic anhydride were reacted under the same condition of Example 6 to obtain N,N,N,N-

Tetra(trifluoromethanesulfonyl)-octane- 1 ,8-diamine (1 ,8-octane-di-TFSI) (yield: 67%, see Reaction Scheme 24). It was confirmed that quantitative substitution reaction was processed in view of disappearing N-H stretch absorption band at 3,300~3, 500cm^"1 in IR spectrum.

¹H NMR (300MHz, CDCl₃): ppm 1.31 (m, 8H), 1.53 (m, 4H), 3.87-3.91 (t, 4H); ¹⁹F NMR (CDCl₃): ppm -72.3 (s). Example 22. Preparation of an anion receptor (22) [Reaction Scheme 25]

H_2Nj Λ ClCN _^ Jj _/J _XN ClCN. (C₂H,hN ^NC> J ^l ™

₄ ^NH-CH₂CHCH₂NH₂C. ^NC ^ J₄ K -(C₂Hs)₃NHCI ^NC T J ₄%_N

I Q N,N-Dicyano-octane-l ,8-diamide N,N,N,N-Tetracyano-octane-l ,8-diamine

As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 72g of 1 ,8-diaminooctane (0.5mol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N,N,N,N-Tetracyano-octane-l,8-diamine (1,8-octane-di-DCN) (see Reaction Scheme 25). 15 ¹H NMR (300MHz, CDCl₃): ppm 1.29 (m, 8H), 1.55 (m, 4H), 2.65 (m, 4H); ¹³C

NMR (CDCl₃): ppm 26.4, 27.8, 30.0, 44.6, 1 18.7 Example 23. Preparation of an anion receptor (23) [Reaction Scheme 26]

N.N.N.N-Tctrafluoro-octane-US-dianiine

20 18.3g of 1,8-octane-di-iodide (50mmol) and 6.7Og of tetrafluorohydrazine

(64mmol) were reacted as Example 3 to obtain N,N,N,N-Tetrafluoro-octane-l ,8-diamine (1,8-octane-di-DFA) (see Reaction Scheme 26).

¹H NMR (300MHz, CDCl₃): ppm 1.30 (m, 8H), 1.56(m, 4H), 2.67 (m, 4H); ¹³C NMR (CDCl₃): ppm 20.8, 27.4, 30.0, 55.7; ¹⁹F NMR (CDCl₃): ppm -53.5 (s).

Example 24. Preparation of an anion receptor (24)

[Reaction Scheme 27]

N,N,N, N-Tetrachloro-octane- 1 ,8-diamine

4Og of N-chlorosuccinimide (0.3mol) and 7.2g of 1 ,8-diaminooctane (0.05mol) were reacted as Example 4 to obtain N,N,N,N-Tetrachloro-octane-l,8-diamine (1,8-octane- di-DCA) (see Reaction Scheme 27). ¹H NMR (300MHz, CDCl₃): ppm 1.31 (m, 8H), 1.61 (m, 4H), 2.73 (m, 4H); ¹³C

NMR (CDCl₃): ppm 24.2, 26.4, 30.0, 59.8

Example 25. Preparation of an anion receptor (25) [Reaction Scheme 28]

yV-{ 8-[Bis-(2,2,2-lπfluoro-acetyl)-amino]-octylj -2, 2,2-ti'ifluoro-Λ'-(2,2,2-trifluoro-acetyl)-aceta?nide 0.3Og of 1 ,8-diaminooctane (2.08mmol), 0.49mL of anhydrous trifluoroacetic acid

(3.2mmol) and 0.637g of 2, 6-di-tert-butyl-4-methyl -pyridine (3.1 lmmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-{8-[Bis-(2,2,2-trifluoro- acetyl)-amino]-octyl}-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (1,8-octane-di- DTFAC) (see Reaction Scheme 28). ¹H NMR (300MHz, CDCl₃): ppm 1.30-1.49 (m, 8H), 1.56(m, 4H), 3.33(m, 4H);

¹³C NMR (CDCl₃): ppm 29.9, 30.3, 27.6, 41.2, 127.8, 167.4. Example 26. Preparation of an anion receptor (26) [Reaction Scheme 29]

ζ N,N-Di(trifluoromethanesulfonyl)hexadecylamine

24.1g of hexadecylamine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted under the same condition of Example 6 to obtain N₅N- Di(trifluoromethanesulfonyl)hexadecylamine (Hexadecyl-TFSI) (see Reaction Scheme 29).

¹H NMR (300MHz, CDCl₃): 0.86 (t, 3H), 1.26-1.29 (m, 24H), 1.53 (m, 2H), 1.78 0 (m, 2H), 3.89(t, 2H); ¹⁹F NMR (300MHz, CDCl₃): ppm - 72.46 (s). Example 27. Preparation of an anion receptor (27) [Reaction Scheme 30]

r _{1 Ku} ^C1CN vf ^Λ J^ ClCN, (C₂H₅J₃N r 1 _N-^/CN

U ^i ^NH ₂ . r j^ CN ^■ y ^N\_CN

I h -CH₂CHCH₂NH₂Cl ^{L J v} -(C₂H₅)₃NHC1 I π

Hexadecyl-cyanamide N,N-Dicyanohexadecylamine

As the same method of Example 2, the first reaction was performed by using 86g of 5 cyanogen chloride (1.4mol) and 241g of hexadecylamine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N₅N- Dicyanohexadecylamine (hexadecyl-DCN) (see Reaction Scheme 30).

¹H NMR (300MHz, CDCl₃): ppm 0.95 (t, 3H), 1.28-1.31 (m, 24H), 1.32 (m, 2H), 1.57 (m, 2H), 2.68 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.9, 22.1, 26.5, 28.2, 30.1 , 44.8, 1 17.8. 0 Example 28. Preparation of an anion receptor (28) [Reaction Scheme 31 ]

N,N-Difluorohexadecylamine

35.2g of hexadecyl iodide (lOOmmol) and 6.7Og of tetrafluorohydrazine (64mmol)

were reacted as Example 3 to obtain N,N-Difluorohexadecylamine (hexadecyl-DFA) (see Reaction Scheme 31).

¹H NMR (300MHz, CDCl₃): ppm 0.84 (t, 3H), 1.19-1.21 (m, 24H), 1.23 (m, 2H), 1.48 (m, 2H), 2.59 (t, 2H); ¹⁹F NMR (CDCl₃): ppm 53.4 (s). Example 29. Preparation of an anion receptor (29) [Reaction Scheme 32]

N.N-Dichlorohexadecylamine 4Og of N-chlorosuccinimide (0.3mol) and 24.1g of hexadecylamine (0.1 mol) were reacted as Example 4 to obtain N,N-Dichlorohexadecylamine (hexadecyl-DCA) (see

Reaction Scheme 32).

¹H NMR (300MHz, CDCl₃): ppm 0.58 (t, 3H), 0.92-0.98 (m, 24H), 1.03 (m, 2H),

1.26 (m, 2H), 2.48 (t, 2H); ¹³C NMR (CDCl₃): ppm 14.2, 24.1 , 24.5, 26.8, 30.3, 30.5, 32.8, 60.2.

Example 30. Preparation of an anion receptor (30)

[Reaction Scheme 33]

yV-Hexadecy]-2,2,2-frifluoro-Λ'-(2,2,2-trifluoro-acctyl)-acetamide 1.1 Ig of hexadecylamine (4.16mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.1 lmmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-Hexadecyl-2,2,2-trifluoro- N-(2,2,2-trifluoro-acetyl)-acetamide (hexadecyl-DTFAC) (see Reaction Scheme 33).

¹H NMR (300MHz, CDCl₃): ppm 0.48 (t, 3H), 0.82-0.88 (m, 24H), 0.97(m, 2H),

1.06 (m, 2H), 2.29 (t, 2H); ¹³C NMR (CDCl₃): ppm 13.7, 22.1 , 26.4, 28.4, 29.8, 30.1, 39.8, 120.6, 167.9.

Example 31. Manufacture of Ionic Conductive Thin Film (1) 0.25g of the anion receptor 1,3-propane-di-TFSI obtained from Example 6 was mixed with 0.25g of bisphenol A ethoxylate dimethacrylate (Aldrich Co., Mw=I, 700, "Bis-15m") of the Formula 3 used as a crosslinking agent, 0.5g of poly(ethylene glycol)

dimethyl ether (Mw=350, "PEGDME 300"), and 0.3943g of lithium trifluoromethane sulfonimide (Li(CF₃SO₂)₂N). To this mixture, 0.0075g of dimethoxyphenyl acetophenone (DMPA) was added. Then, the resulting solution was coated onto a conductive glass substrate and exposed to 350nm UV rays for 30 minutes under nitrogen atmosphere. With this radiation, a solid polymer electrolyte was prepared. Example 32. Manufacture of Ionic Conductive Thin Film (2)

0.175g of the anion receptor butyl-TFSI obtained from Example 11 was mixed with 0.25g of bisphenol A ethoxylate dimethacrylate (Aldrich Co., Mw=l,700, "Bis- 15m") of the Formula 3 used as a crosslinking agent and 0.095g of lithium trifluoromethane sulfonimide (Li(CF₃SCh)₂N). To this mixture, 0.0023g of dimethoxyphenyl acetophenone (DMPA) was added. Then, the resulting solution was coated onto a conductive glass substrate and exposed to 350nm UV rays for 30 minutes under nitrogen atmosphere. With this radiation, a solid polymer electrolyte was prepared.

Examples 33 - 34. Manufacture of Conductive Thin Film (3 - 4)

The same procedure of Example 32 was repeated, with the exception that compositions of compounds used are as shown in the following Table 1 to prepare a solid polymer electrolyte. Comparative Example 1. Manufacture of Film without Anion Receptors

The same procedure of Example 32 was repeated using the compositions of compounds shown in the following Table 1 to prepare a solid polymer electrolyte. As

shown in Table 1 , polymer electrolyte of Comparative Example does not contain an anion receptor. [Table 1]

Experimental Example 1. Ionic Conductivity Test (1) Ionic conductivity of the solid polymer electrolyte film obtained from the Example 31 using 1,3-Propane-di-TFSI prepared from Example 6 was measured as follows.

First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium-copper foil, photo-hardened, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance. To manufacture the band shaped electrodes, masking tapes having a width between 0.5mm and 2mm were adhered to the center of a conductive glass (ITO) at intervals of 0.5 - 2mm, etched in an etching solution, washed and dried. Ionic conductivity of the solid polymer electrolyte film depending on temperature is shown in FIG. 1. Experimental Example 2. Ionic Conductivity Test (2)

Ionic conductivities of the solid polymer electrolyte films obtained from the Examples 32-34 using Butyl-TFSI prepared from Example 11 were measured. The test was carried out using the same procedure described in Experimental Example 1. Ionic conductivity measurement results at a temperature of 3O⁰C are shown in the following Table 2 and FIG. 2. [Table 2]

These results prove that ionic conductivity improves proportionally to the concentration of anion receptors.

Example 35. Manufacture of Cell Using Polymer Electrolyte with Anion Receptors 0.2g of the anion receptor AlIy-TFSA obtained from Example 1 was mixed with

0.133g of bisphenol A ethoxylate diacrylate (Aldrich Co., Mw=688, "Bis-15m") of the Formula 3 used as a crosslinking agent, 0.667g of an organic solvent EC/DMC/DEC (1: 1 :1, IM LiPF₆) and 0.004g of t-butyl peroxypivalate (LUPEROX 1 1M70). A polyethylene separator impregnated with the above mixture solution was inserted between a lithium cathode and a nickel anode and sealed to assemble a cell, then thermally cured in

oven of 80 ^°C for 2 hours. Typical 2-electrode electrochemical cell was used. A nickel

metal was used as a working electrode and a lithium metal was used as reference electrode and counter electrode. A test cell was assembled in glove box and vacuum-sealed in polyethylene bags laminated with metals. Comparative Example 2. Manufacture of Cell Using Polymer Electrolyte without Anion Receptors

0.133g of bisphenol A ethoxylate diacrylate (Aldrich Co., Mw=688, "Bis-15m") of the Formula 3, 0.867g of an organic solvent EC/DMC/DEC (1:1 :1, IM LiPF₆) and 0.004g of t-butyl peroxypivalate (LUPEROX 1 1M70) were mixed and the cell was prepared by the same procedure described in Example 35.

Experimental Example 3. Electrochemical Stability Test

Electrochemical stabilities of the cell prepared from Example 35 and Comparative Example 2 were measured by cyclic voltammography and linear sweep voltammography using Potentiostat (EG&G, model 270A) and the results were shown in FIG. 3. CV was measured in a speed of 5 mV/sec, in a range of -0.5V~6.0V at a temperature of 30 ^°C . The

cell prepared using electrolyte not containing anion receptor deteriorated at electrical potential around 4.0V whereas the cell prepared using electrolyte containing anion receptor was stable without deteriorating at 4.6V of oxidation potential and represented reversible oxidation-reduction reaction of lithium to the working electrode.

Example 36. Manufacture of Cell Using Liquid Electrolyte with Anion Receptors

O.Olg of the anion receptor Octyl-4TFSI obtained from Example 16 was mixed with LOg of an organic solvent EC/DMC/EMC (1:1 :1, IM LiPF₆). A polypropylene separator impregnated with the above solution was inserted between a LiCoO₂ cathode and a graphite carbon anode in a dry room (humidity below 3%) and vacuum-sealed to assemble a cell. The LiCoO₂ cathode was prepared by coating an aluminum foil with a mixture of 94wt% LiCoO₂ (manufactured by Nippon Chemical Industry), 3wt% of acetylene black, and 3wt% of polyvinylidenfluoride (PVDF). Comparative Example 3. Manufacture of Cell Using Liquid Electrolyte without Anion Receptors

The same procedure described in Example 36 was repeated, with the exception that the separator impregnated with an organic solvent EC/DMC/DEC (1 :1 :1 , IM LiPF₆) only was inserted between a LiCoO₂ cathode and a graphite carbon anode. Experimental Example 4. Cell Lithium Cycling Performance and Efficiency Test Lithium cycling performance and efficiency of cells manufactured in Example 36 of the present invention and Comparative Example 3 were tested at room temperature using Maccor 4000. Charging and discharging were carried out to 1 C, respectively. The cells were charged and discharged anywhere between 3.0V and 4.2V at a predetermined current density of 0.6mA/cm² (charging) and 1.5mA/cm² (discharging) with respect to a

LiCoO₂ counter electrode.

FlG. 4 graphically shows a comparison between discharge capacities with respect

to the number of cycling of cells manufactured using electrolytes inclusive of the anion receptor Octyl-4TFSI and those of cells manufactured using electrolytes exclusive of the anion receptor. As shown in FIG. 4, it turned out that the cells manufactured using electrolytes of the anion receptor Octyl-4TFSI exhibited higher capacity.

Industrial Applicability As described above, the novel anion receptor of the present invention can be used as an additive to enhance lithium cycling performance and efficiency of liquid electrolytes for high capacity lithium-ion batteries and cells. In addition, the polymer electrolytes containing the novel anion receptor offer substantially enhanced ionic conductivities and electrochemical stabilities at room temperature, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all kinds of electronic equipments, e.g., camcorders, and large capacity lithium polymer secondary cells used in power storage systems for power equalization and electric vehicles.

Claims

What is claimed is:1. A compound represented by the Formula 1 :

[Formula 1]

R₃ represents a hydrogen atom or a methyl group;

A

X is a hydrogen atom, a methyl group, ^CH2 or ^R2 ;

R₃ and X do not simultaneously represent a hydrogen atom;

n is an integer from 0 to 20.

2. The compound of claim 1 is selected from the group consisting of:

N-Allyltrifluoromethanesulfonarnide, N,N-Dicyanoallylamine,

N,N-Difluoroallylamine,

N,N-Dichloroallylamine,

N-allyl-2,2,2-trifluoro-N-trifluoroacetyl-acetamide,

N,N,N,N-Tetra(trifluoromethanesulfonyl)-propane-l ,3-di amine,

N,N,N,N-Tetracyano-propane-l ,3-diamine,

N,N,N,N-Tetrafluoro-propane-l ,3-diamine, N,N,N,N-Tetrachloro-propane- 1,3 -diamine,

N-{3-[Bis-(2,2,2-trifluoro-acetyl)-amino]-propyl}-2,2,2-trifluoro-N-(2,2,2-

trifluoro-acetyl)-acetamide,

N,N-Di(trifluoromethanesulfonyl)butylamine, N,N-Dicyanobutylamine,

N,N-Difluorobutylamine,

N,N-Dichlorobutylamine,

N-Butyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide,

N,N-Di(trifluoromethanesulfonyl)octylamine, N,N-Dicyanooctylamine,

N,N-Difluorooctylamine,

N,N-Dichlorooctylamine,

N-Octyl-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide,

N,N,N,N-Tetra(trifluoromethanesulfonyl)-octane- 1 ,8-diamine, N,N,N,N-Tetracyano-octane-l ,8-diamine,

N,N,N,N-Tetrafluoro-octane- 1 ,8-diamine,

N,N,N,N-Tetrachloro-octane-l,8-diamine,

N-{8-[Bis-(2,2,2-trifluoro-acetyl)-amino]-octyl}-2,2,2-trifluoro-N-(2,2,2-trifluoro- acetyl)-acetamide, N,N-Di(trifluoromethanesulfonyl)hexadecylamine,

N,N-Dicyanohexadecylamine,

N,N-Difluorohexadecylamine,

N,N-Dichlorohexadecylamine and

N-Hexadecyl-2,2,2-trifluoro-N-(2,2,2-trifluoiO-acetyl)-acetaniide.

3. An electrolyte comprising the compound of claim 1.

4. The electrolyte of claim 3, wherein the electrolyte is selected from the group consisting of nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.

5. A nonaqueous liquid electrolyte, comprising: (i) an anion receptor of the compound of claim 1 ; (ii) a nonaqueous solvent; and

(iii) an alkali metal ion containing substance.

6. A gel polymer electrolyte, comprising: (i) an anion receptor of the compound of claim 1; (ii) a polymer support;

(iii) a nonaqueous solvent; and

(iv) an alkali metal ion containing substance.

7. A solid polymer electrolyte, comprising: (i) an anion receptor of the compound of claim 1 ;

(ii) a polymer compound selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.

8. The electrolyte of claim 7, wherein the solid polymer electrolyte further comprises the substance selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof .

9. The electrolyte of one of claims 5 to 8, wherein the nonaqueous solvent is selected from the group consisting of: ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-l ,3-dioxolane,

1,3-dioxolane, 1 ,2-dimethoxyethane, dimethoxym ethane, γ-butyrolactone, methyl formate,

sulforane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2-pyrrolidinone and mixtures thereof.

10. The electrolyte of one of claims 5 to 7, wherein the alkali metal ion containing substance is selected from the group consisting of LiSO₃CF₃, LiCOOC₂F₅, LiN(SO₂CF₃)₂, LiC(SO₂CF₃)₃, LiClO₄, LiAsF₆, LiBF₄, LiPF₆, LiSbF₆, LiI, LiBr, LiCl, and a mixture thereof.

1 1. The electrolyte of claim 6, wherein the polymer support is polyacrylonitrile type polymer or polyvinylidenfluoride-hexafiuoropropylene type polymer.

12. The electrolyte of claim 7, wherein the polymer selected from the group consisting of net-shaped, comb-shaped and branched polymer compounds are flexible inorganic polymers or linear polyethers.

13. The electrolyte of claim 7, wherein the crosslinkable polymer is a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl.

14. The electrolyte of claim 12 or claim 13, wherein the flexible inorganic polymer is polysiloxane or polyphosphagen, and the linear polyether is a polyalkylene oxide.

15. The electrolyte of claim 8, wherein the polyalkyleneglycol dialkylether is selected from the group consisting of: polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated with dibutylether.

16. The solid polymer electrolyte of claim 7, wherein the electrolyte further comprises a curing initiator when the electrolyte contains a crosslinkable polymer compound.

17. The electrolyte of claim 16, wherein the curing initiator is selected from the group consisting of: a photocuring initiator, a heat-curing initiator, and a mixture thereof.

18. The electrolyte of claim 17, wherein the photocuring initiator is selected from the group consisting of: dimethoxyphenyl acetophenone (DMPA), t-

butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl

ether, benzoin phenyl ether, α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-

dichloroacetophenone, 2-hydroxy-2-methyl- 1 -phenylpropane- 1 -on, 1 -hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone, and a mixture thereof; and the heat-curing initiator is selected from the group consisting of: azoisobutyrontrile compounds, peroxide compounds and mixtures thereof.

19. The electrolyte of one of claims 5 to 7, comprising 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.

20. The electrolyte of claim 6, comprising 5 - 40 parts by weight of the polymer support.

21. The electrolyte of claim 7, comprising 10 - 95 parts by weight of a polymer compound selected from the group consisting of net-shaped, comb-shaped and branched polymer, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator.

22. The electrolyte of claim 8, comprising 10 - 50 parts by weight of the substance selected from the group consisting of polyalkyleneglycol dialkylether, a

nonaqueous solvent and a mixture thereof.

23. An electrochemical cell comprising an anode, a cathode and the electrolyte

of claim 3.

24. The electrochemical cell of claim 23, wherein the anode is made of a material selected from the group that consists of lithium; lithium alloys; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds; lithium metal sulfide intercalation compounds; mixtures thereof;

and mixtures of these and alkali metals, and wherein, the cathode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.

25. The electrochemical cell of claim 24, wherein the transition metal oxides is selected from the group consisting of Li₂. _SV₆Oi₃, LiL₂V₂O₅, LiCoO₂, LiNiO₂, LiMn₂O₄, LiMnO₂, and LiNi_{] -x}M_xO₂ (wherein M is Co, Mg, Al or Ti); wherein the transition metal chalcogenides is selected from the group consisting of: LiNbSe₃, LiTiS₂, and LiMoS₂; wherein the organic disulfide redox polymers are prepared by reversible electrochemical dimerization/division or polymerization/dissociation; and wherein the organic disulfide/polyaniline complexes are mixtures of polyaniline and 2,5-dimercapto-l,3,4-thiadiazole.

26. A gel polymer electrolyte film manufactured using the gel polymer electrolyte of claim 6.

27. A solid polymer electrolyte film manufactured using the solid polymer electrolyte of claim 7.