WO2007126262A1 - Anion receptor, and electrolyte using the same - Google Patents
Anion receptor, and electrolyte using the same Download PDFInfo
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- WO2007126262A1 WO2007126262A1 PCT/KR2007/002080 KR2007002080W WO2007126262A1 WO 2007126262 A1 WO2007126262 A1 WO 2007126262A1 KR 2007002080 W KR2007002080 W KR 2007002080W WO 2007126262 A1 WO2007126262 A1 WO 2007126262A1
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- 0 *c1cc(N(*)*)n[n]1* Chemical compound *c1cc(N(*)*)n[n]1* 0.000 description 1
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Abstract
Disclosed is a novel anion receptor and electrolytes containing the same. A novel anion receptor is an aromatic hydrocarbon compound having an amine substituted with electron withdrawing groups. 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 an aromatic hydrocarbon compound having an amine substituted with electron withdrawing groups 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. Soα, 143 (1996) 3825, 147 (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
(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 (J. Power Sources, 104 (2002) 260). Due to high electron density, aza-ethers are promptly attached by PF5. 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. Armand 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 10" 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, hi 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. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6854) 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, network-structured 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 lO^-lO"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 crosslinkmg agent having a siloxane based main chain and a PEO side branch, the ionic conductivity was increased to δxlO"4 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 (Prog. Solid St. 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 an aromatic hydrocarbon compound having an amine substituted with electron withdrawing groups 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 an aromatic hydrocarbon compound having an amine substituted with electron withdrawing groups: [Formula 1]
R3, R4, R5, R6 and R7 each independently represents a hydrogen atom, Ci~Cio alkyl, vinyl, allyl, phenyl, an electron withdrawing functional group selected from the group
consisting of -CF3, -SO2CF3, -COCF3 and -SO2CN, or
R8 and R9 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;
X is carbon atom or nitrogen atom;
Y is carbon atom, nitrogen atom, oxygen atom or sulfur atom; R6 is not present in the structure when Y is oxygen atom or sulfur atom; n is an integer from O to 20; and q is 0 or 1.
In the compound of the Formula 1, preferably, at least one of R1 and R2 are not - SO2CF3 when R3, R4, R6 and R7 are hydrogen and R5 is hydrogen or vinyl group, and Ri and R2 are not simultaneously -Cl when at least one of X and Y are nitrogen atom.
The compound of the Formula 1 functions as an anion receptor in an electrolyte and preferred examples of the compound include:
(3,5-Bis-trifluoromethyl-phenyl)-di(trifluoromethanesulfonyl)-amine;
(3,5-Bis-trifϊuoromethyl-phenyl)-dicyano-amine; (3 ,5-Bis-trifluoromethyl-phenyl)-difluoro-amine;
(3,5-Bis-trifluoromethyl-phenyl)-dichloro-amine;
N-(3,5-Bis-trifluoromethyl-phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)- acetamide;
(2,4-Difluoro-phenyl)-di(trifluoromethanesulfonyl)-amine; (2,4-Difluoro-phenyl)-dicyano-amine;
(2,4-Difluoro-phenyl)-difluoro-amine;
(2,4-Difluoro-phenyl)-dichloro-amine;
N-(2,4-Difluoro-phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide;
N,N,N,N-Tetra(trifluoromemanesulfonyl)-pyridine-2,6-diamine;
N,N,N,N-Tetracyano-pyridine-2,6-diamine;
N,N,N,N-Tetrachloro-pyridine-2,6-diamine;
N-{6-[Bis-(2,2,2-trifluoro-acetyl)-amino]-pyridin-2-yl}-2,2,2-trifluoro-N-(2,2,2-
trifluoro-acetyl)-acetamide; N,N,N'5N',N",N"-Hexa(trifluoromethanesulfonyl)-benzene- 1,3,5 -triamine;
N,N,N,N,N,N-Hexacyano-benzene- 1 ,3 ,5-triamine;
N,N,N,N,N,N-Hexachloro-benzenee-l,3,5-triamine;
N-{3,5-Bis-[bis-(2,2,2-trifluoro-acetyl)-amino]-phenyl}-2,2,2-trifluoro-N-(2,2,2- trifluoro-acetyl)-acetamide; Di(trifluoromethanesulfonyl)-(4-vinyl-phenyl)-amine;
N,N-Dicyano-(4-vinyl-phenyl)-amine;
Dichloro-(4-vinyl-phenyl)-amine;
2,2,2-Trifluoro-N-(2,2,2-trifluoro-acetyl)-N-(4-vinyl-phenyl)-acetamide;
4-Hexyl-phenyl-di(trifluoromethanesulfonyl)-amine; (4-Hexyl-phenyl) -dicyano-amine;
(4-Hexyl-phenyl)-dichloro-amine;
2,2,2-Trifluoro-N-(4-hexyl-phenyl)-N-(2,2,2-trifluoro-acetyl)-acetamide;
Di(trifluoromethanesulfonyl)-pyrimidin-2-yl-amine;
Dicyano-pyrimidJn-2-yl-amine; Dichloro-pyrimidin-2-yl-amine;
2,2,2-Trifluoro-N-pyrimidin-2-yl-N-(2,2,2-trifluoro-acetyl)-acetamide;
N,N',N"-Trichloro-N,N',N"-tri(trifluoromethanesulfonyl)-[l,3,5]triazine-2,4,6- triamine;
N,Nt,N"-Trichloro-N,Nt,N"-tricyano-[l,3,5]triazine-2,4,6-triamine;
N?N,N',Nt,N",N"-Hexachloro-[l,3,5]triazine-2,4,6-triamine;
N-{4,6-Bis-[chloro-(2,2,2-trifluoro-acetyl)-amino]-[l,3,5]triazin-2-yl}-2,2,2-
trifluoro-N-chloro-acetaniide;
(5-Methyl- 1 -trifluoromethanesulfonyl- 1 H-pyrazol-3 -yl)- di(trifluoromethanesulfonyl)-amine;
(5-Methyl- 1 -cyano- 1 H-pyrazol-3 -yl)-dicyano-amine;
(5 -Methyl- 1 -chloro- 1 H-pyrazol-3 -yl)-dichloro-amine;
2,2,2-Trifluoro-N-[5-methyl-l-(2,2,2-trifluoro-acetyl)-lH-pyrazol-3-yl]-N-(2,2,2- trifluoro-acetyl)-acetamide; Di(trifluoromethanesulfonyl)-thiazol-2-yl-amine;
Dicyano-thiazol-2-yl-amine;
Dichloro-thiazol-2-yl-amine;
2,2,2-Trifluoro-N-thiazol-2-yl-N-(2,2,2-trifluoro-acetyl)-acetamide;
1 -Trifluoromethanesulfonyl-2-phenyl- 1 H-imidazole; l-Cyano-2-phenyl-l H-imidazole; l-Chloro-2-phenyl-l H-imidazole; or
2,2,2-Trifluoro- 1 - (2-phenyl-imidazol- 1 -yl)-ethanone.
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 an aromatic hydrocarbon compound having an amine substituted with electron withdrawing groups.
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 compounds of the Formula Ia and Formula Ib can be synthesized by substitution reaction of an amine group of aromatic hydrocarbon compounds represented by the following Formula 2a and Formula 2b with electron withdrawing groups, such as -SO2CF3, -CN, -F, -Cl, -COCF3, -BF3 and -SO2CN (see Reaction Schemes 1 and 2).
[Reaction Scheme 1]
organic solvent
2a
Ia
[Reaction Scheme 2]
2b Ib wherein, R1, R2, R3, R4, R5, R6, R7, X and n are defined as in the compound of the Formula 1.
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 matrix; (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 network-structured 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,
dimethoxyrnethane, 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, LiCOOC2Fs,
LiN(SO2CFs)2, LiC(SO2CFs)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl or a mixture thereof.
Although there is no limitation on the polymer matrix 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 network-structured, 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 (A is CH3, n is 15, Bis- 15m) or bisphenol A ethoxylate diacrylate (A is H, n is 4, Bis-4) represented by the following Formula 3: [Formula 3]
wherein, A is H or CH3.
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 matrix. The solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of a polymer compound selected from the network-structured, 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 dialkylether, 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 LixWO2 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(carbondisulfide)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(carbondisulfide)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 monofluoride (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 LixWO2 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^V6O13, Lii.2V2O5, LiCoO2, LiNiO2, LiNi1-xMx02 (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.
Manufacture of an anode and a cathode, and assembly of a cell can be achieved by well-known methods.
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 using an electrolyte of the present invention.
A preparation method of a gel or solid polymer electrolyte film 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 matrix is then added to the solution and mixed together. If necessary, heat can be applied to completely dissolve the polymer matrix 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 network-structured, 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 network-structured, 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); and
FIG. 2 and FIG. 3 are showing cycling performance of liquid electrolytes including anion receptor as an additive of the present invention (Experimental example X).
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 3]
22.9g of 3,5-(bis-trifluoromethyl)anilne was mixed with 24.3g of triethylamine in
10OmL of CH2Cl2 at -25 °C, and 62.1g of triflic anhydride was added dropwise thereto
under nitrogen atmosphere. The resultant solution was stirred for one hour at room temperature and poured into distilled water. The organic layer was separated and washed with distilled water three times. Then, the organic extracts was dried over anhydrous
MgSO4 and filtered. CH2Cl2 was removed in vacuum to yield (3,5-bis-trifluoromethyl- phenyl)-di(trifluoromethanesulfonyl)-amine [3,5-(bis-trifluoromethyl)phenyl-l-TFSI] (see the Reaction Scheme 3).
1H NMR (300MHz, CDCl3): 7.76 (s, 2H), 8.03(s, IH); 19F NMR (300MHz,
CDCl3): -64.12, -71.44
Example 2. Preparation of an anion receptor (2) [Reaction Scheme 4]
3,5-Bis-trifluoromethyl-phenyl-cyanamide (3,5-Bis-trifluoromefhyl-phenyl)-dicyano-amine
86g of cyanogen chloride (1.4mol) was dissolved in 15OmL of cold anhydrous ether (-1O0C). A mixed solution of 229.1g of 3,5-(bis-trifluoromethyl)anilne (lmol) and
20OmL of anhydrous ether was added thereto over 2 hours with keeping the temperature below -50C. The reaction mixture was kept at room temperature for 12 hours. A white
precipitate thusly produced was collected and washed once with 10OmL of anhydrous ether and twice more with 75mL of anhydrous ether. Then, a mixed solution of 30.7g of cyanogen chloride (0.5mol) and 15OmL 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 15OmL 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 10OmL 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 3,5-bis-trifluoromethyl-phenyl)-dicyano-amine (see the Reaction Scheme 4).
1H NMR (300MHz, CDCl3): ppm 7.75 (s, 2H), 8.05 (s, IH); 13C NMR (CDCl3): ppm 113.2, 117.2, 118.4, 120.6, 1331, 148.3 19F NMR (300MHz, CDCl3): -64.12 Example 3. Preparation of an anion receptor (3) [Reaction Scheme 5]
ClCHCCl3
1H NMR (300MHz, CDCl3): ppm 7.75 (s, 2H), 8.05 (s, IH); 13C NMR (CDCl3): ppm 112.1, 113.2, 115.2, 119.6; 19F NMR (CDCl3): ppm -53.7, -64.12 Example 4. Preparation of an anion receptor (4) [Reaction Scheme 6]
(3,5-Bis-trifluoromethyl-phenyl)-dichloro-amine
A mixture of 106g of chromatographic alumina and 4Og of N-chlorosuccinimide
(0.3mol), a chlorinating agent 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. 22.9g of 3,5-(bis-trifluoromethyl)aniline (O.lmol) which was precooled to -3O0C was slowly introduced into the system over 1 hour. Later, vapor was
condensed in liquid nitrogen trap to yield (S^-bis-trifluoromethyl-pheny^-dichloro-amine (see the Reaction Scheme 6).
1H NMR (300MHz, CDCl3): ppm 7.75 (s, 2H), 8.05 (s, IH); 13C NMR (CDCl3): ppm 112.1, 115.2, 119.6, 132.1, 147.3; 19F NMR (300MHz, CDCl3): -64.12. Example 5. Preparation of an anion receptor (5) [Reaction Scheme 7]
At<3,5-Bis-trifluoromethyl-phenyl>2,2,2-trifluoro-iV-(2,2,2-trifluoro-acetyl)-acetamide
0.476g of 3,5-(bis-trifluoromethyl)aniline (2.08mmol) and 0.49mL of anhydrous trifluoroacetic 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-(3,5-bis-trifluoromethyl- phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (see the Reaction Scheme 7).
1H NMR (300MHz, CDCl3): ppm 7.75 (s, 2H), 8.05 (s, IH); 13C NMR (CDCl3): ppm 117.7, 119.6, 120.5, 122.2, 131.5, 141.4, 166.2; 19F NMR (CDCl3): ppm -64.12, -71.3. Example 6. Preparation of an anion receptor (6)
[Reaction Scheme 8]
2,4-Difluoro-phenylamine (2,4-Difluoro-phenyl)-di(trifluoromethanesulfonyl)-amine
Under the same conditions as in Example 1, 12.9g of 2,4-difluoro-phenyl amine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield (2,4-difluoro- phenyl)-di(trifluoromethanesulfonyl)-amine (2,4-difluoroaniline-di-TFSI) (see the
Reaction Scheme 8).
Example 7. Preparation of an anion receptor (7) [Reaction Scheme 9]
2,4-Difluoro-phenyIamine 2,4-Difluoro-phenyl-cyanamide (2,4-Difluoro-phenyl)-dicyano-amine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4rnol) and 129. Ig of 2,4-difluoro-phenyl amine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain (2,4-difluoro-phenyl)-dicyano-amine (see Reaction Scheme 9).
1H NMR (300MHz, CDCl3): ppm 6.42-6.49 (m, 3H); 13C NMR (CDCl3): ppm 103.3, 111.9, 118.0, 118.3, 129.3, 150.3, 153.7 Example 8. Preparation of an anion receptor (8) [Reaction Scheme 10]
ClCHCCl3
2,4-Difluoro- 1 -iodo-benzene (2,4-Difluoro-phenyl)-difluoro-amine
24.Og of 2,4-difluoro-iodo-benzene (lOOmmol), 35mL of tetrachloroethane and 6.7Og of tetrafluorohydrazine (64mmol) were reacted as Example 3 to obtain (2,4-difluoro- phenyl)-difluoro-amine (see Reaction Scheme 10).
1H NMR (300MHz, CDCl3): ppm 6.42-6.49 (m, 3H); 13C NMR (CDCl3): ppm 103.3, 111.9, 118.3, 129.3, 150.3, 153.7 Example 9. Preparation of an anion receptor (9) [Reaction Scheme 11]
2,4-Difluoro-phenylamine (2,4-Difluoro-phenyl)-dichloro-amine
4Og of N-chlorosuccinimide (0.3mol) and 12.9g of 2,4-difluoro-phenyl amine (0.1 mol) were reacted as Example 4 to obtain (2,4-difluoro-phenyl)-dichloro-amine (see Reaction Scheme 11).
1H NMR (300MHz, CDCl3): ppm 6.42-6.49 (m, 3H); 13C NMR (CDCl3): ppm 103.3, 111.9, 118.3, 129.3, 150.3, 153.7 Example 10. Preparation of an anion receptor (10) [Reaction Scheme 12]
2,4-Difluoro-phenylamine iV-(2,4-Difluoro-phenyl)-2,2,2-trifluoro-iV-(2,2,2-trifluoro-acefyl)-acetamide
0.54g of 2,4-difluoro-phenyl amine (4.17mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-(2,4-difluoro-phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction
Scheme 12).
1H NMR (300MHz5 CDCl3): ppm 6.42-6.49 (m, 3H); 13C NMR (CDCl3): ppm 102.7, 111.3, 122.2, 123.4, 123.6, 155.6, 159.3, 166.2 Example 11. Preparation of an anion receptor (11) [Reaction Scheme 13]
triethylamine
Pyridine-2,6-diamine
j Q N,N,N,N-Tetra(trifluoromethanesulfonyl)-pyridine-2,6-diamine
Under the same conditions as in Example 1, 5.46g of pyridine-2,6-diamine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield N,N,N,N- tetra(trifluoromethanesulfonyl)-pyridine-2,6-diamine (see the Reaction Scheme 13).
1H NMR (300MHz, CDCl3): ppm 7.23 (d, 2H), 8.21 (t, IH); 19F NMR (CDCl3): 15 ppm -72.6 (s)
Example 12. Preparation of an anion receptor (12) [Reaction Scheme 14]
N,N-Dicyano-pyridine-2,6-diamide N,N,N,N-Tetracyano-pyridine-2,6-diamine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 54.6g of pyridine-2,6-diamine (0.5mol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain NsN,N,N-tetracyano-pyridine-2,6-diamine (see Reaction Scheme 14).
1H NMR (300MHz5 CDCl3): ppm 7.23 (d, 2H), 8.21 (t, IH); 13C NMR (CDCl3): ppm 98.3, 118, 140.3, 160.2
Example 13. Preparation of an anion receptor (13) [Reaction Scheme 15]
N,N,N,N-Tetrachloro-pyridine-2,6-diamine 4Og of N-chlorosuccinimide (0.3mol) and 5.46g of pyridine-2,6-diamine (0.05mol) were reacted as Example 4 to obtain N,N,N,N-tetrachloro-pyridine-2,6-diamine (see
Reaction Scheme 15).
1H NMR (300MHz, CDCl3): ppm 7.23 (d, 2H), 8.21 (t, IH); 13C NMR (CDCl3): ppm 98.3, 140.3, 160.2 Example 14. Preparation of an anion receptor (14)
[Reaction Scheme 16]
Λr-{6-[Bis-(2,2,2-trifluoro-acetyl)-amino]-pyridin-2-yl} -2,2,2-trifluoro-Λr-(2,2,2-trifluoro-acetyl)-acetamide
0.1 Ig of pyridine-2,6-diamine (2.08mmol), 0.49mL of anhydrous trifluoroacetic
acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain N-{6-[bis-(2,2,2- trifluoro-acetyl)-amino]-pyridin-2-yl}-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction Scheme 16). 1H NMR (300MHz, CDCl3): ppm 8.07 (t, IH), 8.12 (d, 2H); 13C NMR (CDCl3):
ppm 110.7, 122.2, 141.1, 150.2, 166.2 Example 15. Preparation of an anion receptor (15) (Example 15-1) Method 1
(Step 1) Preparation of methanesulfonic acid 3,5-bis-methanesuIfonyIoxy-phenyI ester [Reaction Scheme 17]
Methanesulfonic acid 3,5-bis-methanesulfonyloxy-phenyl ester
12.6g of methanesulfonyl chloride (CHsSO2Cl) was slowly added with stirring for
30 minutes at -5°C into 60OmL THF in which 4.2g of benzene-l,3,5-triol and 11.2g of
triethylamine were dissolved. After adding, temperature of the reaction mixture was
elevated to 0°C, and then the reaction mixture was stirred for 2 hours. Obtained
triethylammonium hydrochloride salt was filtered and the filtrate was poured into distilled water. The resultant was extracted with CH2Cl2 and CH2Cl2 layer was dried over anhydrous MgSO4. CH2Cl2 was removed in vacuum to yield methanesulfonic acid 3,5-bis- methanesulfonyloxy-phenyl ester (see the Reaction Scheme 17).
1H NMR (300MHz, CDCl3): ppm 2.94 (s, 3H)3 7.15 (s, 3H); 13C NMR (300MHz,
CDCl3): ppm 33.98, 95.5, 160.1 (Step 2) Preparation of 1,3,5-triazido-benzene [Reaction Scheme 18]
1,3,5-Triazido-benzene
12g of methanesulfonic acid 3,5-bis-methanesulfonyloxy-phenyl ester obtained from (step 1) was added drop wise over 30 minutes into the suspension solution prepared by adding 9.77g of NaN3 into 40OmL of dimethylacetamide. The reaction mixture was
stirred for 16 hours at 100°C and extracted with CH2Cl2. Volatile components were
removed to yield 1,3,5-triazido-benzene (see the Reaction Scheme 18).
1H NMR (300MHz, CDCl3): ppm 7.3 (s, 3H); 13C NMR (300MHz5 CDCl3): ppm 128.
(Step 3) Preparation of benzene-l,3,5-triamine [Reaction Scheme 19]
Benzene- 1 ,3,5-triamine
3.8g of 1,3,5-triazido-benzene obtained from (step 2) was dissolved into 20OmL of ethanol, 10.7g of zinc powder was added thereto, and then 16.4mL of ION HCl was added
dropwise thereto. The reaction mixture was stirred for 7 hours at 0°C and filtered to
remove the residual zinc powder. The filtrate free of zinc powder was neutralized with
NaOH and extracted with CH2Cl2. Volatile components were removed under reduced pressure to yield benzene-l,3,5-triamine having amine terminal groups (see the Reaction Scheme 19).
1H NMR (300MHz, CDCl3): ppm 2.49 (m, 6H)5 5.13 (s, 3H); 13C NMR (300MHz, CDCl3): ppm 91.7, 148.3 (Step 4) Preparation of benzene-l,355-tri-TFSI [Reaction Scheme 20]
4.1g of benzene- 1,3 ,5 -triamine obtained from (step 3) was mixed with 24.3g of
triethylamine in 10OmL of CH2Cl2 at -25 °C, and 62.1g of triflic anhydride was added
dropwise thereto under nitrogen atmosphere. The resultant solution was stirred for one hour at room temperature and poured into distilled water. The organic layer was separated and washed with distilled water three times. Then, the organic extracts was dried over anhydrous MgSO4 and filtered. CH2Cl2 was removed in vacuum to yield N,N,N',N',N",N"- hexa(trifluoromethanesulfonyl)-benzene-l,3,5-triamine (benzene-l,3,5-tri-TFSI) (see the Reaction Scheme 20).
1H NMR (300MHz5 CDCl3): 5.02 (s, 3H); 19F NMR (CDCl3): ppm -71.4 (s) (Example 15-2) Method 2
(Step 1) Preparation of benzene-l,3,5-triamine
[Reaction Scheme 21]
1,3,5-Trinitro-benzene Benzene-l,3,5-triamine
lOOmg of 1,3,5-tiinitrobenzene was dissolved in 1OmL of ethyl acetate, and 3g of
Raney nickel was added thereto. The mixture was stirred for 12 hours at 40 °C with
supplying hydrogen under a pressure of 40 bar in an iron autoclave. The reaction mixture was filtered through a fritted funnel under argon gas into a Schlenk flask. The filtrate was cooled overnight in a refrigerator to obtain 58mg of colorless needle-like product having
melting point of 112°C (see the Reaction Scheme 21).
1H NMR (300MHz, CDCl3): ppm 2.49 (m, 6H), 5.13 (s, 3H); 3C NMR (300MHz5
CDCl3): ppm 91.7, 148.3
(Step 2) Preparation of benzene-l,3,5-tri-TFSI
Bnzene-l,3,5-tri-TFSI was obtained by same method of the (step 4) of the Example
(15-1) (see the Reaction Scheme 20).
1H NMR (300MHz, CDCl3): 5.02 (s, 3H); 19F NMR (CDCl3): ppm -71.4 (s)
Example 16. Preparation of an anion receptor f!6)
[Reaction Scheme 22]
N,N,N-Tricyano-benzene-l,3,5-triamide N,N,N,N,N,N-Hexacyano-benzene-l,3,5-triamine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 41. Ig of benzene- 1,3,5 -triamine (0.33mol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N,N,N,N,N,N-hexacyano-benzene-l,3,5-triamine (see Reaction Scheme 22).
1H NMR (300MHz, CDCl3): ppm 5.18 (s, 3H); 13C NMR (CDCl3): ppm 84.5, 118, 159.9, 161.1
Example 17. Preparation of an anion receptor (17) [Reaction Scheme 23]
N,N,N,N,N,N-Hexachloro-benzenee-l,3,5-triamine 4Og of N-chlorosuccinimide (0.3mol) and 4.11g of benzene-l,3,5-triamine
(0.033mol) were reacted as Example 4 to obtain N,N,N,N,N,N-hexachloro-benzenee- 1,3,5 - triamine (see Reaction Scheme 23).
1H NMR (300MHz, CDCl3): ppm 5.02 (s, 3H); 13C NMR (CDCl3): ppm 91.7, 148.3 Example 18. Preparation of an anion receptor (18) [Reaction Scheme 24]
#-{3,5-Bis-|Ws-(2,2,2-trifluoro-acetyl)-amino]-phenyl} -2,2,2-trifluoro-Λ'-(2,2,2-trifluoro-acetyl)-acetamide
0.17g of benzene-l,3,5-triamine (1.39mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in
3mL of carbon tetrachloride were reacted as Example 5 to obtain N-{3,5-bis-[bis-(2,2,2- trifluoro-acetyl)-amino]-phenyl}-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction Scheme 24).
1H NMR (300MHz, CDCl3): ppm 7.76 (s, 3H); 13C NMR (CDCl3): ppm 107.9, 122.2, 141.1, 166.2
Example 19. Preparation of an anion receptor (19) (Step 1) Preparation of l-(2-bromo-ethyI)-4-nitro-benzene [Reaction Scheme 25]
fuming HNO3
Mixture of 204g of anhydrous acetic acid and 12Og of acetic acid is cooled to 0°C,
and 204g of fuming HNO3 was slowly added thereto. The mixture was cooled to -5 °C and
185g of phenyl ethyl bromide was added dropwise thereto over 3 hours with keeping the temperature below O0C. The resultant mixture was stirred for 2.5 hours after adding. The reaction mixture was poured into the suspension solution prepared by adding 265 g of sodium carbonate into 2L of ice water. The yellow product was taken up in benzene and completely washed with water and then with saturated sodium bicarbonate solution. Benzene was removed by steam bath, and residual product was recrystallized with 3 L of
petroleum ether to obtain l-(2-bromo-ethyl)-4-nitro-benzene (see Reaction Scheme 25).
1H NMR (300MHz5 CDCl3): ppm 3.26 (t, 2H), 3.59(t, 2H)5 7.36(d5 2H), 8.16(d,
2H); 13C NMR (CDCl3): ppm 32.7, 38.6, 77.O5 123.8, 129.6, 146.2, 147.0
(Step 2) Preparation of l-nitro-4-vinyl-benzene [Reaction Scheme 26]
1 -Nitro-4-vinyl-benzene
5Og of nitrophenyl ethyl bromide, 30OmL of triethanolamine and 15OmL of water were added into a IL round flask which was fitted with a Dean-Stark trap and a reflux condenser, and refluxed for 1 hour. Nitrostyrene was isolated into the trap as deep yellow liquid. After about 90 minuites, i.e. when the isolation of nitrostyrene was almost completed, 5Og of nitrophenyl ethyl bromide was additionally added, and this procedure was repeated until 20Og in all had been decomposed to obtain l-nitro-4-vinyl-benzene (see Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 5.68 (m, 2H)5 6.77 (m, IH)5 7.56(d, 2H), 8.14(d, 2H); 13C NMR (CDCl3): ppm 112.3, 123.75, 127.1, 135.8, 141.0, 147.6 (Step 3) Preparation of p-aminostyrene [Reaction Scheme 27]
4-Vinyl-phenylamine
1Og of aluminum amalgam and 40OmL of ether was added into a IL round flask fitted with condenser, 12g of nitrostyrene dissolved in 5OmL of ether was gradually poured into the upper part of the condenser and 8mL of water was slowly added dropwise thereto. Vigorous reaction occurred, and added amount of nitrostyrene was controlled for adequate reflux. Resultant mixture of nitrostyrene and water was left until precipitates generate, refluxed for 10 minuites in water bath and then filtered. The precipitates was washed with ether several times and solvent was removed under reduced pressure to obtain 4-vinyl- phenylamine (p-aminostyrene) (see Reaction Scheme 27).
1U NMR (300MHz, CDCl3): ppm 3.61(s-broad, 2H), 5.39(m, 2H), 6.67 (m, IH), 6.41(d, 2H), 7.05(d, 2H); 13C NMR (CDCl3): ppm 112.3, 115.0, 124.9, 127.1, 135.8, 145.9 (Step 4) Preparation of styrene-TFSI [Reaction Scheme 28]
Di(trifluoromethanesulfonyl)-(4-vinyl-phenyl)-amine
11.9g of 4-vinyl-phenylamine obtained from (step 3) was mixed with 24.3g of
triethylamine in 10OmL of CH2Cl2 at -25 °C, and 62.1g of triflic anhydride was added
dropwise thereto under nitrogen atmosphere. The resultant solution was stirred for one hour at room temperature and poured into distilled water. The organic layer was separated and washed with distilled water three times. Then, the organic extracts was dried over anhydrous MgSO4 and filtered. CH2Cl2 was removed in vacuum to yield di(trifluoromethanesulfonyl)-(4-vinyl-phenyl)-amine (styrene-TFSI) (see the Reaction Scheme 28).
1H NMR (300MHz, CDCl3): 5.39(m, 2H), 6.63 (m, IH), 6.41 (d, 2H), 7.05(d, 2H); 19F NMR (CDCl3): ppm -71.5 (s) Example 20. Preparation of an anion receptor (20) [Reaction Scheme 29]
4-Vinyl-phenyl-cyanamide N,N-Dicyano-(4-vinyl-phenyl)-amine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 119.2g of 4-vinyl-phenyl amine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain N,N-dicyano-(4-vinyl-phenyl)-amine (see Reaction Scheme 29).
1H NMR (300MHz, CDCl3): 5.39(m, 2H), 6.63 (m, IH), 6.41(d, 2H), 7.05(d, 2H); 13C NMR (CDCl3): ppm 112.3, 115.0, 118.0, 127.0, 124.9, 135.8, 145.9 Example 21. Preparation of an anion receptor (21) [Reaction Scheme 30]
Dichloro-(4-vinyl-phenyl)-amine
4Og of N-chlorosuccinimide (0.3mol) and 11.9g of 4-vinyl-phenyl amine (O.lmol) were reacted as Example 4 to obtain dichloro-(4-vinyl-phenyl)-amine (see Reaction Scheme 30).
1H NMR (300MHz, CDCl3): 5.39(m, 2H), 6.63 (m, IH), 6.41(d, 2H), 7.05(d, 2H); 13C NMR (CDCl3): ppm 112.3, 115.0, 127.0, 124.9, 135.8, 145.9 Example 22. Preparation of an anion receptor (22) [Reaction Scheme 31]
2,2,2-Trifluoro-Λ'-(2,2,2-trifluoro-acetyl)-ΛL(4-vinyl-phenyl)-acetamide 0.5Og of 4-vinyl-phenyl amine (4.17mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain 2,2,2-trifluoro-N-(2,2,2- trifluoro-acetyl)-N-(4-vinyl-phenyl)-acetamide (see Reaction Scheme 31).
1U NMR (300MHz, CDCl3): 5.39(m, 2H), 6.63 (m, IH), 7.28(d, 2H), 7.59(d, 2H); 13C NMR (CDCl3): ppm 112.3, 120.3, 122.2, 126.4, 130.5, 135.8, 166.2 Example 23. Preparation of an anion receptor (23)
[Reaction Scheme 32]
4-Hexylphenyl-TFSI
Under the same conditions as in Example 1, 17.7g of 4-hexylaniline, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield 4-hexyl-phenyl- di(trifluoromethanesulfonyl)-amine (4-hexylphenyl-TFSI) (see the Reaction Scheme 32).
1H NMR (300MHz, CDCl3): 0.78 (t, 3H)5 1.09-1.20 (m, 6H)5 1.44-1.51 (m, 2H), 2.46-2.51 (t, 2H), 7.11 (s, 4H); 19F NMR (300MHz5 CDCl3): -71.52 Example 24. Preparation of an anion receptor (24) [Reaction Scheme 33]
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 177.2g of 4-hexylaniline (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain (4-Hexyl- phenyl)-dicyano-amine (see Reaction Scheme 33). 1H NMR (300MHz, CDCl3): 0.96 (t, 3H)5 1.29-1.33 (m, 6H)5 1.44-1.62 (m, 2H),
2.46-2.51 (t, 2H)5 6.87 (s, 4H); 13C NMR (CDCl3): ppm 14.0, 23 J, 29.6, 32.5, 114.9, 118.0, 129.1, 129.4, 143.9
Example 25. Preparation of an anion receptor (25)
[Reaction Scheme 34]
(4-Hexyl-phenyl)-dichloro-aniine
4Og of N-chlorosuccinimide (0.3mol) and 17.7g of 4-hexylaniline (O.lmol) were reacted as Example 4 to obtain (4-hexyl-phenyl)-dichloro-amine (see Reaction Scheme 34).
1H NMR (300MHz, CDCl3): 0.96 (t, 3H), 1.29-1.33 (m, 6H), 1.44-1.62 (m, 2H),
2.46-2.51 (t, 2H), 6.87 (s, 4H); 13C NMR (CDCl3): ppm 14.0, 23.1, 29.6, 32.5, 35.8, 114.9,
129.1, 129.4, 143.9
Example 26. Preparation of an anion receptor (26) [Reaction Scheme 35]
2,2,2-Trinuoro-Λf-(4-hexyl-phenyl)-Λ'-(2,2,2-trifluoro-acetyl)-acetamide
0.74g of 4-hexylaniline (4.17mmol), 0.49mL of anhydrous trifluoroacetic acid
(3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL
of carbon tetrachloride were reacted as Example 5 to obtain 2,2,2-trifluoro-N-(4-hexyl- phenyl)-N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction Scheme 35).
1H NMR (300MHz, CDCl3): 0.96 (t, 3H), 1.29-1.33 (m, 6H), 1.44-1.62 (m, 2H), 2.46-2.55 (t, 2H), 7.10 (s, 4H); 13C NMR (CDCl3): ppm 14.0, 23.1, 29.6, 32.5, 35.8, 120.2, 122.2, 128.5, 135.0, 138.6, 166.2
Example 27. Preparation of an anion receptor (27) [Reaction Scheme 36]
C Λ triethylamine fi A .SO2CF3
V-NH2 + (CF3SO2)2O *- { V- < N' chloroform \=N SO2CF3
Pyrimidin-2-ylamine Di(trifluoromethanesulfonyl)-pyrimidin-2-yl-amine
Under the same conditions as in Example 1, 9.5g of pyrimidine-2-yl-amine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield di(trifluoromethanesulfonyl)-pyrimidin-2-yl-amine (see the Reaction Scheme 36).
1H NMR (300MHz, CDCl3): 5.9 (m, IH), 8.1 (d, 2H); 19F NMR (300MHz, CDCl3): -71.35
Example 28. Preparation of an anion receptor (28) [Reaction Scheme 37]
Pyrimidin-2-ylamine Cyano-pyrimidin-2-yl-amine Dicyano-pyrimidin-2-yI-amine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 95.1g of pyrimidine-2-yl-amine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain dicyano-pyrimidin-2-yl-amine (see Reaction Scheme 37).
1H NMR (300MHz, CDCl3): 5.9 (m, IH), 8.1 (d, 2H); 13C NMR (CDCl3): ppm
110.8, 118.0, 157.1, 169.3
Example 29. Preparation of an anion receptor (29)
[Reaction Scheme 38]
Pyrimidin-2-yIamine Dichloro-pyrimidin-2-yl-amine
4Og of N-chlorosuccinimide (0.3mol) and 9.5g of pyrimidine-2-yl-amine (O.lmol) were reacted as Example 4 to obtain dichloro-pyrimidin-2-yl-amine (see Reaction Scheme 38).
1U NMR (300MlHz, CDCl3): 5.9 (m, IH), 8.1 (d, 2H); 13C NMR (CDCl3): ppm 110.8, 157.1, 169.3 Example 30. Preparation of an anion receptor (30)
[Reaction Scheme 39]
l
yrimidin-2-ylamiπe
2,2,2-Trifluoro-iV-pyriniidin-2-yl-iV-(2,2,2-trinuoro-acetyl)-acetamide
0.39g of pyrimidin-2-yl-amine (4.17mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain 2,2,2-trifluoro-N- pyrimidin-2-yl-N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction Scheme 39).
1H NMR (300MlHz, CDCl3): 6.9 (m, IH), 8.8 (d, 2H); 13C NMR (CDCl3): ppm 117.3, 122.2, 156.6, 160.7, 166.2 Example 31. Preparation of an anion receptor (31) [Reaction Scheme 40]
' L > > J Λ^^^ -Tπchloro-iV^^V"-tπ(tπfluoromethanesulfonyl)
-[l,3,5]triazine-2,4,6-triamine
Under the same conditions as in Example 1, 15.3g of N,N',N"-trichloro- [l,3,5]triazine-2,4,6-triamine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield N,N',N"-trichloro-N,N',N"-tri(trifluoromethanesulfonyl)-[l,3,5]triazine- 2,4,6-triamine (see the Reaction Scheme 40).
13C NMR (30OMlHz, CDCl3): 143.9, 179.2; 19F NMR (300MHz, CDCl3): -71.46 Example 32. Preparation of an anion receptor (32) [Reaction Scheme 41]
Λ',Λ'',Λ'"-Trichloro-Λf^V^V"-tricyano-[l,3,5]triazine-2,4,6-triamine As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 153g of N,N',N"-trichloro-[l,3,5]triazine-2,4,6-triamine (0.67mol) to obtain N,N',N"-trichloro-N,N',N"-tricyano-[l,3:,5]triazine-2,4,6-triamine (see Reaction Scheme 41).
13C NMR (300MHz, CDCl3): 118.0, 179.2 Example 33. Preparation of an anion receptor (33) [Reaction Scheme 42]
AyVA"-Trichloro-[l,3,S]triazine-2,4,6-triamine
ΛWiV'^V'/i/"^V"-HexachIoro-[l,3,51triazine-2,4,6-triaiiiine
4Og of N-chlorosuccinimide (0.3mol) and 15.3g of N,N',N"-trichloro- [l,3,5]triazine-2,4,6-triamine (0.07mol) were reacted as Example 4 to obtain N,N,Nl,N',N",N"-hexachloro-[l,3,5]triazine-2,4,6-triamine (see Reaction Scheme 42).
13C NMR (300MHz, CDCl3): 179.2
Example 34. Preparation of an anion receptor (34) [Reaction Scheme 43]
W-{4,6-Bis-[chloro-(2,2,2-trifluoro-acetyI>amino]-[l,3>5] triazin-2-yl}-2,2,2-trifluoro-Λf-chloro-acetamide
0.64g of N,N',N"-trichloro-[l,3,5]triazine-2,4,6-triamine (2.78mmol), 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-{4,6-bis-[chloro-(2,2,2-trifluoro-acetyl)-amino]-[l,3,5]triazin-2-yl}-2,2,2-trifluoro-N- chloro-acetamide (see Reaction Scheme 43).
13C NMR (CDCl3): ppm 119.8, 168.0, 169.6 Example 35. Preparation of an anion receptor (35) [Reaction Scheme 44]
5-Met
hyl-li/-pyrazol-3-ylamine
(5-Methyl-l-(trifluoromethanesulfonyl)-l//-pyrazol-3-yl) -di(trifluoromethanesulfonyl)-amine
Under the same conditions as in Example 1, 9.7g of 5-methyl-lH-pyrazol-3-yl- amine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield (5- methyl- 1 -trifluoromethanesulfonyl- 1 H-pyrazol-3 -yl)-di(trifluoromethanesulfonyl)-amine 5 (see the Reaction Scheme 44).
1H NMR (300MHz, CDCl3): 2.73(s, 3H), 6.1(s, IH); 19F NMR (300MHz, CDCl3): - 72.13.
Example 36. Preparation of an anion receptor (36) [Reaction Scheme 45]
5
(S-Methyl-l-cyano-l/f-pyrazol-S- \ Q yl)-dicyano-amine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 64.8g of 5-methyl-lH-pyrazol-3-yl-amine (0.67mol), and
the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain (5-methyl-l-cyano-lH-pyrazol-3-yl)-dicyano-amine (see Reaction Scheme 45). 15 1H NMR (300MHz, CDCl3): 2.79 (s, 3H), 6.1 (s, IH); 13C NMR (CDCl3): ppm 6.2,
92.1, 118.0, 143.2, 156.4 Example 37. Preparation of an anion receptor (37)
[Reaction Scheme 46]
4Og of N-chlorosuccinimide (0.3mol) and 6.5g of 5-methyl-lH-pyrazol-3-yl-amine (0.07mol) were reacted as Example 4 to obtain (5 -methyl- 1-chloro-l H-pyrazol-3-yl)- dichloro-amine (see Reaction Scheme 46).
1H NMR (300MHz, CDCl3): 2.79 (s, 3H), 6.1 (s, IH); 13C NMR (CDCl3): ppm 4.4, 92.1, 143.3, 156.1
Example 38. Preparation of an anion receptor (38) [Reaction Scheme 47]
5-MethyI-l£r-pyrazol-3-ylamine
l^^-Trifluoro-^-IS-methyl-l^Al-trinuoro-acetyl)- lfir-pyrazol-3yl]-iV-{2,2,2-trinuoro-acetyl)-acetamide
2.7g of 5-methyl-lH-pyrazol-3-yl-amine (2.78mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain 2,2J2-trifluoro-N-[5-methyl-l-(2,2,2-trifluoro-acetyl)-lH-pyrazol-3-yl]-N-(2J2,2-trifluoro- acetyl)-acetamide (see Reaction Scheme 47).
1H NMR (300MHz, CDCl3): 2.79 (s, 3H), 6.1 (s, IH); 13C NMR (CDCl3): ppm 6.8, 92.1, 120.9, 122.3, 153.2, 156.7, 166.2, 200.3
Example 39. Preparation of an anion receptor (39)
[Reaction Scheme 48]
T azol-2-ylamine
Di(trifluoromethanesulfonyl)-thiazol-2-yI-amine
Under the same conditions as in Example 1, 10. Ig of thiazol-2-yl-amine, 24.3g of triethylamine and 62.1g of triflic anhydride were reacted to yield
di(trifluoromethanesulfonyl)-thiazol-2-yl-amine (see the Reaction Scheme 48).
1H NMR (300MHz, CDCl3): 6.24 (d, IH), 7.23 (d, 2H); 19F NMR (300MHz, CDCl3): -71.23
Example 40. Preparation of an anion receptor (40) [Reaction Scheme 49]
ThiazoI-2-ylamine Cyano-thiazol-2-yl-amine Dicyano-thiazoI-2-yI-amine
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and lOO.lg of thiazol-2-yl-amine (lmol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain dicyano-thiazol-2-yl-amine (see Reaction Scheme 49).
1H NMR (300MHz, CDCl3): 6.24 (d, IH), 7.23 (d, 2H); 13C NMR (300MHz5 CDCl3): 108.0, 118.1, 138.7, 171.7 Example 41. Preparation of an anion receptor (41) [Reaction Scheme 50]
ThiazoI-2-ylamine Oichloro-thiazol-2-yl-amine
4Og of N-chlorosuccinimide (0.3mol) and 10. Ig of thiazol-2-yl-amine (0.1 mol) were reacted as Example 4 to obtain dichloro-thiazol-2-yl-amine (see Reaction Scheme 50).
1H NMR (300MHz, CDCl3): 6.24 (d, IH), 7.23 (d, 2H); 13C NMR (300MHz, CDCl3): 108.0, 138.7, 171.7
Example 42. Preparation of an anion receptor (42)
[Reaction Scheme 51]
Z^-Trifluoro-Λ'-thiazoW-yl-Λ'-Cl^^-trifluoro-acetyO-acetamide
0.42g of thiazol-2-yl-amine (4.17mmol), 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 2,2,2-trifluoro-N-thiazol-2-yl- N-(2,2,2-trifluoro-acetyl)-acetamide (see Reaction Scheme 51).
1H NMR (300MHz, CDCl3): 6.24 (d, IH), 7.23 (d, 2H); 13C NMR (300MHz, CDCl3): 108.0, 122.2, 138.7, 166.2, 171.7 Example 43. Preparation of an anion receptor (43) [Reaction Scheme 52]
+ ( (CCFF33SSOO22))22OO
2-PhenyI-lfl-imidazoIe l-TrifluornmethancsulfonyI-2-phcnyl-l//-imidazolc
Under the same conditions as in Example 1, 28.8g of 2-phenyl-lH-imidazole, 24.3g of triethylamine and 62.1g of trifϊic anhydride were reacted to yield 1- trifluoromethanesulfonyl-2-phenyl-lH-imidazole (see the Reaction Scheme 52).
1H NMR (300MHz, CDCl3): 7.24(d, 2H), 7.43(t, IH), 7.49(t, 2H), 7.60(d, 2H); 19F NMR (300MHz, CDCl3): -73.21
Example 44. Preparation of an anion receptor (44)
[Reaction Scheme 53]
2-Phenyl-l//-imidazole l-Cyano^-phenyl-lfl-imidazole
As the same method of Example 2, the first reaction was performed by using 86g of cyanogen chloride (1.4mol) and 288.3g of 2-phenyl-lH-imidazole (2mol), and the second reaction was performed by further adding 30.7g of cyanogen chloride (0.5mol) to obtain 1- cyano-2-phenyl-lH-imidazole (see Reaction Scheme 53).
1H NMR (300MHz5 CDCl3): 7.20 (s, 2H), 7.34 (t, IH), 7.35(t, 2H), 7.49(d, 2H); 13C NMR (CDCl3): ppm 6.2, 92.1, 118.O5 143.2, 156.4 Example 45. Preparation of an anion receptor (45) [Reaction Scheme 54]
2-Phenyl-LH-imidazole l-ChIoro-2-phenyl-lø-imidazole
4Og of N-chlorosuccinimide (0.3mol) and 28.8g of 2-phenyl-lH-imidazole (0.2mol) were reacted as Example 4 to obtain l-chloro-2 -phenyl- lH-imidazole (see Reaction Scheme 54).
1H NMR (300MHz, CDCl3): 7.20 (s, 2H), 7.34 (t, IH), 7.35(t, 2H), 7.49(d, 2H);
13C NMR (CDCl3): ppm 122.0, 127.4, 128.5, 129.1, 136.4, 136.7.
Example 46. Preparation of an anion receptor (46)
[Reaction Scheme 55]
^ 2-Pheπyl-UWmidazole 2,2^-Trifluoro-l-(2-phenyl-imidazoH-yl)-ethanone
1.2g of 2-phenyl-lH-imidazole (8.34mmol), 0.49mL of anhydrous trifluoroacetic acid (3.2mmol) and 0.637g of 2,6-di-tert-butyl-4-methyl-pyridine (3.11mmol) dissolved in 3mL of carbon tetrachloride were reacted as Example 5 to obtain 2,2,2-trifluoro-l-(2- phenyl-imidazol-l-yl)-ethanone (see Reaction Scheme 55). 0 1H NMR (300MHz, CDCl3): 7.20 (s, 2H), 7.34 (t, IH), 7.35(t, 2H), 7.49(d, 2H); 13C
NMR (CDCl3): ppm 122.0, 123.3, 127.1, 128.5, 129.2, 136.1, 136.5, 200.2
Example 47. Manufacture of Ionic Conductive Thin Film
0.2g of the anion receptor 4-hexylphenyl-TFSI obtained from Example 23 was 5 mixed with 0.8g of bisphenol A ethoxylate dimethacrylate (Aldrich Co., Mw=l,700, "Bis-
15m") of the Formula 3 used as a crosslinking agent and 0.1137g of lithium triflate
(LiCF3SO3). To this mixture was added 0.008g of dimethoxyphenyl acetophenone
(DMPA). 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, 0 a solid polymer electrolyte was prepared.
Comparative Example 1. Manufacture of Film without Anion Receptors
The same procedure of Example 47 was repeated using the composition 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
Ionic conductivity of the solid polymer electrolyte film obtained from the Example 47 using 4-hexylphenyl-TFSI prepared from Example 23 was measured as follows.
First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium-copper foil, photo-cured, 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 0.5mm - 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. The solid polymer electrolyte comprising 4-hexylphenyl-TFSI as an anion receptor has higher ionic conductivity than the electrolyte without anion receptor as temperature raises.
Example 48. Manufacture of Cell Using Liquid Electrolyte with Anion Receptor
0.015g of the anion receptor 3,5-(bis-trifluoromethyl)phenyl-l-TFSI obtained from Example 1 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). Example 49. Manufacture of Cell Using Liquid Electrolyte with Anion Receptor
The same procedure of Example 48 was repeated, with the exception that 0.015g of 2,4-difluoroaniline-di-TFSI obtained from Example 6 was used as an anion receptor to assemble a cell.
Comparative Example 2. Manufacture of Cell Using Liquid Electrolyte without Anion Receptors
The same procedure described in Example 48 was repeated, with the exception that the separator impregnated with an organic solvent EC/DMC/DEC (1:1:1, IM LiPF6) 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 Examples 48 and 49 of the present invention and Comparative Example 2 were tested at room temperature using Maccor 4000. Charging and discharging were carried out to 1C, respectively. The cells were charged and discharged anywhere between 3.0V and 4.2V at
a predetermined current density of 0.6mA/cm (charging) and 1.5mA/cm (discharging) with respect to a LiCoO2 counter electrode.
FIG. 2 and FIG. 3 graphically show a comparison between discharge capacities with respect to the number of cycling of cells manufactured using electrolytes inclusive of the anion receptors 2,4-difluoroaniline-di-TFSI (Example 6) and 3,5-(bis- trifluoromethyl)phenyl-l-TFSI (Example 1), and those of cells manufactured using electrolytes exclusive of the anion receptor. It turned out that the cells manufactured using electrolytes of the anion receptors 3,5-(bis-trifluoromethyl)phenyl-l-TFSI and 2,4- difluoroaniline-di-TFSI exhibited higher capacity and excellent stability.
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
1. A compound represented by the Formula 1 : [Formula 1]
R3, R4, R5, R6 and R7 each independently represents a hydrogen atom, Ci~Cio alkyl, vinyl, allyl, phenyl, an electron withdrawing functional group selected from the group
consisting of -CF3, -SO2CF3, -COCF3 and -SO2CN, or 
n R 9;
R8 and R9 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;
X is carbon atom or nitrogen atom; Y is carbon atom, nitrogen atom, oxygen atom or sulfur atom;
R6 is not present in the structure when Y is oxygen atom or sulfur atom; n is an integer from O to 20; and q is O or 1.
2. The compound of claim 1, wherein at least one of R1 and R2 are not -SO2CF3 when R3, R4, R6 and R7 are hydrogen and R5 is hydrogen or vinyl group, and Ri and R2 are not simultaneously -Cl when at least one of X and Y are nitrogen atom.
3. The compound of claim 1, wherein the compound is selected from the group consisting of:
(3,5-Bis-trifluoro]methyl-phenyl)-di(trifluoromethanesulfonyl)-amine;
(S^-Bis-trifluoromethyl-pheny^-dicyano-amine;
(3,5-Bis-trifluoromethyl-phenyl)-difluoro-amine;
(3,5-Bis-trifluoromethyl-phenyl)-dichIoro-amine; N-(3,5-Bis-trifluoromethyl-phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-
acetamide;
(2,4-Difluoro-phenyl)-di(trifluoromethanesulfonyl)-amine;
(2,4-Difluoro-phenyl)-dicyano-amine;
(2,4-Difluoro-phenyl)-difluoro-amine; (2,4-Difluoro-phenyl)-dichloro-amine;
N-(2,4-Difluoro-phenyl)-2,2,2-trifluoro-N-(2,2,2-trifluoro-acetyl)-acetamide;
N,N,N,N-Tetra(trifluoromethanesulfonyl)-pyridine-2,6-diamine;
N,N,N,N-Tetracyano-pyridine-2,6-diamine;
N,N,N,N-Tetrachloro-pyridine-2,6-diamine; N-{6-[Bis-(2,2,2-trifluoro-acetyl)-amino]-pyridin-2-yl}-2,2,2-trifluoro-N-(2,2,2-
trifluoro-acetyl)-acetamide;
N,N,N',N',N",N"-Hexa(trifluoromethanesulfonyl)-benzene-l,3,5-triamine;
N,N,N,N,N,N-He;xacyano-benzene- 1 ,3,5-triamine;
N,N,N,N,N,N-Hexachloro-benzenee-l,3,5-triamine; N-{3,5-Bis-[bis-(2,2,2-trifluoro-acetyl)-amino]-phenyl}-2,2,2-trifluoro-N-(2,2,2-
trifluoro-acetyl)-acetamide;
Di(trifluoromethanesulfonyl)-(4-vinyl-phenyl)-amine;
N,N-Dicyano-(4-vinyl-phenyl)-amine; Dichloro-(4-vinyl-phenyl)-amine;
2,2,2-Trifluoro-N-(2,2,2-trifluoro-acetyl)-N-(4-vinyl-ρhenyl)-acetamide;
4-Hexyl-phenyl-di(trifluoromethanesulfonyl)-amine;
(4-Hexyl-phenyl)-dicyano-amine;
(4-Hexyl-phenyl)-dichloro-amine; 2,2,2-Trifluoro-N-(4-hexyl-phenyl)-N-(2,2,2-trifluoro-acetyl)-acetamide;
Di(trifluoromethanesulfonyl)-pyrimidin-2-yl-amine;
Dicyano-pyrimidin-2-yl-amine;
Dichloro-pyrimid in-2-yl-amine;
2,2,2-Trifluoro-N-pyrimidin-2-yl-N-(2,2,2-trifluoro-acetyl)-acetamide; N,Nl,N"-Trichloro-N,Nt,N"-tri(trifluoromethanesulfonyl)-[l,3,5]triazine-2,4,6- triamine;
N,N',N"-Trichloro-N,N',N"-tricyano-[l,3,5]triazine-2,4,6-triamine;
N,N,N',N',N",N"-Hexachloro-[l,3,5]triazine-2,4,6-triamine;
N-{4,6-Bis-[chloro-(2,2,2-trifluoro-acetyl)-amino]-[l,3,5]triazin-2-yl}-2,2,2- trifluoro-N-chloro-acetamide;
(5-Methyl- 1 -trifluoromethanesulfonyl- 1 H-pyrazol-3 -yl)- di(trifluoromethanesulfonyl)-amine;
(5 -Methyl- 1 -cyano- 1 H-pyrazol-3 -yl)-dicyano-amine;
(5 -Methyl- 1 -chloro- 1 H-pyrazol-3 -yl)-dichloro-amine; 2,2,2-Trifluoro-N-[5-methyl-l-(2,2,2-tτifluoro-acetyl)-lH-pyrazol-3-yl]-N-(2,2,2-
trifluoro-acetyl)-acetamide;
Di(trifluoromethanesulfonyl)-thiazol-2-yl-amine; Dicyano-thiazol-2-yl-amine; Dichloro-thiazol-2-yl-amine;
2,2,2-Trifluoro-N-thiazol-2-yl-N-(2,2,2-trifluoro-acetyl)-acetamide; 1 -Trifluoromethanesulfonyl-2-phenyl- 1 H-imidazole; 1 -Cyano-2-pheny 1- 1 H-imidazole; l-Chloro-2-phenyl-l H-imidazole; and 2,2,2-Trifluoro- 1 -(2-phenyl-imidazol- 1 -yl)-ethanone.
4. An electrolyte comprising the compound of claim 1.
5. The electrolyte of claim 4, wherein the electrolyte is selected from the group consisting of nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.
6. 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.
7. A gel polymer electrolyte, comprising: (i) an anion receptor of the compound of claim 1; (ii) a polymer matrix;
(iii) a nonaqueous solvent; and
(iv) an alkali metal ion containing substance.
8. 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 network-structured polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and
(iii) an alkali metal ion containing substance.
9. The electrolyte of claim 8, wherein the solid polymer electrolyte further comprises the substance selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof .
10. The electrolyte of one of claims 6 to 9, 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, dimethoxymethane, γ-butyrolactone, methyl formate,
sulforane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2-pyrrolidinone and mixtures thereof.
11. The electrolyte of one of claims 6 to 8, wherein the alkali metal ion containing substance is selected from the group consisting of LiSO3CF3, LiCOOC2F5, LiN(SO2CF3);), LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl, and a mixture thereof.
12. The electrolyte of claim 7, wherein the polymer matrix is polyacrylonitrile type polymer or polyvinylidenfluoride-hexafluoropropylene type polymer.
13. The electrolyte of claim 8, wherein the polymer selected from the group
consisting of network-structured, comb-shaped and branched polymer compounds are flexible inorganic polymers or linear polyethers.
14. The electrolyte of claim 8, 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.
15. The electrolyte of claim 13 or claim 14, wherein the flexible inorganic polymer is polysiloxane or polyphosphagen, and the linear polyether is a polyalkylene oxide.
16. The electrolyte of claim 9, 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.
17. The solid polymer electrolyte of claim 8, wherein the electrolyte further comprises a curing initiator when the electrolyte contains a crosslinkable polymer compound.
18. The electrolyte of claim 17, wherein the curing initiator is selected from the group consisting of: a photocuring initiator, a heat-curing initiator, and a mixture thereof.
19. The electrolyte of claim 18, 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.
20. The electrolyte of one of claims 6 to 8, 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.
21. The electrolyte of claim 7, comprising 5 — 40 parts by weight of the polymer matrix.
22. The electrolyte of claim 8 or claim 17, comprising 10 - 95 parts by weight of a polymer compound selected from the group consisting of network-structured, 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.
23. The electrolyte of claim 9, comprising 10 - 50 parts by weight of the substance selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
24. An electrochemical cell comprising an anode, a cathode and the electrolyte of claim 4.
25. The electrochemical cell of claim 24, 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.
26. The electrochemical cell of claim 25, wherein the transition metal oxides is
selected from the group consisting of Li2 5 V6O13, Li1 2V2O5, LiCoO2, LiNiO2, LiMn2O4,
LiMnO2, and LiNi1-xMx02 (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- 1 ,3 ,4-thiadiazole.
27. A gel polymer electrolyte film manufactured using the gel polymer electrolyte of claim 7.
28. A solid polymer electrolyte film manufactured using the solid polymer electrolyte of claim 8.
Applications Claiming Priority (2)
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| KR20060038047 | 2006-04-27 | ||
| KR10-2006-0038047 | 2006-04-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2485094C1 (en) * | 2012-06-07 | 2013-06-20 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Method of producing 4-aminostyrene |
| US9564597B2 (en) | 2010-09-08 | 2017-02-07 | Semiconductor Energy Laboratory Co., Ltd. | Fluorene compound, light-emitting element, light-emitting device, electronic device, lighting device, and organic compound |
| WO2021167428A1 (en) * | 2020-02-21 | 2021-08-26 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN113812027A (en) * | 2020-12-04 | 2021-12-17 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device containing electrolyte and electronic device |
| CN113948774A (en) * | 2021-10-18 | 2022-01-18 | 九江天赐高新材料有限公司 | Power type lithium secondary battery electrolyte and battery |
| CN114373987A (en) * | 2020-10-15 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| WO2023070674A1 (en) * | 2021-11-01 | 2023-05-04 | 东莞新能源科技有限公司 | Electrolytic solution, electrochemical device containing electrolytic solution, and electronic device |
| WO2023167431A1 (en) * | 2022-03-02 | 2023-09-07 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution composition and lithium secondary battery comprising same |
| CN117525573A (en) * | 2023-12-25 | 2024-02-06 | 中国科学院长春应用化学研究所 | Low-temperature-resistant gel polymer electrolyte and lithium ion battery using same |
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| RU2485094C1 (en) * | 2012-06-07 | 2013-06-20 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Method of producing 4-aminostyrene |
| CN114641883A (en) * | 2020-02-21 | 2022-06-17 | 株式会社Lg新能源 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| WO2021167428A1 (en) * | 2020-02-21 | 2021-08-26 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN114373987B (en) * | 2020-10-15 | 2024-04-19 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN114373987A (en) * | 2020-10-15 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN113812027A (en) * | 2020-12-04 | 2021-12-17 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device containing electrolyte and electronic device |
| CN113812027B (en) * | 2020-12-04 | 2024-03-08 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device and electronic device comprising same |
| CN113948774B (en) * | 2021-10-18 | 2023-12-22 | 九江天赐高新材料有限公司 | Power type lithium secondary battery electrolyte and battery |
| CN113948774A (en) * | 2021-10-18 | 2022-01-18 | 九江天赐高新材料有限公司 | Power type lithium secondary battery electrolyte and battery |
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| WO2023167431A1 (en) * | 2022-03-02 | 2023-09-07 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution composition and lithium secondary battery comprising same |
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