Ionic liquid electrolyte

Abstract

An ether-bridged dication is provided with two monovalent cations bonded via a carbon chain having ether group(s). The ether-bridged dication, monovalent cations, and anions are contained together within an ionic liquid electrolyte which is applied to a charge storage device. The ether-bridged dication, the ionic liquid electrolyte, and the charge storage device have operational abilities at room temperatures or below, and a reachable working potential of 3.5 V.

Claims

1. An ionic liquid electrolyte, comprising: an ether-bridged dication; at least one monovalent cation; and at least one anion; wherein the ionic liquid electrolyte is formed without organic solvents; wherein the ether-bridged dication has two monovalent cations represented by X.sub.1 and X.sub.2, and the monovalent cations are bonded through a carbon chain having at least one ether group, wherein the ether-bridged dication has the molecular structure given as follows: ##STR00012## wherein X.sub.1 and X.sub.2 are quaternary ammonium cations selected from the group consisting of an imidazolium cation, a pyrrolium cation, a pyridinium cation, a pyrazolium cation, a benzimidazolium cation, an indolium cation, a carbazolium cation, a quinolium cation, a pyrrolidinium cation, a piperidium cation, a piperalium cation, and an alkyl ammonium cation, wherein at least one of X.sub.1 and X.sub.2 is a 1-butyl pyrrolium cation which bonds to the carbon chain of the ether-bridged dication at N atom of the pyrrolium ring; and each of a, b and c is an integral selected from 1 to 10, wherein the ether-bridged dication is 2-20 wt % of the ionic liquid electrolyte.

2. The ionic liquid electrolyte according to claim 1, wherein the anion is selected from a group consisting of [BF.sub.4].sup.−, [PF.sub.6].sup.−, a Bis(fluorosulfonyl)imide anion, and a Bis(trifluorosulfonyl)imide anion.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a chemical structure of an ether-bridged dication (EMIm-TFSI) according to the present invention.

(2) FIG. 2 shows ionic conductivity of an ionic liquid electrolyte (EMIm-TFSI+[C.sub.6H.sub.12O.sub.2(MIm).sub.2]) according to one embodiment of the present invention compared with EMIm-TFSI and [C.sub.6H.sub.12O.sub.2(MIm).sub.2]-TFSI.sub.2.

(3) FIG. 3 shows a DSC result of the ionic liquid electrolyte (EMIm-TFSI+[C.sub.6H.sub.12O.sub.2(MIm).sub.2]) according to one embodiment of the present invention.

(4) FIGS. 4A and 4B show specific capacities of super capacitors produced by the ionic liquid electrolyte (EMIm-TFSI+[C.sub.6H.sub.12O.sub.2(MIm).sub.2]) according to one embodiment of the present invention and the ionic liquid electrolyte (EMIm-TFSI) of the control group at different temperature.

(5) FIG. 5 shows specific energies at different temperatures of the ionic liquid electrolyte (EMIm-TFSI+[C.sub.6H.sub.12O.sub.2(MIm).sub.2]) according to one embodiment of the present invention and the ionic liquid electrolyte (EMIm-TFSI) of the control group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiments. Furthermore, if there is no specific description in the invention, singular terms such as “a”, “one”, and “the” include the plural number. For example, “a compound” or “at least one compound” may include a plurality of compounds, and the mixtures thereof. If there is no specific description in the invention, “%” means “weight percentage (wt %)”, and the numerical range (e.g., 10%˜11% of A) contains the upper and lower limit (i.e., 10%≤A≤11%). If the lower limit is not defined in the range (e.g., less than, or below 0.2% of B), it means that the lower limit may be 0 (i.e., 0%≤B≤0.2%). The proportion of “weight percent” of each component can be replaced by the proportion of “weight portion” thereof. The abovementioned terms are used to describe and understand the present invention, but the present invention is not limited thereto.

(7) According to one embodiment, the present invention provides an ether-bridged dication with two monovalent cations, X1 and X2, bonded through a carbon chain having at least one ether group, having the molecular structure given as follows:

(8) ##STR00005##

(9) The abovementioned X1 and X2 are independently selected from a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation; and each of a, b and c is an integral selected from 1 to 10. That is, X.sub.1 can be the same as or different from X.sub.2. Furthermore, X.sub.1 has a position for bonding to the carbon chain having the ether group(s), and X.sub.2 also has a position for bonding to the carbon chain. The carbon chain with the ether group(s) can be provided with alkyl substituents without specific limitations thereto.

(10) Preferably, the quaternary ammonium cation is selected from an imidazolium cation, a pyrrolium cation, a pyridinium cation, a pyrazolium cation, a benzimidazolium cation, an indolium cation (C.sub.8H.sub.8N.sup.+), a carbazolium cation, a quinolium cation, a pyrrolidinium cation, a piperalium cation, and an alkyl ammonium cation. In one embodiment of the present invention, the quaternary ammonium cation is an imidazolium cation, for example, N-methyl imidazolium cation which bonds to the carbon chain having at least one ester group at N atom of the imidazolium ring

(11) ##STR00006##
or a pyrrolium cation, for example, 1-butyl pyrrolium cation which bonds to the carbon chain having the ester group at N atom of the pyrrolium ring

(12) ##STR00007##

(13) According to one embodiment, the present invention provides an ionic liquid electrolyte, in addition to the ether-bridged dication as above-mentioned, comprising at least one monovalent cation and at least one anion. Preferably, the ionic liquid electrolyte is formed without organic solvents. The ionic liquid electrolyte has excellent fluidity so that it can work at a temperature below 0° C. to expand the operational range of the electrochemical devices. In one embodiment of the present invention, the ether-bridged dication is preferably 2-20% by weight of the ionic liquid electrolyte, for example, 2, 5, 10, or 15 w.t. %, but it is not limited thereto. Moreover, the monovalent cation is selected from a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation. The anion mainly serves as a charge balancer for the ionic liquid electrolyte, such as

(14) ##STR00008##
Tetrafluoroborate),

(15) ##STR00009##
Hexafluorophosphate),

(16) ##STR00010##
Bis(fluorosulfonyl)imide), or

(17) ##STR00011##
Bis(trifluorosufonyl)imide), but it is not limited thereto.

(18) Refer to FIG. 1, which shows an ether-bridged dication and the suitable anion according to one embodiment of the present invention. The ether-bridged dication can be produced by, for example, heating N-methylimidazole and 1,2-bis(2-chloroethoxy)ethane in methanol to 100° C. for reaction, and then replacing the chloride ion with TFSI.sup.− by using Lithium trifluoromethanesulfonyl imide (LiTFSI). With the ether-bridged dication shown in FIG. 1, only a small amount (less than 1 wt %) in the ionic liquid electrolyte is added for improving the ionic conductivity of the ionic liquid electrolyte. As shown in FIG. 2, the ionic conductivities of the ionic liquid electrolytes made of [C.sub.6H.sub.12O.sub.2(MIm).sub.2]-TFSI.sub.2 and EMIm-TFSI (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) as the comparison groups, respectively, and the ionic conductivity of an ionic liquid electrolyte with 5 wt % [C.sub.6H.sub.12O.sub.2(MIm).sub.2]-TFSI.sub.2 in EMIm-TFSI (mixture group) according to one embodiment of the present invention, are measured. From FIG. 2, compared with the comparison groups ([C.sub.6H.sub.12O.sub.2(MIm).sub.2]-TFSI.sub.2 and EMIm-TFSI), the mixture group still has the ionic conductivity at −20° C.; the ionic conductivity can reach around 2.5 mS/cm at 20° C., which is about 30% higher than that of EMIm-TFSI group; the enhancement is at least 80% at 60° C., and the ionic conductivity can reach over 4.5 mS/cm.

(19) Furthermore, as shown in FIG. 3, the DSC (Differential Scanning calorimetry) test shows that the chemical stability of the dication [C.sub.6H.sub.12O.sub.2(MIm).sub.2]-TFSI.sub.2 is excellent. There is no obvious freezing phenomenon at −90° C., and the freezing point of the mixture can be lowered, and thus the conductivity can be maintained in an environment of −20° C. In addition, the mixture contains no organic solvent so as to avoid the safety problems caused by its high volatility, such as explosion or fire. Therefore, the cycle time of the ionic liquid electrolyte, or the cycle time of the element with the ionic liquid electrolyte can be improved.

(20) A further embodiment of the present invention provides a charge storage device having the abovementioned ionic liquid electrolyte. The charge storage device can be a super capacitor (or double layer capacitor) formed by the ionic liquid electrolyte and a high porosity activated carbon. As shown in FIGS. 4A and 4B, the super capacitor according to the present invention has a specific capacitance more than 160 F/g at a discharge rate of 0.5 A/g at −20° C., and up to 208 F/g at 60° C. In addition, as shown in FIG. 5, the working potential (potential window) of the ionic liquid electrolyte according to the present invention has a maximum value of 3.5 V when the specific power is 20000 W/kg, the specific energy reaches 70 Wh/kg.

(21) Compared to the traditional technologies, the ether-bridged dication of the present invention can bond two monovalent cations through a carbon chain having ether group(s) to form a flexible molecule. The ether group allows the dication to be more flexible. The oxygen (O) in the ether group can form hydrogen bonds when mixing with the monovalent cation to form the ionic liquid electrolyte, so as to improve the chemical stability of the ionic liquid electrolyte, and provide excellent capacitor characteristics in a wide temperature range.

(22) The present invention has been described with preferred embodiments thereof and it is understood that many changes and modifications to the described embodiments can be carried out without departing from the scope and the spirit of the invention that is intended to be limited only by the appended claims.