KR20150093204A - Electolyte compositions and electrochemical double layer capacitors formed there from - Google Patents

Abstract

The present invention generally includes phosphonium ionic liquids, salts, compositions and uses thereof in a variety of applications including: Among other applications, electrolytes in electronic devices, such as, but not limited to, memory devices including static, permanent and dynamic random access memories, include batteries, electrochemical double layer capacitors (EDLC), supercapacitors or ultra capacitors, electrolytic capacitors , As an electrolyte in a dye-sensitized solar cell (DSSC), as an electrolyte in a fuel cell, and as a heat transfer medium. In particular, the present invention relates generally to phosphonium ionic liquids, salts and compositions, wherein said compositions exhibit excellent combinations of thermodynamic stability, low volatility, broad liquid line range, ionic conductivity, and electrochemical stability. The present invention further comprises such phosphonium ionic liquids, salts and methods of making the compositions, and an operating device and system comprising the same.

Description

[0001] Electrolyte compositions and electrochemical double layer capacitors formed therefrom [

The present invention generally includes phosphonium ionic liquids, salts, electrolyte compositions based on compositions and their use in many applications. Other applications include, but are not limited to, electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memories; Electrolytes in batteries, electrochemical double layer capacitors (EDLC) or energy storage devices such as supercapacitors or ultracapacitors, electrolytic capacitors; An electrolyte in a dye-sensitized solar cell (DSSC); Electrolytes in fuel cells; Heat transfer media, high temperature reactions and / or as extraction media. In particular, the present invention relates to a molecule having phosphonium ionic liquids, salts, compositions and structural features, wherein the composition has at least two of the thermodynamic stability, low volatility, wide liquidus range and ionic conductivity, Or more. The present invention further comprises a process for preparing such phosphonium ionic liquids, salts, compositions and molecules, and an operational apparatus and system comprising the same.

Ionic liquids have attracted considerable attention due in part to their wide potential applications and applications. The term "ionic liquid" is commonly used for salts having relatively low melting points (below 100 DEG C). Salts that are liquid at room temperature are commonly referred to as room temperature ionic liquids. Early researchers used dialkylimidazolium salt based ionic liquids. For example, Wilkes et al. Have attempted to use dialkylimidazolium salt based ionic liquids with aluminum metal anodes and chlorine cathodes in an attempt to generate batteries ( J. Wilkes, J. Levisky , R. Wilson, C. Hussey , Inorg . Chem . , 21, 1263 (1982) ).

Some of the most extensively studied and commonly used ionic liquids are the pyridinium salts, and N-alkylpyridinium and N, N'-dialkylimidazolium pyridiniums are used heavily. Pyridinium-based ionic liquids including N-alkyl-pyridinium and N, N'-dialkylimidazoliums and nitrogen-based ionic ionic liquids have a limited thermodynamic stability to 300 ° C or less generally, Distillable and tends to have a measurable vapor pressure at temperatures significantly below 200 ° C. These properties limit their utility as well as their application. For example, such ionic liquids are susceptible to degradation during back end of line (BEOL) thermal processing. Additionally, such ionic liquids may also be decomposed during other heat transfer processing steps, which continuously heat cyclize the ionic liquid to temperatures in excess of < RTI ID = 0.0 > 300 C. < / RTI >

Various properties of ionic liquids have been studied and additional applications of ionic liquids have been considered. For example, electrochemical methods and applications require electrolytes to improve conductivity in a variety of devices and applications. As a possible alternative to the conventional solvent-based electrolytes, researches have been conducted in the field of room temperature ionic liquids.

Continued development, but continued demand for new developments of ionic liquids, salts and electrolyte compositions and use in electrochemical bi-layer capacitors, lithium metal and lithium ion cells, fuel cells, dye-sensitized solar cells and molecular memory devices It is clear that there is a continuing need for materials and uses in which the electrolyte can be used.

The present invention broadly includes phosphonium ionic liquids, salts, compositions and their use in many applications. Other applications include, but are not limited to, electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memories; Electrolytes in batteries, electrochemical double layer capacitors (EDLC) or energy storage devices such as supercapacitors or ultracapacitors, electrolytic capacitors; An electrolyte in a dye-sensitized solar cell (DSSC); Electrolytes in fuel cells; Heat transfer media, high temperature reactions and / or use as extraction media. In particular, the present invention relates to phosphonium ionic liquids, salts, compositions and molecules having structural characteristics, wherein said composition exhibits a desirable combination of at least two of thermodynamic stability, low volatility, broad liquid line range and ionic conductivity.

In one aspect, a phosphonium cation of one or more of the following general formulas: And at least one anion; wherein the ionic liquid composition comprises:

R ¹ R ² R ³ R ⁴ P

Wherein R ¹ , R ² , R ³ and R ⁴ are optionally and independently of each other a substituent. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently a different alkyl group consisting of 2 to 14 carbon atoms. In some embodiments, at least one of R ¹ , R ² , R ^3, and R ⁴ is an aliphatic, heterocyclic moiety. Alternatively, at least one of R ¹ , R ² , R ³ and R ⁴ is an aromatic, heterocyclic moiety. In other embodiments, R ¹ and R ² are the same and are composed of tetramethylene phospholane, pentamethylene phosphorinane, tetramethynyl phosphole, phospholane, or phospholane. do. In other embodiments, R ² , R ^3, and R ⁴ are the same and consist of a phospholane, a phospholane, or a phosphole.

In another embodiment, there is provided an ionic liquid composition comprising at least one phosphonium cation and at least one anion, wherein the ionic liquid composition has a thermodynamic stability of greater than 375 DEG C, a liquidus line range of greater than 400 DEG C, And an ionic conductivity of 10 mS / cm or less.

In another aspect, the present invention includes an electrolyte composition comprised of a phosphonium-based cation with an appropriate anion. In some embodiments, the terms "electrolyte" or "electrolyte" or "electrolyte composition" or "ionic electrolyte" or "ionic conductive electrolyte" or "ionic conductive composition" or "ionic composition" Is defined as one or more of the following in the specification: (a) an ionic liquid, (b) a room temperature ionic liquid, (c) at least one salt dissolved in at least one solvent, and (d) at least one One or more salts which are dissolved in a solvent to form a gel electrolyte. In addition, the at least one salt is defined as comprising: (a) one or more salts that are solid at a temperature of less than or equal to 100 占 폚; and (b) one or more salts that are liquid at a temperature of less than or equal to 100 占 폚.

In another embodiment, the at least one salt is composed of at least one salt dissolved in a solvent, wherein the at least one salt is a phosphonium cation of the general formula: And an electrolyte composition comprising at least one anion are provided:

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ^3, and R ⁴ are each independently a substituent, for example, but not limited to, an alkyl group as described later. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group comprised of 1 to 6 carbon atoms, more typically 1 to 4 carbon atoms. The one or more salts may all be liquid or solid at a temperature of less than or equal to 100 < 0 > C. In some embodiments, the salt is composed of one cation and one anion pair. In other embodiments, the salt consists of one cation and multiple anions. In other embodiments, the salt consists of one anion and a plurality of cations. In further embodiments, the salt is comprised of a plurality of cations and a plurality of anions.

In another embodiment, the electrolyte composition further comprises at least one conventional non-phosphonium salt. In some embodiments, the electrolyte composition can be composed of conventional salts, and the phosphonium ionic liquids or salts disclosed herein are additives. In some embodiments, the electrolyte composition is comprised of a phosphonium ionic liquid or salt and one or more conventional salts, which are in the range of 1: 100 to 1: 1 phosphonium ionic liquid or salt: Mol (or molar) ratio. Conventional salts Examples _{include, CH 3 CH 2) 4 N} +, (CH 3 CH 2) 3 (CH 3) N +, (CH 3 CH 2) 2 (CH 3) 2 N +, (CH 3 CH 2) (CH ₃ ) ₃ N ⁺ , (CH ₃ ) ₄ N ⁺ from the group consisting of tetraalkylammonium, imidazolium, pyrazolium, pyridinium, pyranidinium, pyrimidinium, pyridazinium, pyrrolidinium At least one cation selected; And ^{_{ClO 4 -, BF 4 -,}} CF 3 SO 3 -, PF 6 -, AsF 6 -, SbF 6 - 2 N, (CF 3 CF 2 SO 2) - -, (CF 3 SO 2) 2 N, ( CF ₃ SO ₂ ) ₃ C ^- , and the like. In some embodiments, one or more conventional salts include, but are not limited to, tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), 1- Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-ethyl-1-methylpyrrolidinium tetrafluoroborate (EMPBF ₄ ) Romero tansul sulfonyl) imide (EMIIm), phosphate (EMIPF ₆₎ 1-ethyl-3-methylimidazolium hexafluoro. In some embodiments, the at least one conventional salt is a lithium-based salt including, but not limited to, lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ) Lithium perchlorate (LiClO ₄ ), lithium hexafluoroacetate (LiAsF ₆ ), lithium trifluoromethanesulfonate or lithium triflate (LiCF ₃ SO ₃ ), lithium bis (trifluoromethanesulfonyl) imide (Li (CF ₃ SO _{2) 2} N or LiIm) and lithium bis (pentafluoroethyl methanesulfonyl) imide _{(Li (CF3CF 2 SO 2)} 2 N or LiBETI).

Additional aspects of the present invention include a positive electrode; cathode; A separator between the anode and the cathode; And an electrolyte. The electrolyte being comprised of an ionic liquid composition or one or more salts dissolved in a solvent; Wherein the at least one ionic liquid composition or salt comprises at least one phosphonium cation and at least one anion of the following general formula:

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In one embodiment, the electrolyte is comprised of an ionic liquid having at least one phosphonium-based cation and at least one anion, the ionic liquid composition having a thermodynamic stability to 375 DEG C, a liquidus line range of greater than 400 DEG C, At least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm. In other embodiments, the electrolyte is comprised of at least one phosphonium cation dissolved in a solvent and at least one salt having at least one anion, wherein the electrolyte composition has a conductivity of at least 5 mS / cm, or at least 10 mS / cm, or at least 15 mS / cm, or at least 20 mS / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm. In a further aspect, the phosphonium electrolyte reduces flammability as compared to conventional electrolytes, thereby improving the safety of battery operation. In a further aspect, the phosphonium ionic liquid or salt may be used as an additive to facilitate the formation of a soild electrolyte interphase (SEI) layer or electrode protection layer. The SEI layer can broaden the electrochemical stability range, inhibit the deterioration or decomposition reaction of the battery, and thereby improve the battery cycle life.

Further embodiments of the present invention include a positive electrode; cathode; A separator between the anode and the cathode; And an electrolyte; and an electrochemical double layer capacitor (EDLC). The electrolyte comprises an ionic liquid composition comprising at least one phosphonium cation and at least one anion of the following general formula or at least one salt dissolved in a solvent:

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In one embodiment, the electrolyte is comprised of an ionic liquid having at least one phosphonium-based cation and at least one anion, wherein the ionic liquid composition or salt has a thermodynamic stability to 375 DEG C, a liquidus line range of greater than 400 DEG C, And at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm at room temperature. In other embodiments, the electrolyte is comprised of at least one phosphonium cation dissolved in a solvent and at least one salt having at least one anion, wherein the electrolyte composition has a conductivity of at least 5 mS / cm, or at least 10 mS / cm, or at least 15 mS / cm, or at least 20 mS / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm. In a further aspect, the phosphonium electrolyte reduces flammability compared to conventional electrolytes and thus improves the safety of EDLC operation. In a further aspect, the phosphonium ionic liquid or salt may be used as an additive to facilitate formation of a solid electrolyte interface (SEI) layer or electrode protection layer. Without wishing to be bound by any particular theory, the inventors believe that the protective layer can broaden the electrochemical stability range, inhibit the EDLC deterioration or decomposition reaction, and thereby improve the EDLC cycle life.

Embodiments of the present invention further provide a heat transfer medium comprising an ionic liquid composition or one or more salts dissolved in a solvent, wherein the heat transfer medium comprises at least one phosphonium cation and at least one anion, Thermodynamic stability at temperature, liquid-line range exceeding 400 ° C.

The phosphonium ionic liquid compositions and salts are useful in forming a variety of hybrid electronic devices. For example, in one embodiment, a first electrode; A second electrode; And one or more phosphonium cations of the formula: And an electrolyte composed of an ionic liquid composition or one or more salts dissolved in a solvent comprising at least one anion,

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. Here, the electrolyte is electrically coupled to at least one of the first electrode and the second electrode. In some embodiments, the first electrode is comprised of a redox active molecule (ReAM).

In another embodiment, a working electrode and a counter electrode configured to provide an electrical capacitance; And an ion conductive composition comprising at least one phosphonium cation of the above general formula, wherein the ion conductive composition is at least electrically coupled to the working electrode and the counter electrode.

 In another embodiment, the present invention provides a device comprising a switching device, a molecule comprising a bit line coupled to the switching device and a word line (word line) and a molecular storage device accessible via the switching device. Memory device. The molecular storage device may be disposed in two or more discrete, wherein the molecular storage device may be placed in one of the bit lines and the discrete state by a signal applied to the word line. The molecular reservoir includes a first electrode, a second electrode, and an electrolyte of a phosphonium-based cation and a suitable anion between the first electrode and the second electrode.

Another embodiment includes a molecular memory array comprising a plurality of molecular storage elements, wherein each molecular storage element can be placed in two or more discrete states. Each of the molecular storage elements is coupled to at least one bit line and at least one word line, and a plurality of bit lines and word lines are coupled to the plurality of molecular storage elements so as to be addressable.

Other aspects, embodiments and advantages of the present invention will become apparent from the detailed description of the invention, Taken in conjunction with the appended claims and the accompanying drawings.
1 is a cross-sectional view of an electrochemical double layer capacitor (EDLC) according to one embodiment of the present invention.
2A and 2B are cross-sectional views of a bipolar electrode and an EDLC multi-cell stack structure according to an embodiment of the present invention.
Figure 3 shows one scheme for forming a phosphonium ionic liquid according to some embodiments of the present invention.
Figure 4 shows another scheme to form other embodiments of the phosphonium ionic liquid of the present invention.
Figure 5 illustrates another scheme for forming a phosphonium ionic liquid according to other embodiments of the present invention.
Figure 6 illustrates another scheme for forming a phosphonium ionic liquid in accordance with further embodiments of the present invention.
FIG. 7 is a thermogravimetric analysis (TGA) graph performed for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 1. FIG.
8A shows a reaction scheme for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 2, and FIGS. 8B and 8C are respectively a thermogravimetric analysis (TGA) and an evolved gas analysis (EGA) FIG.
9A and 9B are graphs showing thermogravimetric analysis (TGA) and product gas analysis (EGA) for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 3, respectively.
FIG. 10a shows the reaction formulas of exemplary embodiments of the phosphonium ionic liquids prepared as described in FIG. 4 and Example 4, and FIG. 10b shows ¹ H NMR spectra.
FIG. 11A is a reaction formula of exemplary embodiments of a phosphonium ionic liquid prepared according to Example 5, and FIG. 11B is a graph showing a result of thermogravimetric analysis (TGA). FIG.
12 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of a phosphonium ionic liquid prepared according to Example 6. FIG.
13 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of a phosphonium ionic liquid prepared according to Example 7. FIG.
FIG. 14A shows a reaction scheme of exemplary embodiments of a phosphonium ionic liquid prepared according to Example 8, and FIG. 14B is a graph showing thermogravimetric analysis (TGA) results.
15A and 15B show ¹ H and ³¹ P NMR spectra for exemplary embodiments of the phosphonium salt prepared as described in Example 9, respectively.
16 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of the phosphonium salt prepared according to Example 9. FIG.
17A and 17B show ¹ H and ³¹ P NMR spectra for exemplary embodiments of the phosphonium salt prepared as described in Example 10, respectively.
18 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of the phosphonium salt prepared according to Example 10. FIG.
Figures 19A and 19B show ¹ H and ³¹ P NMR spectra for an exemplary embodiment of a phosphonium salt prepared as described in Example 11, respectively.
20 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of the phosphonium salt prepared according to Example 11. FIG.
FIGS. 21A and 21B are graphs showing differential scanning calorimetry (DSC) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 12. FIG.
22 is a graph showing the ionic conductivity of a phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ in acetonitrile (ACN) / ≪ / RTI > volume ratio.
23 is a graph showing the ionic conductivity of a phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ in propylene carbonate (PC) / ≪ / RTI > volume ratio.
Figure 24 shows the ionic conductivity as a function of molar concentration with respect to the phosphonium salt compared to the ammonium salt in propylene carbonate as described in Examples 42-45.
Figure 25 shows the vapor pressures of acetonitrile as described in Example 46, acetonitrile with a 1.0 M ammonium salt, and acetonitrile with a 1.0 M phosphonium salt as a function of temperature.
Figure 26 is an embodiment in a variety of temperatures of -30 to 60 ℃ as described in 51 EC: DEC 1: phosphonium salt for ion conductivity of 1.0 M LiPF6 in _{1 (CH 3 CH 2 CH 2} ) (CH 3 CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ .
27 is from 20 to various temperatures of 90 ℃ as described in Example 52 EC: DEC 1: phosphonium salt for ion conductivity of 1 of _{1.0 M LiPF6 (CH 3 CH 2} CH 2) (CH 3 CH 2 ) (CH ₃ ) ₂ PCF ₃ BF ₃ .
28 is a cross-sectional view of an EDLC coin cell according to one embodiment of the present invention as described in Example 53;
29 is a polypropylene 1.0 M phosphonium salt of carbonate, as described in Example _{53 - (CH 3 CH 2 CH} 2) (CH 3 CH 2) (CH 3) Charging for a coin cell having a ₂ CF ₃ F ₃ - Show the discharge curves.
30A is a cross-sectional view of an EDLC pouch cell according to one embodiment of the present invention as described in Examples 54-57.
FIG. 30B illustrates a manufacturing process of an EDLC pouch cell according to an embodiment of the present invention as described in Examples 54 to 57. FIG.
Figure 31a is an embodiment of the propylene carbonate as described in the 54 to 57 1.0 M phosphonium salt _{- (CH 3 CH 2 CH 2} ) (CH 3 CH 2) (CH 3) a pouch cell having a ₂ CF ₃ F ₃ Shows the charge-discharge curve.
FIG. 31B shows the carbon positive electrode as measured with a silver reference electrode as described in Examples 54 to 57 and the separated electrode potential at the carbon negative electrode.
32 is an exploded view of an EDLC cylindrical cell according to an embodiment of the present invention as described in Example 58;
33 is Example 58. The 1.0 M phosphonium salt in propylene carbonate as described in the _{- (CH 3 CH 2 CH 2} ) (CH 3 CH 2) (CH 3) on a cylindrical cell having a ₂ CF ₃ F ₃ The charge-discharge curve is shown.
Figure 34 shows the results of a comparison of the 2.7 < RTI ID = 0.0 > and 70 < / RTI > of pouch cells with 1.0 M phosphonium salt as compared to the ammonium salt in propylene carbonate as described in Examples 59-61. ^o Capacitance retention at C is shown.
Figure 35 shows the capacitance retention at various temperatures of a pouch cell having a 1.0 M phosphonium salt as compared to the ammonium salt in propylene carbonate as described in Example 62.

generalization

The present invention relates generally to phosphonium ionic liquids, salts and compositions and their use in a variety of applications.

General description

The present invention includes, but is not limited to, novel phosphonium ionic liquids, salts, compositions and their use in a variety of applications, including, but not limited to, those found in electronic devices such as memory devices including static, permanent and dynamic random access memories Electrolyte; Batteries, electrochemical double layer capacitors, electrolytic capacitors, dye-sensitized solar cells and electrochromic devices. Additional applications include, among other applications, heat transfer media, high temperature reactions, and / or use as extraction media. In particular, the present invention relates to phosphonium ionic liquids, salts, compositions and molecules having structural characteristics, wherein said composition is a composition comprising at least two of the following: thermodynamic stability, low volatility, broad liquid line range, ionic conductivity and electrochemical stability Combination. The present invention further comprises a process for the preparation of such phosphonium ionic liquids, compositions and molecules and an operating device and system comprising the same.

In another aspect, embodiments of the present invention provide an apparatus having an electrolyte comprising a phosphonium ionic liquid composition or one or more salts dissolved in a solvent. In another aspect, embodiments of the present invention provide a cell comprising an electrolyte comprising a phosphonium ionic liquid composition or one or more salts dissolved in a solvent. In a further aspect, embodiments of the present invention provide electrochemical double layer capacitors (EDLC) comprising an electrolyte composed of a phosphonium ionic liquid composition or one or more salts dissolved in a solvent.

The advantageous properties of the phosphonium ionic liquid composition are particularly suitable for use as electrolytes in electronic devices, batteries, EDLC, fuel cells, dye-sensitized solar cells (DSSC) and electrochromic devices.

In a further aspect of the present invention, there is provided a heat transfer medium comprising a phosphonium ionic liquid composition or one or more salts dissolved in a solvent. Advantageous properties of the compositions of the present invention are very suitable as heat transfer media and are useful in processes and systems where heat transfer media such as heat extraction processes and high temperature reactions are used.

Justice

In this specification, unless otherwise indicated, the terms "electrolyte" or "electrolyte" or "electrolyte composition" or "ionic electrolyte" or "ionically conductive electrolyte" or "ionically conductive composition" or "ionic composition" , Which is defined herein as one or more of: (a) an ionic liquid, (b) a room temperature ionic liquid, (c) at least one salt dissolved in at least one solvent, and (d) at least one polymer At least one salt that is dissolved in at least one solvent to form a gel electrolyte. In addition, the at least one salt is defined as comprising: (a) one or more salts that are solid at a temperature of less than or equal to 100 占 폚; and (b) one or more salts that are liquid at a temperature of less than or equal to 100 占 폚.

Unless otherwise indicated, the term "acyl" refers to an organic acid group (RCO-) in which the OH of the carboxyl group is replaced by some other substituent described herein as the "R" substituent. Include, but are not limited to, halo, acetyl, and benzoyl.

In this specification, unless otherwise indicated, "alkoxy group" means an -O-alkyl group, wherein the alkyl group is as defined herein. The alkoxy group may be unsubstituted or substituted with one, two or three suitable substituents. Preferably, the alkyl chain of the alkoxy group is 1 to 6 carbon atoms in length and is referred to herein as, for example, "(CrC6) alkoxy ".

As used herein, unless otherwise indicated, the term "alkyl group", by itself or as part of another substituent, refers to a saturated or unsaturated, saturated or unsaturated, saturated or unsaturated, saturated or unsaturated, Quot; refers to branched, straight-chain or cyclic monovalent hydrocarbon radicals. Also included in the definition of alkyl groups are cycloalkyl groups such as C5, C6 or other rings and heterocyclic rings (heterocycloalkyl) having nitrogen, oxygen, sulfur or phosphorus. Alkyl groups also include heteroalkyl groups having heteroatoms such as sulfur, oxygen, nitrogen, phosphorus, and silicon used in certain applications in certain embodiments. The alkyl group may be optionally substituted with an R group, and the R group is independently selected at each position described below.

Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl, Butyl, 2-methyl-3-butyl, 2,2-dimethyl-1 -propyl, Methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl , (C1-C6) alkyl groups such as t-butyl, pentyl, isopentyl, neopentyl and hexyl; And longer alkyl groups such as heptyl and octyl.

The term "alkyl" refers to a group having any degree of saturation or saturation level, i.e., a group having only a carbon-carbon single bond, a group having at least one carbon-carbon double bond, , A group having a mixture of double and triple carbon-carbon bonds. When a particular saturation level is intended, the expressions "alkanyl", "alkenyl" and "alkynyl" are used.

"Alkynyl" by itself or as part of another substituent refers to a saturated branched chain, straight chain or cyclic alkyl radical derived from the removal of one hydrogen atom from a single carbon atom of the parent alkane. Includes "heteroalkanyl" as defined above.

"Alkenyl" by itself or as part of another substituent refers to an unsaturated branched chain, straight chain or cyclic alkyl radical derived from the removal of one hydrogen atom from a single carbon atom of the parent alkene. And may be cis or trans configuration (conformation) with respect to the alkenyl group double bond (s). Suitable alkenyl groups include but are not limited to (C2-C6) alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, 2- Ethylhexenyl, 2-propyl-2-butyl, 4- (2-methyl-3-butene) -pentenyl. The alkenyl group may be unsubstituted or substituted with one or more R groups selected independently.

"Alkynyl" by itself or as part of another substituent refers to an unsaturated branched chain having at least one carbon-carbon triple bond derived from the removal of one hydrogen atom from a single carbon atom of the parent alkyne, a linear or cyclic alkyl radical Quot;

The term "alkyl" also includes "substituted alkyl ". "Substituted" refers to a group denoted herein as "R" wherein one or more hydrogen atoms are independently replaced with the same or different substituent (s). The R substituent may be independently selected from the group consisting of hydrogen, halogen, alkyl (including substituted alkyl (alkylthio, alkylamino, alkoxy, etc.), cycloalkyl, substituted cycloalkyl, cycloheteroalkyl and substituted cycloheteroalkyl (Including substituted aryl, heteroaryl or substituted heteroaryl), carbonyl, alcohol, amino, amido, nitro, ether, ester, aldehyde, sulfonyl, sulfoxyl, carbamoyl, acyl , Cyano, thiocyanato, silicon moieties, halogens, sulfur containing moieties, phosphorous containing moieties, and the like. In some embodiments, as described herein, the R substituent comprises redox active moieties (ReAMs). In some embodiments, optionally, R and R 'together with the atoms to which they are attached form a cycloalkyl (including cycloheteroalkyl) and / or a cycloaryl (including cycloheteroaryl) May be further substituted as desired. In the structure depicted herein, R is hydrogen when the position is unsubstituted. It should be noted that some positions may allow R, R 'and R "as two or three substituents, in which case the R, R' and R" groups may be the same or different.

In some embodiments, the R group (subunit) is used to adjust the redox potential (s) of the compound of interest. Thus, as is more fully described below and in the references cited herein, the R group, such as a redox active subunit, can have a macrocycle, in particular, Porphyrin can be added to the macrocycle. Specific preferred substituents include, but are not limited to, 4-chlorophenyl, 3-acetamidophenyl, 2,4-dichloro-4-trifluoromethyl, and ferrocene (including ferrocene derivatives). When such substituents are used to change the redox potential, the preferred substituents provide an oxidation-reduction potential range of less than about 5 volts, preferably less than about 2 volts, more preferably less than about 1 volt.

In certain embodiments, the R group is as defined and shown in the drawings and text of US Provisional Application No. 60 / 687,464, incorporated herein by reference. Numerous suitable proligand and complexes as well as suitable substituents are disclosed in U.S. Patent Nos. 6,212,093; 6,728,129; 6,451, 942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484, 394; And U.S. Serial No. 040,059; 10 / 682,868; 10 / 445,977; 10 / 834,630; 10 / 135,220; 10 / 723,315; 10 / 456,321; 10 / 376,865, both of which are expressly incorporated by reference. In particular, the structures and descriptions shown in these documents are expressly incorporated as substitutable implementations for all of the specific macrocycle substituents and additionally substituted derivatives shown herein.

The term "aryl" or grammatical equivalents herein refers to an aromatic monocyclic or polycyclic hydrocarbon moiety generally containing 5 to 14 carbon atoms (although of course it may be a larger polycyclic ring structure, of course) Means any carbocyclic ketone derivative, imine derivative or thioketone derivative in which the carbon atom having a free valence is a member of an aromatic ring. The aromatic group includes an arylene group and an aromatic group in which two or more atoms are removed. For purposes of the present application, aryl includes heteroaryl. "Heteroaryl" means an aromatic group wherein the indicated one to five carbon atoms are replaced by a heteroatom selected from nitrogen, oxygen, sulfur, phosphorus, boron and silicon, and the atoms having a free valence are replaced by an aromatic ring and any hetero Cyclic ketone derivatives and thioketone derivatives. Heterocycles thus include both single ring and multiple ring systems and include, for example, thienyl, furyl, pyrroyl, pyrimidinyl, indolyl, purinyl, quinolyl, isoquinolyl, thiazolyl, imida Naphthalene, phenanthroline, and the like. Also included in the definition of aryl is aryl, as defined herein and substituted with one or more substituents "R" as described above. Includes, for example, "perfluoroaryl" and refers to an aryl group in which all hydrogen atoms are replaced by fluorine atoms. Oxalic diaries are also included.

As used herein, the term "halogen " refers to one of the electronegative elements of the VIIA family of the periodic table (fluorine, chlorine, bromine, iodine and astatine).

The term "nitro" refers to the group -NO ₂ .

"Amino group" or grammatical equivalents herein means -NH2, -NHR and -NRR 'groups, and R and R' are independently as defined herein.

As used herein, the term "pyridyl" refers to an aryl group in which the CH unit is replaced by a nitrogen atom.

As used herein, the term "cyano" refers to a -CN group.

As used herein, the term "thiocyanato" refers to a -SCN group.

Refers to a group of the formula RS (O) - wherein R is a substituent as defined herein, such as alkyl, (cycloalkyl, perfluoroalkyl, etc.) or aryl (e.g., perfluoro Aryl group). Examples include, but are not limited to, methylsulfolyl, phenylsulfoxyl, and the like.

The term "sulfonyl" refers to a group of the formula RSO2-, wherein R has as substituent as defined herein alkyl, aryl, (including cycloalkyl, perfluoroalkyl or perfluoroaryl groups). Examples include, but are not limited to, methylsulfonyl, phenylsulfonyl, p-toluenesulfonyl, and the like.

The term "carbamoyl" refers to the group of the formula R (R ') NC (O) - wherein R and R' are as defined herein and include, N, N-dimethylcarbamoyl, and the like.

The term "amido" refers to a group of the formula R ₁ CONR ₂ -, wherein R ₁ and R ₂ are substituents as defined herein. Examples include, but are not limited to, acetamido, N-ethylbenzamido, and the like.

The term "immune" refers to = NR.

In certain embodiments, when the metal is denoted, for example, as "M" or "Mn" (where n is an integer), the metal may be recognized as associated with a counterion .

In this specification, unless otherwise indicated, the term "amperometric device" is a device capable of measuring the current generated in an electrochemical cell by applying a specific field potential (" .

In this specification, unless otherwise indicated, the term "aryloxy group" means an -O-aryl group, wherein aryl is as defined herein. The aryloxy group may be unsubstituted or substituted with one or two suitable substituents. Preferably, the aryl ring of the aryloxy group is a monocyclic ring containing 6 carbon atoms, which is referred to as "(C6) aryloxy. &Quot;

In this specification, unless otherwise indicated, the term "benzyl " means-CH2-phenyl.

In this specification, unless otherwise indicated, the term "carbonyl" group is a divalent group of the formula -C (O) -.

Unless otherwise indicated, the term "coulometric device " refers to a device that measures the net charge generated during the application of a potential field (" voltage ") to an electrochemical cell It is a device that can do.

In this specification, unless otherwise indicated, the term "cyano" refers to a -CN group.

As used herein, unless otherwise indicated, the term " different and distinguishable " as used to refer to two or more oxidation states refers to the net charge for the whole (atom, molecule, aggregate, subunit, etc.) ≪ / RTI > This state is referred to as "distinguishable" if the difference in state of action is greater than the thermal energy at room temperature.

In the present specification, unless otherwise indicated, the term "E _1/2" is a practical definition of the type of the oxidation-reduction potential of the process _{(formal potential) (E 0)} , E = E 0 + (RT / nF) ln (D _oxidation / D _reduction ). Where R is the gas constant, T is the temperature (K), n is the number of electrons involved in the process, F is the Faraday constant (96,485 coulombs per mole), D _oxidation is the oxidation of the species and diffusivity (diffusion coefficient), D is the diffusion coefficient of _reduced species undergoing reduction.

In this specification, unless otherwise indicated, the term "electrically coupled ", when referring to storage molecules and / or storage media and electrodes, means that electrons are transferred from the storage medium / Refers to an association between a molecule and an electrode or a storage medium that moves from the electrode to the storage medium / molecule and thereby changes the oxidation state of the storage medium / molecule. The electrical coupling may be a direct linkage between the storage medium / molecule and the electrode, an indirect shared coupling (e.g. via a linker), a direct or indirect ionic bond between the storage medium / molecule and the electrode , Or other bonds (e. G., Hydrophobic bonds). In addition, practical coupling may not be required, and the storage medium / molecule may simply be in contact with the electrode surface. Also, if the electrode is sufficiently close to the storage medium / molecule and it is possible to tunnel electronically between the medium / molecule and the electrode, contact between the electrode and the storage medium / molecule is not necessary.

As used herein, unless otherwise indicated, the term "electrochemical cell" encompasses, at a minimum, a reference electrode, a working electrode, a redox active medium (eg, a storage medium) (E. G., Dielectric) for providing electrical conductivity. In some embodiments, the dielectric is a component of the storage medium.

As used herein, unless otherwise indicated, the term "electrode" refers to any medium capable of transporting charge (e.g., electrons) from and / or to a storage molecule. A preferred electrode is a metal or a conductive organic molecule. The electrodes can be fabricated in almost any two-dimensional or three-dimensional shape (e.g., discrete lines, pads, planes, spheres, cylinders).

In this specification, unless otherwise indicated, the term "fixed electrode" is intended to reflect the fact that it is an essentially stable, immovable electrode for the storage medium. That is, the electrodes and the storage medium are arranged in an essentially fixed geometric relationship with each other. Of course, this relationship is perceived to be somewhat altered due to expansion and contraction of the medium as a result of thermal changes or due to changes in the shape of the electrodes and / or storage medium comprising the molecules. Nevertheless, the overall spatial layout is essentially unchanged.

In this specification, unless otherwise indicated, the term "linker" is a molecule used to couple two different molecules, two molecular subunits or molecules to a substrate.

Many of the compounds described herein employ substituents that are generally described herein as "R ". Suitable R groups include but are not limited to hydrogen, alkyl, alcohol, aryl, amino, amido, nitro, ether, ester, aldehyde, sulfonyl, silicon moiety, halogen, cyano, acyl, Phosphorus containing moieties, Sb, imido, carbamoyl, linkers, attachment moieties, ReAM, and other subunits. Some sites may allow R and R 'as two substituents, in which case the R and R' groups may be the same or different, and it is generally noted that one of the substituents is preferably hydrogen. In some embodiments, the R groups are the same as defined and described in the drawings and texts of the United States. Numerous suitable proligand and complexes as well as suitable substituents are disclosed in U.S. Patent Nos. 6,212,093; 6,728,129; 6,451, 942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484, 394; And U.S. Serial No. 040,059; 10 / 682,868; 10 / 445,977; 10 / 834,630; 10 / 135,220; 10 / 723,315; 10 / 456,321; 10 / 376,865, both of which are expressly incorporated by reference. In particular, the structures and descriptions shown in these documents are expressly incorporated as substitutable implementations for all of the specific macrocycle substituents and additionally substituted derivatives shown herein.

In this specification, unless otherwise indicated, the term "subunit " refers to the redox active ingredient of the molecule.

The Phosphonium  Ionic liquids, salts and compositions

As described in detail herein, embodiments of the novel phosphonium ionic liquids, salts, and compositions of the present invention have desirable properties, particularly high thermodynamic stability, low volatility, broad liquid line range, And a stability range. In some embodiments, it has been unexpected that the combination of all of these properties in one composition is at a desirable level and provides significant advantages over known ionic compositions. Embodiments of the present phosphonium compositions exhibiting these properties enable applications and devices not previously available.

In some embodiments, the phosphonium ionic liquid of the present invention comprises a phosphonium cation of a selected molecular weight and substitution pattern, and the selected anion (s) coupled thereto, thereby providing thermodynamic stability, ionic conductivity, To form an ionic liquid having an adjustable combination of volatility characteristics.

In some embodiments, "ionic liquid" as used herein refers to a salt that is in a liquid state at 100 占 폚 or lower. As used herein, the "room temperature" ionic liquid is further defined as being a salt that is liquid at room temperature or lower.

In some embodiments, the terms "electrolyte" or "electrolyte" or "electrolyte composition" or "ionic electrolyte" or "ionic conductive electrolyte" or "ionic conductive composition" or "ionic composition" Is defined herein as one or more of the following: (a) an ionic liquid, (b) a room temperature ionic liquid, (c) at least one salt dissolved in at least one solvent, and (d) at least one (A) one or more salts that are solid at a temperature of 100 DEG C or less, and (b) one or more salts that are solid at 100 DEG C or less and 100 DEG C or less At < / RTI >

In some embodiments, the present invention includes a phosphonium ionic liquid and a phospho electrolyte that exhibits thermodynamic stability to a temperature of up to about 400 ° C, and more typically about 375 ° C. It is a significant development to exhibit thermal stability to such a high temperature, which allows the phosphonium ionic liquid of the present invention to be used in a wide range of applications. Embodiments of the phosphonium ionic liquids and phosphonium electrolytes of the present invention may be at least at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm, or at least 15 mS / cm, / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm. Embodiments of the phosphonium ionic liquids and phosphonium electrolytes of the present invention exhibit about 20% lower volatility compared to their nitrogen based analogs. This combination of high thermal stability, high ionic conductivity, wide liquid line range and low volatility is highly desirable and unexpected. Generally, in the prior art, the thermal stability and ionic conductivity of ionic liquids are found to exhibit inverse relationships.

In some embodiments, the phosphonium ionic liquid and the phosphonium electrolyte are comprised of a cation having a molecular weight of less than or equal to 500 daltons. In other embodiments, in the case of ionic liquids with a lower thermal stability range, the phosphonium ionic liquid and the phosphonium electrolyte are composed of cations having a molecular weight in the range of 200 to 500 daltons.

The phosphonium ionic composition of the present invention is composed of a phosphonium-based cation represented by the following general formula:

R ¹ R ² R ³ R ⁴ P (1)

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In some embodiments, the cation is comprised of an open chain.

In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group. In one embodiment, at least one alkyl group is different from the other two alkyl groups. In one embodiment, none of the alkyl groups is methyl. In some embodiments, the alkyl group consists of 2 to 7 carbon atoms, more typically 1 to 6 carbon atoms. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently a different alkyl group consisting of 2 to 14 carbon atoms. In some embodiments, the alkyl group does not include a branch. In one embodiment, R ¹ = R ² and is an aliphatic, heterocyclic moiety. Alternatively, R ¹ = R ² and is an aromatic, heterocyclic moiety.

In some embodiments, R ¹ or R ² is comprised of phenyl or substituted alkylphenyl. In some embodiments, R ¹ and R ² are the same and are composed of tetramethylene (phospholane) or pentamethylene (phospholane). Alternatively, R ¹ and R ² are the same and are composed of tetramethynyl (phosphol). In a further embodiment, R ¹ and R ² are the same and are comprised of a phospholane or a phospholane. Additionally, in other embodiments, R ² , R ^3, and R ⁴ are the same and consist of a phospholane, a phosphorolane, or a phosphole.

In some embodiments, at least one or both of R ¹ , R ² , R ^3, and R ⁴ are each selected so as not to contain a functional group capable of reacting with a redox active molecule (ReAM) described below. In some embodiments, at least one, more, or all of R ¹ , R ² , R ^3, and R ⁴ do not contain halide, metal or O, N, P, or Sb.

In some embodiments, the alkyl group contains 1 to 7 carbon atoms. In other embodiments, the total carbon atoms from all alkyl groups are 12 or less. In yet other embodiments, the alkyl groups are each independently comprised of 1 to 6 carbon atoms, more typically 1 to 5 carbon atoms.

In another embodiment, the at least one salt is composed of at least one salt dissolved in a solvent, wherein the at least one salt is at least one phosphonium cation of the general formula: And a phosphonium ionic composition comprising at least one anion:

R ¹ R ² R ³ R ⁴ P (1)

Here, R ¹ , R ² , R ^3, and R ⁴ are each independently a substituent, for example, but not limited to, an alkyl group as described later. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group comprised of one to six carbon atoms, more typically one to four carbon atoms. In some embodiments, at least one of the one or more R groups is substituted with fluorine. The one or more of the salts may all be liquid or solid at a temperature of 100 DEG C or lower. In some embodiments, the salt consists of one cation and one anion. In other embodiments, the salt consists of one cation and a number of anions. In other embodiments, the salt consists of one anion and a plurality of cations. In further embodiments, the salt is comprised of a plurality of cations and a plurality of anions. Exemplary embodiments of suitable solvents include but are not limited to acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC) (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinylethylene carbonate (VEC) , Phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), gamma -butyrolactone (GBL) 0.0 > (GVL). ≪ / RTI >

In an exemplary embodiment, the phosphonium cation is composed of the following formula:

In another exemplary embodiment, the phosphonium cation is composed of the following formula:

In another exemplary embodiment, the phosphonium cation is composed of the following formula:

In a further exemplary embodiment, the phosphonium cation is composed of the following formula:

In a further exemplary embodiment, the phosphonium cation is composed of the following formula:

In a further exemplary embodiment, the phosphonium cation is composed of the following formula:

In a further exemplary embodiment, the phosphonium cation is composed of the following formula:

In another exemplary embodiment, the phosphonium cation is composed of the following formula:

In a further exemplary embodiment, the phosphonium cation is composed of the following formula:

In another exemplary embodiment, the phosphonium cation is composed of the following formula:

In another exemplary embodiment, the phosphonium cation is composed of the following formula:

Another exemplary embodiment provides a phosphonium cation of the formula:

In addition, there is provided a phosphonium cation of the formula:

In some embodiments, examples of suitable phosphonium cations include, but are not limited to, di-n-propylethylphosphonium; n-butyl n-propylethylphosphonium; n-hexyl n-butyl ethyl phosphonium; And the like.

In other embodiments, examples of suitable phosphonium cations include, but are not limited to, ethylphospholane; n-propylphospholane; n-butylphospholane; n-hexylphospholane; And phenylphospholanes.

In further embodiments, examples of suitable phosphonium cations include, but are not limited to, ethyl phosphol; n-propylphosphole, n-butylphosphole; n-hexylphosphole; And phenylphosphole.

In other embodiments, examples of suitable phosphonium cations include, but are not limited to, 1-ethylphosphacyclohexane; n-propylphosphacyclohexane; n-butylphosphacyclohexane; n-hexylphosphacyclohexane; And phenylphosphacyclohexane.

The phosphonium ionic liquid or salt of the present invention consists of a cation and an anion. It will be appreciated by those of ordinary skill in the art that there is a wide variety of possible combinations of cations and anions. The phosphonium ionic liquid or salt of the present invention comprises anions generally selected from compounds which are readily ion-exchanged with the abovementioned cations and reagents or solvents of the formula:

C ⁺ A ^-

Here, C ⁺ is a cation and A ⁺ is an anion. In the example of the organic solvent, C ⁺ is preferably Li ⁺ , K ⁺ , Na ⁺ , NH ₄ ⁺ or Ag ⁺ . In the example of an aqueous liquid, C ⁺ is preferably Ag ⁺ .

Many negative ions can be selected. In a preferred embodiment, the anion is bis-perfluoromethylsulfonyl imide. Exemplary embodiments of suitable anions include, but are not limited to, NO ₃ ^- , O ₃ SCF ₃ ^- , N (SO ₂ CF ₃ ) ₂ ^- , PF ₆ ^- , O ₃ SC ₆ H ₄ CH ₃ ^- , O ^{_{3 SCF 2 CF 2 CF 3 -}} , O 3 SCH 3 -, I -, C (CN) 3 -, - O 3 SCF 3, - N (SO 2) 2 CF 3, CF 3 BF 3 -, - O 3 It includes N (CN) than any one of ^{_{2 - SCF 2 CF 2 CF 3}} , SO 4 2-, - O 2 CCF 3, - O 2 CCF 2 CF 2 CF 3 or.

In some embodiments, the phosphonium ionic liquid or salt of the present invention is comprised of a single cation-anion pair. Alternatively, two or more phosphonium ionic liquids or salts may be used to form a common binary, a mixed binary, a common ternary, a mixed ternary system, and the like. The composition ranges of the binary and ternary systems can range from 1 ppm to 999,999 ppm for each constituent cation and each constituent anion. In another embodiment, the phosphonium electrolyte is composed of one or more salts dissolved in a solvent, and the salts may be liquid or solid at a temperature of 100 ° C. In some embodiments, the salt consists of a single cation-anion pair. In other embodiments, the salt consists of one cation and a number of anions. In other embodiments, the salt consists of one anion and a plurality of cations. In yet other embodiments, the salt comprises a plurality of cations and a plurality of anions.

Electrolyte compositions according to some embodiments of the present invention are described further in co-pending U.S. Patent Application No. ______________________________________________ (Attorney Docket No. 057472-058), filed concurrently herewith, the entire disclosure of which is incorporated herein by reference Lt; / RTI >

In a preferred embodiment, the phosphonium ionic liquid composition consists of a combination of cations and anions as shown in Tables 1A and 1B below. In another preferred embodiment, the phosphonium electrolyte consists of the cations and anions shown in Tables 1C, 1D, 1E and 1F below. For clarity, the representation of the charge in the formula is omitted.

Table 1A illustrates an example of an anionic bicomponent having a common cation:

[Table 1A]

Table 1B illustrates examples of combinations of cations and anions:

[Table 1B]

In other embodiments, the phosphonium electrolyte is comprised of salts having the cations shown in Table 1C-1 to 1C-3 below:

[Table 1C-1]

[Table 1C-2]

[Table 1C-3]

In another embodiment, the phosphonium electrolyte is comprised of a salt having an anion as shown in Tables 1D-1 to 1D-4 below:

[Table 1D-1]

[Table 1D-2]

[Table 1D-3]

[Table 1D-4]

In further embodiments, the phosphonium electrolyte composition is comprised of a salt having a combination of cations and anions as shown in the following Tables 1E-1 to 1E-4:

[Table 1E-1]

[Table 1E-2]

[Table 1E-3]

[Table 1E-4]

In some embodiments, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is at least one cation of the formula:

_{P (CH 3 CH 2 CH 2} ) y (CH 3 CH 2) x (CH 3) 4-xy (x, y = 0 to 4; x + y ≤ 4)

_{P (CF 3 CH 2 CH 2} ) y (CH 3 CH 2) x (CH 3) 4-xy (x, y = 0 to 4; x + y ≤ 4)

_{P (-CH 2 CH 2 CH 2} CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy (x, y = 0 to 2; x + y ≤ 2 )

_{P (-CH 2 CH 2 CH 2} CH 2 CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy (x, y = 0 to 2; x + y 2); And

At least one anion of the formula:

(CF ₃ ) _x BF _{4 -x} (x = 0 to 4)

(CF ₃ (CF ₂ ) _n ) _x PF _{6 -x} (n = 0 to 2; x = 0 to 4)

(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _{2 -x} (n = 0 to 2; x = 0 to 2)

_{(-OCO (CF 2) n COO} -) (CF 3) x BF 2 -x (n = 0 to 2; x = 0 to 2)

(-OCO (CH ₂ ) _n COO-) ₂ B (n = 0 to 2)

_{(-OCO (CF 2) n COO-} ) 2 B (n = 0 to 2)

_{(-OOR) x (CF 3)} BF 3 -x (x = 0 to 3)

_{(-OCOCOCOO -) (CF 3)} x BF 2 -x (x = 0 to 2)

(-OCOCOCOO-) ₂ B

_{(-OSOCH 2 SOO -) (CF} 3) x BF 2 -x (x = 0 to 2)

(-OSOCF ₂ SOO -) (CF ₃ ) _x BF _{2 -x} (x = 0 to 2)

_{(-OCOCOO-) x (CF 3)} y PF 6 -2x-y consists of; (x = 1 to 3; y = 0 to 4; 2x + y ≤ 6) .

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is at least one cation of the formula:

_{P (CH 3 CH 2 CH 2} ) y (CH 3 CH 2) x (CH 3) 4-xy ( where x, y = 0 to 4; x + y ≤ 4) ; And

At least one anion of the formula:

_{(CF 3) x BF 4 -x} ( where, x = 0 to 4)

(CF ₃ (CF ₂ ) _n ) _x PF _{6 -x} (where n = 0 to 2; x = 0 to 4)

(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _{2 -x} (where n = 0 to 2; x = 0 to 2)

(-OCO (CH ₂ ) _n COO-) ₂ B (where n = 0 to 2)

(-OSOCH ₂ SOO -) (CF ₃ ) _x BF _{2 -x} (where x = 0 to 2)

_{(-OCOCOO-) x (CF 3)} y PF 6 -2x-y consists of; (x = 1 to 3; y = 0 to 4; 2x + y ≤ 6) .

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is at least one cation of the formula:

_{P (-CH 2 CH 2 CH 2} CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy ( where, x, y = 0 to 2; x + y ≤ 2)

_{P (-CH 2 CH 2 CH 2} CH 2 CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy ( where, x, y = 0 to 2; x + y < / = 2); And

At least one anion of the formula:

_{(CF 3) x BF 4 -x} ( where, x = 0 to 4)

(CF ₃ (CF ₂ ) _n ) _x PF _{6 -x} (where n = 0 to 2; x = 0 to 4)

(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _{2 -x} (where n = 0 to 2; x = 0 to 2)

(-OCO (CH ₂ ) _n COO-) ₂ B (where n = 0 to 2)

(-OSOCH ₂ SOO -) (CF ₃ ) _x BF _{2 -x} (where x = 0 to 2)

_{(-OCOCOO-) x (CF 3)} y PF 6 -2x-y consists of; (x = 1 to 3; y = 0 to 4; 2x + y ≤ 6) .

In one embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt consists of at least one anion selected from the group consisting of: PF ₆ , (CF ₃ ) ₃ PF ₃ , (CF _{3 ) 4 PF 2, (CF 3} CF 2) 4 PF 2, (CF 3 CF 2 CF 2) 4 PF 2, (-OCOCOO-) PF 4, (-OCOCOO -) (CF 3) 3 PF, (-OCOCOO _{-) 3 P, BF 4,} CF 3 BF 3, (CF 3) 2 BF 2, (CF 3) 3 BF, (CF 3) 4 B, (-OCOCOO-) BF 2, (-OCOCOO-) BF ( _{CF 3), (-OCOCOO -)} (CF 3) 2 B, (-OSOCH 2 SOO-) BF 2, (-OSOCF 2 SOO-) BF 2, (-OSOCH 2 SOO-) BF (CF 3), ( _{-OSOCF 2 SOO-) BF (CF 3} ), (-OSOCH 2 SOO-) B (CF 3) 2, (-OSOCF 2 SOO-) B (CF 3) 2, CF 3 SO 3, (CF 3 SO 2 _{) 2 N, (-OCOCOO-) 2} PF 2, (CF 3 CF 2) 3 PF 3, (CF 3 CF 2 CF 2) 3 PF 3, (-OCOCOO-) 2 B, (-OCO (CH 2) _{n COO-) BF (CF 3)} , (-OCOCR 2 COO-) BF (CF 3), (-OCOCR 2 COO-) B (CF 3) 2, (-OCOCR 2 COO-) 2 B, CF 3 BF _{(-OOR) 2, CF 3 B} (-OOR) 3, CF 3 B (-OOR) F 2, (-OCOCOCOO-) BF (CF 3), (-OCOCOCOO-) B (CF 3) 2, (- OCOCOCOO-) ₂ B, (-OCOCR ¹ R ² CR ¹ R ² COO-) BF (CF ₃ ) and (-OCOCR ¹ R ² CR ¹ R ² COO-) B (CF ₃ ) ₂ wherein R, R ¹ and R ² are each independently H or F.

In one embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is a cation of the formula (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P ⁺ ; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In other embodiments, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt of the formula _{(CH 3) (CH 3 CH} 2) ₃ P ⁺ of the cation; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In other embodiments, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt of the formula _{(CH 3 CH 2 CH 2)} (CH 3 CH 2) ₃ P ⁺ of the cation; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is a cation of the formula (CH ₃ CH ₂ CH ₂ ) ₃ (CH ₃ ) P ⁺ ; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In other embodiments, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt of the formula _{(CH 3 CH 2 CH 2)} 3 (CH 3 CH 2) P ⁺ cations; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is a cation of the formula (CH ₃ CH ₂ CH ₂ ) ₂ (CH ₃ CH ₂ ) (CH ₃ ) P ⁺ ; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is a cation of the formula (CH ₃ CH ₂ ) ₄ P ⁺ ; And

Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof.

In a further embodiment, the phosphonium electrolyte is the salt consists of the salt dissolved in a solvent, a 1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 P / (CH 3 CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P / (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P; And the general formula ^{_{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO ₃ ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or a combination thereof. In some embodiments, the anion is comprised of a mixture of BF ₄ ^- and CF ₃ BF ₃ ^- and the molar ratio of [BF ₄ ^- ]: [CF ₃ BF ₃ ^- ] ranges from 100/1 to 1/1 to be. In other embodiments, the anion is composed of a mixture of PF ₆ ^- and CF ₃ BF ₃ ^- and the molar ratio of [PF ₆ ^- ]: [CF ₃ BF ₃ ^- ] is in the range of 100/1 to 1/1 Range. In other further embodiments, the anion PF ₆ ^- and BF ₄ ^- consists of a mixture ^{_{of, [PF 6 -]: [}} BF 4 -] The molar ratio of the concentration in the range of 100/1 to 1/1.

In another preferred embodiment, the phosphonium ionic liquid composition consists of a combination of cations and anions as shown in Table 2 below:

[Table 2]

In another preferred embodiment, the phosphonium ionic liquid composition comprises a combination of cations and anions as shown in Table 3 below:

[Table 3]

In a further preferred embodiment, the phosphonium ionic liquid composition consists of a combination of cations and anions as shown in Table 4 below:

[Table 4]

In another further preferred embodiment, the phosphonium ionic liquid composition comprises a combination of cations and anions as shown in Table 5 below:

[Table 5]

In another preferred embodiment, the phosphonium ionic liquid composition is comprised of a combination of cations and anions as shown in Table 6 below:

[Table 6]

In another preferred embodiment, the phosphonium ionic liquid composition is comprised of a combination of cations and anions as shown in Table 7 below:

[Table 7]

In another preferred embodiment, the phosphonium ionic liquid composition is comprised of a combination of cations and anions as shown in Table 8 below:

[Table 8]

In another preferred embodiment, the phosphonium ionic liquid composition consists of a combination of cations and anions as shown in Table 9 below:

[Table 9]

In another preferred embodiment, the phosphonium ionic liquid composition is comprised of a combination of cations and anions as shown in Table 10 below:

[Table 10]

Additional preferred embodiments include a phosphonium ionic liquid composition consisting of a combination of cations and anions as shown in Table 11 below:

[Table 11]

Further preferred embodiments of the phosphonium ionic liquid composition consisting of combinations of cations and anions as shown in Table 12 below are provided:

[Table 12]

Other preferred exemplary embodiments include a phosphonium ionic liquid composition consisting of a combination of cations and anions as shown in Table 13 below:

[Table 13]

In some embodiments, additional examples of suitable phosphonium ionic liquid compositions include, but are not limited to, di-n-propylethyl methylphosphonium bis- (trifluoromethylsulfonyl) imide; n-butyl n-propylethyl methylphosphonium bis- (trifluoromethylsulfonyl) imide; n-hexyl n-butylethylmethylphosphonium bis- (trifluoromethylsulfonyl) imide; And the like.

Illustrative examples of suitable phosphonium ionic liquid compositions include, but are not limited to, 1-ethyl-1-methylphosphoraniumbis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphoraniumbis- (trifluoromethylsulfonyl) imide; n-butyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-hexyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide; And phenyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide.

In other embodiments, examples of suitable phosphonium ionic liquid compositions include, but are not limited to, 1-ethyl-1-methylphosphoraniumbis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphoraniumbis- (trifluoromethylsulfonyl) imide; n-butyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-hexyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide; And phenyl methylphosphoranium bis- (trifluoromethylsulfonyl) imide.

Additional exemplary embodiments of suitable phosphonium ionic liquid compositions include, but are not limited to, 1-ethyl-1-methylphosphacyclohexane bis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphacyclohexane bis- (trifluoromethylsulfonyl) imide; n-butyl methylphosphacyclohexane bis- (trifluoromethylsulfonyl) imide; n-hexyl methylphosphacyclohexane bis- (trifluoromethylsulfonyl) imide; And phenylmethylphosphocyclohexane bis- (trifluoromethylsulfonyl) imide.

According to some embodiments, the phosphonium ionic liquid of the present invention may also form one or more solids or solid and eutectic from liquid. In this example, the term "ionic liquid" is further defined to include eutectic solids from ionic solids or ionic liquids and ionic solids, e.g., bidentate, ternary, and the like.

Redox activity ( redox -active) molecule

The phosphonium ionic liquids of the present invention described herein can be used to synthesize a wide variety of hybrid components and / or devices, such as memory devices and devices. In one exemplary embodiment, the phosphonium ionic liquid herein is used to form a molecular memory device in which the information is stored in a redox information storage molecule.

As used herein, the term "redox active molecule (ReAM) " refers to a molecule or molecule component that can be oxidized or reduced, for example, by the application of an appropriate voltage. As discussed below, ReAM is not limited to macrocycles comprising porphyrin and porphyrin derivatives, but may also include non-macrocyclic compounds, including, for example, sandwich compounds as described herein . In certain embodiments, for example, in the case of a dyad or a triad, the ReAM may comprise multiple subunits. ReAM can include ferrocene, Bipy, PAH, viologen, and the like. Generally, as described below, there are several types of ReAMs useful in the present invention, all based on polydentate proligands, which include macrocyclic moieties and non-macrocycled moieties do. Numerous suitable proligand and complexes as well as suitable substituents are disclosed in U.S. Patent Nos. 6,212,093; 6,728,129; 6,451, 942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484, 394; And U.S. Serial No. 10 / 040,059; 10 / 682,868; 10 / 445,977; 10 / 834,630; 10 / 135,220; 10 / 723,315; 10 / 456,321; 10 / 376,865, both of which are specifically incorporated herein by reference, in particular the structures and descriptions disclosed in these documents.

Suitable proligands belong to two categories: ligands which use nitrogen, oxygen, sulfur, carbon or phosphorus atoms (depending on the metal ion) as coordinating atoms (generally referred to in the literature as sigma sigma donors) being); And organometallic ligands, such as metallocene ligands (generally referred to in the literature as pi (pi), and described herein as Lm).

In addition, a single ReAM can have two or more oxidation-reduction activities. For example, Figure 13a of U.S. Publication No. 2007/0108438 shows porphyrins (shown without a metal) and ferrocene as two redox active subunits. Similarly, a sandwich coordination compound is considered a single ReAM. This is to distinguish the case where such ReAM is polymerized as a monomer. In addition, the metal ion / complexes of the present invention can be associated with counter ions that are not generally described herein

Macro cyclic click  Ligand ( Macrocyclic Ligands )

In one embodiment, ReAM is a macrocyclic ligand, which includes both a macrocyclic prolyl ligand and a macrocyclic complex. As used herein, the term "macrocyclic prolylide" refers to a cyclic compound that is oriented to bind a metal ion and contains a donor atom (sometimes referred to herein as "coordination atom" . Generally, the donor atom is a heteroatom and the heteroatom includes, but is not limited to, nitrogen, oxygen, and sulfur, with electrons being particularly preferred. It will be appreciated, however, by one of ordinary skill in the art that various metal ions may be bonded to various heteroatoms, and thus the heteroatoms used may vary depending upon the metal ion required. Additionally, in some embodiments, a single macrocyclic may contain several types of heteroatoms.

"Macrocyclic complex" is a macrocyclic prolyl ligand having at least one metal ion; In some embodiments, macrocyclic complexes include a single metal ion, but also polynuclear complexes, including polynucleate macrocyclic complexes as discussed below, are also contemplated.

The use of a wide variety of macrocyclic pro-ligands is found in the present invention, including those that are electronically conjugated and not; The macrocyclic prolyl ligands of the present invention preferably have at least one, and preferably two or more oxidation states with 4, 6 and 8 oxidation states of particular importance.

A schematic diagram of a suitable macrocyclic prolyligand is shown and described in Figures 11 and 14 of U.S. Publication No. 2007/0108438, the entirety of which is incorporated herein by reference in addition to Figures 11 and 14. In this embodiment, a 16-membered ring, approximately a porphyrin system (where the -X-moiety contains a single atom, one of carbon and a heteroatom), a 17-membered ring (of the -X- (If two of the -X-moieties contain two skeletal atoms), a 19-membered ring (three of the -X-moieties, if one contains two skeletal atoms), a 18-membered ring Two skeletal atoms), or a 20-membered ring (when all four of the -X-moieties contain two skeletal atoms) are contemplated. Each -X- group is independently selected. The -Q- moiety is optionally substituted with 1 or 2 (5 membered rings < RTI ID = 0.0 > , Or 1, 2, or 3 (in the case of a 6-membered ring) are optionally substituted 5 or 6 membered rings. In some embodiments, rings, bonds and substituents are selected to have at least two oxidation states to a minimum, such that the compounds result in electron conjugation.

In some embodiments, the macrocyclic prolyl ligand of the present invention is selected from the group consisting of porphyrin (specifically porphyrin derivatives as defined below), and cyclen derivatives.

Porphyrin

A particularly preferred subset of macrocyclists suitable for the present invention is porphyrins including porphyrin derivatives. Such derivatives may be ortho-fused to the porphyrin nucleus, or porphyrin with an ortho-perifused extra ring, with one or more carbon atoms of the porphyrin ring being replaced by atoms of another element (Skeleton-substituted) porphyrin, a derivative in which the nitrogen atom of the porphyrin ring is substituted (atomically substituted with nitrogen) by another atom, a substituent located in the peripheral meso-, 3-, or nuclear atom of porphyrin in addition to hydrogen (Hydropyrine, e.g., chlorins, bacterioclopene, isobacteriolopyrine, corphins, pyrrocorphins, etc.), one or more of the derivatives of porphyrin (Extended porphyrin) having at least one atom (including pyrrole and pyrromethenyl units) inserted into the porphyrin ring, at least one group in the porphyrin ring (E. G., Phthalocyanine, sub-phthalocyanine, and porphyrin isomers) of substituted derivatives (contraction porphyrins such as corrin, corrole) and the derivatives described above. In addition, suitable porphyrin derivatives include chlorophyll groups including etiophyllin, pyrroporphyrin, rhodoporphyrin, phylloporphyrin, phylloerythrin, chlorophyll a and b, But are not limited to, deuteroporphyrin, deuterohemin, hemin, hematin, protoporphyrin, mesohemin, hematoporphyrin, mesoporphyrin, But are not limited to, hemoglobin groups including coproporphyrin, uroporphyrin and turacin, and a series of tetraarylazapyrromethines.

As with the compounds outlined herein, to those of ordinary skill in the art, each unsaturated position, whether carbon or heteroatom, whether according to the required valency of the system, It will be appreciated that one or more substituents may be included.

In one preferred embodiment, the redox-active molecule may be metallocene, which may be substituted at any suitable position using an R group independently selected herein. Metallocenes in which certain uses are found in the present invention include ferrocene and its derivatives. In this embodiment, preferred substituents include, but are not limited to, 4-chlorophenyl, 3-acetamidophenyl, 2,4-dichloro-4-trifluoromethyl. Preferred substituents provide an oxidation-reduction potential range of less than about 2 volts.

The oxidation potential of the members of the series can be routinely changed by changing the metal (M) or the substituent.

Another example of a redox-active molecule composed of porphyrin is shown in Figure 12H of U.S. Publication No. 2007/0108438, wherein F is a redox-active subunit (e.g., ferrocene, substituted ferrocene, metalloporphyrin, M is a metal such as Zn, Mg, Cd, Hg, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Mn, B , Al, Ga, Pb and Sn), wherein S1 and S2 are selected from the group consisting of aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, Wherein said substituent is independently selected from the group of halo, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbamoyl, said substituent providing a redox potential range of less than about 2 volts, K1, K2, K3 and K4 are independently selected from the group of N, O, S, Se, Te and CH; L is a linker and X is selected from the group of the substrate, the coupling with the substrate, and the reaction site capable of ionically coupling to the substrate. In a preferred embodiment, X or L-X may be an alcohol or a thiol. In some embodiments, L-X may be removed or substituted with a substituent independently selected from the same group as S 1 or S 2.

As a control over the hole-storage and hole-hopping characteristics of the redox-active unit of the redox-active molecule used in the memory device of the present invention, It is possible.

Such accommodation is practiced through composite design. The hole-storing properties depend on the oxidation potential of the redox-active unit or subunit, which is used by itself or to assemble the storage medium used in the apparatus of the present invention. Hole storage properties and redox potentials can be precisely tuned by the choice of base molecule (s), associated metal and peripheral substituents (Yang et al. (1999) J. Porphyrins Phthalocyanines, 3: 117- 147), the disclosure of which is incorporated herein by this reference.

For example, in the case of porphyrin, Mg porphyrin is more easily oxidized than Zn porphyrin, and electron withdrawing or electron releasing aryl groups can control the oxidation characteristics in a predictable manner. Hole hopping occurs in isoenergetic porphyrins and is transmitted through shared linkers connecting porphyrins (Seth et al. (1994) J. Am. Chem. Soc., 116: 10578-10592, Seth et al 1996) J. Am. Chem. Soc., 118: 11194-11207, Strachan et al. (1997) J. Am. Chem. Soc., 119: 11191-11201; Li et al. Chem., 7: 1245-1262, Strachan et al. (1998) Inorg. Chem., 37: 1191-1201, Yang et al., (1999) J. Am. Chem. Soc., 121: 4008-4018) The disclosure of which is expressly incorporated herein by reference in its entirety.

The design of compounds with predicted redox potentials is well known to those of ordinary skill in the art. In general, the oxidation potential of a redox-active unit or subunit is well known to those skilled in the art and can be retrieved (see, e. G., Handbook of Electrochemistry of the Elements). Moreover, in general, the effect of various substituents on the redox potential of a molecule is generally additive. Thus, the theoretical oxidation potential can be easily predicted for any potential data storage molecule. The actual oxidation potential, specifically the information storage molecule (s) or the oxidation potential of the information storage medium, can be measured according to standard methods. Typically the oxidation potential is predicted by comparison of the experimentally measured oxidation potential of the basic molecule with the experimentally determined oxidation potential of the basic molecule with one substituent and measures the shift of the potential by that particular substituent . The sum of such substituent-dependent potential changes for each substituent then yields the predicted oxidation potential.

The suitability of a particular redox-active molecule for use in the methods of the present invention can be readily determined. The interesting molecule (s) are simply polymerized according to the method of the present invention and coupled to a surface (e.g., a hydrogen passivated surface). Thereafter, a sinusoidal voltammetry (see, for example, US Pat. Nos. 6,272,038; 6,212,093; and 6,208,553; PCT Publication WO 01/03126; or Roth et al. (As described by Roth et al. (2003) J. Am. Chem. Soc. 125: 505-517) (S) is coupled to the surface or not; 2) degree of coverage (coupling); 3) whether or not the molecule (s) has been degraded during the coupling procedure; And 4) assess the stability of the molecule (s) for multiple read / write operations.

In addition, within the definition of "porphyrin" includes porphyrin complexes, which include porphyrin proligand and at least one metal ion. Suitable metals for porphyrin compounds will vary depending on the heteroatom used as coordinating atom, but are generally selected from transition metal ions. As used herein, the term "transition metal" typically refers to 38 elements of groups 3 to 12 of the periodic table. Typically, transition metals are characterized by the fact that their valence electrons, or the electrons used to couple with other elements, are in one or more shells, and thus often exhibit several common oxidation states. In certain embodiments, the transition metal of the present invention comprises at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt. And / or a metal selected from the group consisting of nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, Oxides, and / or nitrides thereof, and / or alloys, and / or mixtures thereof.

Other Macro cyclic

There are several macrocycles based on cyclene derivatives. Figures 17 and 13C of U.S. Publication No. 2007/0108438 generally show some macroscyclic pro-ligands of the cyclin / cyclam inducible system, which is a skeletal extension due to the incorporation of independently selected carbon or heteroatoms . ≪ / RTI > In some embodiments, at least one R group is preferably a redox active subunit that is electronically conjugated to a metal. In some embodiments, at least one R group is a redox active subunit, and two or more adjacent R2 groups form a cycle or an aryl group.

Moreover, in some embodiments, macrocyclic complexes that rely on organometallic ligands are used. In addition to various transition metal coordination complexes having a pure organic compound for use as a redox moiety and a delta-linked organic ligand having a tridentate atom as a heterocyclic or exocyclic substituent, a [pi] -linked organic ligand (Advanced Inorganic Chemistry, 5th Ed., Cotton Wilkinson, John Wiley Sons, 1988, chapter 26, Organometallics, A Concise Introduction, Elschenbroich et al., 2nd Ed. 7, 8, 10 & 11, Pergamon Press, which is hereby incorporated by reference in its entirety for all purposes and is incorporated herein by reference in its entirety. Lt; / RTI > Such an organometallic ligand is a cyclic aromatic compound such as a cyclopentadienide ion [C5H5 (-1)] and an indenylide compound that produces a class of bis (cyclopentadienyl) metal compounds Ring-and ring-fused derivatives, such as the (-) - (- 1) ion, which is described, for example, in Robins et al., J. Am. Chem. Soc. 104: 1882-1893 (1982); And Gassman et al., J. Am. Chem. Soc. 108: 4228-4229 (1986). Of these, the ferrocene [(C5H5) 2Fe] and its derivatives have been used in a wide variety of chemistry (Connelly et al., Chem. Rev. 96: 877-910 (Geiger et al., Advances in Organometallic Chemistry 23: 1-93; and Geiger et al., Advances in Organometallic Chemistry 24:87) are typical examples that have been used for electron transfer or "redox" reactions. Metallocene derivatives of transition metals of various first, second and third periods are useful as redox moieties (and redox subunits). Other potentially suitable organometallic ligands include cyclic arenes such as benzene, which produce bis (arene) metal compounds and their ring substituted and cyclic condensed derivatives, of which bis (benzene) chromium is a typical example. Other acyclic π-bonded ligands, such as allyl (-1) ions or butadiene, produce potentially suitable organometallic compounds, and all such ligands have different π-and δ-bonded ligands In addition, it forms a general class of organometallic compounds in which metal and carbon bonds are present. Both electrochemical studies of various dimers and oligomers of such compounds with or without metal-metal bonds, as well as such compounds with crosslinked organic ligands and additional non-bridging ligands are useful.

Where one or more co-ligands is an organometallic ligand, the ligand is typically attached through one of the carbon atoms of the organometallic ligand, but attachment may be through other atoms in the case of a heterocyclic ligand . Preferred organometallic ligands include metallocene ligands, which include substituted derivatives and meta rosé neo plates (see Cotton and Wilkenson, page 1174, supra). For example, derivatives of metallocene ligands such as methylcyclopentadienyl are preferred to have a number of methyl groups such as pentamethylcyclopentadienyl, which can be used to increase the stability of the metallocene. In some embodiments, the metallocene is derivatized with one or more substituents as outlined herein, in particular to alter the redox potential of the subunit or moiety.

As described herein, any combination of ligands may be used. Preferred combinations include: a) all ligands are nitrogen-donating ligands; b) all ligands are organometallic ligands.

Sandwich Coordination Complex

In some embodiments, ReAM is a sandwich coordination complex. The term "sandwich coordination compound" or "sandwich coordination complex" refers to a compound of the formula L-Mn-L wherein each L is a heterocyclic ligand (as described below) Is 2 or more, most preferably 2 or 3, each metal is located between a pair of ligands, and one or more heteroatoms in each ligand (and typically a plurality of heteroatoms, e.g., 2, 3 , 4, 5) (depending on the oxidation state of the metal). Thus, the sandwich coordination compound is not an organometallic compound such as ferrocene, where the metal is bonded to a carbon atom. The ligands in the sandwich coordination compound are generally arranged in a laminated orientation (i.e. they are generally oriented facing each other and aligned axially with respect to each other, but may or may not rotate about their axis with respect to each other) (See, for example, Ng and Jiang (1997) Chemical Society Reviews 26: 433-442, which is incorporated herein by reference). The sandwich coordination complexes include, but are not limited to, "double-decker sandwich coordination compounds" and "triple-decker sandwich coordination compounds. The synthesis and use of sandwich coordination compounds is described in U.S. Patent No. 6,212,093; 6,451, 942; 6,777, 516; the polymerization of these molecules is described in U.S. Publication No. 2007/0123618, all of which are incorporated herein, and particularly in both sandwich complexes and "single macrocyclic" Each substituent used is included herein.

The term "double-decker sandwich coordination compound" refers to a sandwich coordination compound having the formula L'-M'-LZ wherein L 'and LZ can each be the same or different, (See, for example, Jiang et al. (1999) J. Porphyrins Phthalocyanines 3: 322-328 and US Patents 6,212,093; 6,451,942; 6,777,516; 2007/0123618, which is hereby incorporated by reference in its entirety.

The term "triple-decker sandwich coordination compound" refers to a compound of the formula L'-M 'LZ-MZ-L3 wherein L', LZ and L3 are each the same or different and M ' And MZ may each be the same or different) (see, for example, Arnold et al. (1999) Chemistry Letters 483-484 and U.S. Patents 6,212,093; 6,451,942; 6,777,516 Polymerization of these molecules is described in U.S. Publication No. 2007/0123618, which is hereby incorporated by reference in its entirety.

In addition, polymers of these sandwich compounds are also useful, as are described in U.S. Patent Nos. 6,212,093; U.S. Patent No. 6,451,942; Quot; dyads "and" triads "as described in U.S. Patent No. 6,777,516, and the polymerization of these molecules is described in U.S. Publication No. 2007/0123618, Which is incorporated herein by reference.

Non-macro cyclic Pro-ligand  And Complex

According to general rules, ReAM, which includes non-macrocyclic chelators, combine with metal ions to form non-macrocyclic chelate compounds, which, due to the presence of metals, So that a plurality of oxidation states can be obtained.

In some embodiments, a nitrogen-containing pro-ligand is used. Suitable nitrogen donor proligands are well known in the art and include NH2; NFIR; NRR '; Pyridine; Pyrazine; Isonicotinamide; Imidazole; Substituted derivatives of bipyridine and bipyridine; Terpyridine and substituted derivatives thereof; Phenanthrolines, especially substituted phenanthroline derivatives such as 1,10-phenanthroline (abbreviated phen) and 4,7-dimethylphenanthroline, and substituted derivatives of dipyridol [3,2-a: 3'-c] phenazine (abbreviated as dppz); Dipyridophenazine; 1,4,5,8,9,12-hexaazatriphenyl (abbreviated hat); 9,10-phenanthrenequinone diimine (abbreviated as phi); 1,4,5,8-tetraazaphenanthrene (abbreviated as tap); 1,4,8,11-tetra-azacyclotetradecane (abbreviated as cyclam), and isocyanide. Substituted derivatives containing condensed derivatives may also be used. It should be noted that macrocyclic ligands which do not saturate metal ions concomitantly and require the addition of other proligands are considered macrocycles for this purpose. It will be appreciated by those of ordinary skill in the art that it is possible to covalently attach some "nonmacrocyclic" ligands to form a coordinatively saturated compound, but in this case there is no cyclic skeleton.

Suitable sigma initiator ligands using carbon, oxygen, sulfur, and phosphorus are known in the art. For example, suitable sigma carbon donors are found in Cotton and Wilkenson, Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, 1988, which is incorporated herein by reference; For example, see page 38. Similarly, suitable oxygen ligands include crown ethers, water, and others known in the art. Phosphines and substituted phosphines are also suitable; See page 38 of Cotton and Wilkenson.

The oxygen, sulfur, phosphorus and nitrogen-donor ligands are attached in such a way that the heteroatom can act as coordinating atoms.

Polynuclear Pro-ligand  And Complex

In addition, some embodiments utilize polydentate, a polynuclear ligand, which, for example, can bind more than one metal ion. These may be macrocyclic or nonmacrocyclic.

Some suitable proligand and complexes, as well as suitable substituents, are described in U.S. Patent Nos. 6,212,093; 6,728,129; 6,451, 942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484, 394; And U.S. Patent Application No. 10 / 040,059; 10 / 682,868; 10 / 445,977; 10 / 834,630; 10 / 135,220; 10 / 723,315; 10 / 456,321; 10 / 376,865, both of which are expressly incorporated by reference in their entirety, particularly the structures and descriptions of those depicted therein.

Phosphonium  Applications and uses of ionic liquids or salts

The term "memory element "," memory cell ", or "storage cell" refers to an electrochemical cell that can be used for storage of information, as used herein and unless otherwise indicated. A preferred "storage cell" is a discrete region of the storage medium addressed by at least one, preferably two, electrodes (e.g., a working electrode and a reference electrode). The storage cells may be addressed individually (e.g., a single electrode is combined with a respective memory element), or, in particular, if the oxidation states of several memory elements are distinguishable, Can be addressed by an electrode. The memory device may optionally include a dielectric (e. G., A dielectric containing counter ions).

As used herein, the term "electrode" refers to any medium capable of transporting charge (e.g., electrons) from a storage molecule and / or from a storage molecule. Preferred electrodes are metals and conductive organic molecules, which include Group III elements (including doped and oxidized Group III elements), Group IV elements (including doped and oxidized Group IV elements), Group V But are not limited to, elements (including doped and oxidized Group V elements) and transition metals (including transition metal oxides and transition metal nitrides). The electrodes may be fabricated in substantially two or three dimensional shapes (e.g., discrete lines, pads, planes, spheres, cylinders).

Unless otherwise indicated and used herein, the term "multiple oxidation states" means more than one oxidation state. In a preferred embodiment, the oxidation state may reflect the acquisition (reduction) of electrons or the loss (oxidation) of electrons.

The term "multi-porphyrin array" refers to the discrete number of two or more covalently linked porphyrin macrocycles unless used and indicated otherwise herein. The multi-porphyrin array may be linear, cyclic, or branched.

The term "output of an integrated circuit" refers to a voltage or signal generated by one or more integrated circuit (s) and / or components of one or more integrated circuits, unless used and indicated otherwise herein.

The term "on a single plane ", as used herein and unless otherwise indicated, when used in connection with a memory device of the present invention means that the component (s) (e.g., storage medium, electrode (s) ) Is on the same physical plane in the device (for example, it is on a single lamina). The components present on the same plane can typically be produced simultaneously, for example by a single operation. Thus, for example, all electrodes on a single plane can typically be applied in a single (e.g., sputtering) step (assuming they are all made of the same material).

The term "potentiometric device ", as used herein and unless otherwise indicated, is a device capable of measuring the potential across an interface resulting from the difference in the equilibrium concentration of redox molecules in an electrochemical cell.

The term "oxidation" refers to the loss of one or more electrons in an element, compound, or chemical substituent / subunit, unless used and indicated otherwise herein. In the oxidation reaction, electrons are lost by atoms of the element (s) involved in the reaction. Since then, the charge on these atoms must be more positive. The electrons are lost from the species undergoing oxidation, and so electrons appear as products in the oxidation reaction. Oxidation takes place in the reaction Fe2 + (aq) → Fe3 + (aq) + e- because the electrons are lost from the species to be oxidized, Fe2 + (aq), despite the obvious generation of electrons as "free" to be. Conversely, the term "reduction" refers to the acquisition of one or more electrons by an element, compound, or chemical substituent / subunit.

As used herein and unless otherwise indicated, the term "oxidized state" refers to a state generated by the acquisition or loss of electrons in an electrically neutral state, or in an element, compound, or chemical substituent / subunit. In a preferred embodiment, the term "oxidation state" refers to a state comprising any state other than the neutral state and the neutral state caused by the acquisition or loss (reduction or oxidation) of electrons.

The term "read" or "interrogate" refers to the measurement of the oxidation state (s) of one or more molecules (e.g., molecules comprising a storage medium), unless used and indicated otherwise herein.

The term "redox-active unit" or "redox-active subunit" as used herein and unless otherwise indicated refers to a molecule or molecule component that can be oxidized or reduced by the application of an appropriate voltage.

The term "refresh ", as used herein and unless otherwise indicated, refers to the application of a voltage to a storage molecule or storage medium, when used in connection with the storage molecule or storage medium, To a predetermined state (e. G., The oxidation state in which the storage molecule or storage medium was placed just prior to reading).

The term "reference electrode" refers to one or more electrodes that provide a reference (e.g., a specific reference voltage) for measurements recorded from a working electrode, unless used and indicated otherwise herein. In a preferred embodiment, the reference electrodes of the inventive memory device are at the same potential, but in some embodiments this is not required.

Unless otherwise indicated and used herein, the term "sine wave voltage ammeter" is a voltage current measurement device capable of measuring the frequency domain characteristics of an electrochemical cell.

The term "storage density" as used herein and unless otherwise indicated refers to the number of bits per volume and / or the number of bits per molecule that can be stored. When the storage medium is said to have a storage density greater than one bit per molecule, this refers to the storage medium preferably containing molecules in which a single molecule can store at least one bit of information.

As used herein and unless otherwise indicated, the term "storage location" refers to the discrete domain or domain in which the storage medium is located. If addressed to one or more electrodes, the storage location may form a storage cell. However, if two storage locations include the same storage medium, they have essentially the same oxidation state, and both storage locations are commonly addressed, they can form one functional storage cell.

The term "storage medium" refers to a composition comprising a storage molecule of the invention, preferably conjugated to a substrate, as used herein and unless otherwise indicated.

The substrate is preferably a solid, suitable material for attachment of one or more molecules. The substrate can be formed of materials including, but not limited to, glass, plastic, silicon, minerals (e.g., quartz), semiconductor materials, ceramics, metals and the like.

Unless used or indicated otherwise herein, the term "voltage / current measurement device" is a device capable of measuring a current generated in an electrochemical cell as a result of voltage application or as a result of voltage change.

A voltage source is any source (e.g., a molecule, device, circuit, etc.) that is capable of applying a voltage to a target (e.g., an electrode), as used herein and unless otherwise indicated.

The term "working electrode" is used herein to refer to one or more electrodes used to set or read the state of the storage medium and / or the storage molecule, unless used and indicated otherwise.

Device

Some embodiments of the phosphonium ionic liquid compositions of the present invention are useful in forming a variety of hybrid electrical devices. For example, in one embodiment, an apparatus comprising: a first electrode; A second electrode; And an electrolyte composed of an ionic liquid composition, wherein the ionic liquid composition comprises one or more phosphonium cations of the general formula: And one or more anions;

R ¹ R ² R ³ R ⁴ P

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent and the electrolyte is electrically coupled to at least one of the first and second electrodes. In some embodiments, the first electrode comprises redox active molecules (ReAMs) as described in detail above.

In another embodiment, a molecular storage device includes: a working electrode and a counter electrode configured to provide electrostatic capacitance; An ion conductive composition comprising an ion conductive composition comprising at least one phosphonium cation of the above formula, wherein the ion conductive composition is electrically coupled to at least a working electrode and a counter electrode.

In another embodiment, the invention includes a molecular memory device comprising a switching device, a bit line and a word line coupled to the switching device, and a molecular storage device accessible through the switching device. The molecular storage device may be disposed in two or more discrete states wherein the molecular storage device is disposed in one of the discrete states by a signal applied to the bit and word lines. The molecular reservoir comprises a first electrode, a second electrode and an electrolyte of a phosphonium-based cation and a suitable anion between the first and second electrodes. Another embodiment includes a molecular memory array comprising a plurality of molecular storage elements, wherein each molecular storage element can be arranged in two or more discrete states. A plurality of bit lines and word lines are coupled to the plurality of storage molecular elements such that each molecular storage element is coupled to and addressable by at least one bit line and at least one word line.

The molecular memory device may comprise an addressable array of molecular storage elements. An address decoder receives the coded address and generates a word line signal corresponding to the coded address. A word line driver is coupled to the address decoder to generate the amplified word line signal. The amplified word line signal controls a switch that selectively couples the members of the array of molecular storage elements to the bit line. The read / write logic coupled to the bit line determines whether the molecular memory device is in read mode or in write mode. In the read mode, sense amplifiers coupled to each bit line detect the electronic state of the selectively coupled molecular storage element and selectively couple the bit line to the bit line representing the electronic state of the coupled molecular storage element Thereby generating a data signal. In the write mode, the read / write logic drives the data signal onto the bit line and the selectively coupled molecular storage element.

Other implementations include an apparatus comprising logic integrated into a recessed molecular memory device, such as an application specific integrated circuit (ASIC) and a system on chip (SOC) device. Such an implementation includes one or more functional elements that are monolithically formed in a molecular memory device and connected to one another. The functional element may comprise a solid state electronic device and / or a molecular electronic device.

In certain embodiments, the molecular storage device is implemented as a stacked structure formed thereon following a semiconductor substrate having an active device formed therein. In another embodiment, the molecular storage device is implemented as a micron or nanometer sized hole in a semiconductor substrate having an active device formed therein. Molecular storage devices are fabricated using processing techniques that are compatible with semiconductor substrates and active devices previously formed in semiconductor substrates. Molecular storage devices include, for example, electrochemical cells having two or more electrode surfaces separated by an electrolyte (e.g., a ceramic or solid electrolyte). A storage molecule (e.g., a molecule having one or more oxidation states that can be used for storage information) is coupled to the electrode surface within the electrochemical cell.

Another embodiment of the invention is a transistor switching device comprising a field effect transistor; A row decoder coupled to the word line; A column decoder connected to the bit line; A current preamplifier connected to the bit line; A sense amplifier connected to the bit line; An address decoder receiving the coded address and generating a word line signal corresponding to the coded address; A line driver coupled to the address decoder, the amplified word line signal generating optionally an amplified word line signal, wherein the amplified word line signal controls a member of the array of molecular storage elements to selectively control a switch coupled to the bit line, Line driver; The read / write logic coupled to the bit line, the read / write logic determining whether the molecular storage device is in read mode or in write mode; A sense amplifier coupled to each bit line, wherein the sense amplifier coupled to each bit line when the device is in a read mode detects the electronic state of the selectively coupled molecular storage element, (When the device is in the write mode, the read / write logic drives the data signal onto the bit line and the selectively coupled molecular storage element) to generate a data signal for the bit line representing the electronic state of the molecular storage element Sense amplifier); An electrolyte layer; ≪ / RTI > and combinations thereof.

Additional embodiments include a second electrode coupled to the ground, and bit and word lines that are vertically or horizontally present.

Additional implementations include memory arrays of the present invention including volatile memory such as DRAM or SRAM, or non-volatile memory such as flash or ferroelectric memory.

A further embodiment is an array, wherein a molecular storage device comprises an adhesion layer formed on a first electrode, the adhesion layer comprising an opening, molecular material being in the opening and being on the second electrode layer and on the adhesion layer And provides an electronically coupled array to the formed electrolyte layer.

Other implementations include a logic device configured to perform a particular function and a monolithic integrated device including the embedded type molecular memory device of the present invention coupled to the logic device. The device may optionally include an application specific integrated circuit (ASIC), a system on chip (SOC), a solid state electronic device, or a molecular electronic device.

The memory device of the present invention may be fabricated using standard methods well known to those skilled in the art. In a preferred embodiment, the electrode (s) may be deposited according to standard well-known methods (e.g., see Rai-Choudhury (1997) The Handbook of Microlithography, Micromachining, and Microfabrication, SPIE Optical Engineering Press, Bard Faulkner (1997) Fundamentals of Microfabrication) The layer (s) are applied to a suitable substrate (e.g., silica, glass, plastic, ceramic, etc.). A variety of techniques are described below and in U. S. Patents 6,212, 093; 6,728,129; 6,451, 942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484, 394; U.S. Patent Application No. 10 / 040,059; 10 / 682,868; 10 / 445,977; 10 / 834,630; 10 / 135,220; 10 / 723,315; 10 / 456,321; 10 / 376,865; And U.S. Publication No. 2007/0123618, all of which are expressly incorporated herein by reference, particularly to fabrication techniques outlined therein.

There are a wide variety of device and system architectures that benefit from the use of molecular memory.

The memory device is operated by receiving the N-bit row address into the row address decoder and the M-bit column address into the column address decoder. The row address decoder generates a signal on one word line. The word line may include a word line driver circuitry that drives a high current signal on the word line. Because the word lines tend to be long, thin conductors that extend over most of the chip surface, a significant current and large power switch is needed to drive the word line signals. As a result, the line driver circuit often has a power supply in addition to a power supply circuit (not shown) that provides operating power for the other logic. Thus, wordline drivers tend to include large components, and high speed switching of large currents tends to create noise, constrain the limits of power and power conditioners, and stress the insulation structure.

In a typical memory array, there are more columns (bit lines) than rows (word lines), because during a refresh operation, each word line is activated to refresh all the storage elements coupled to that word line. Thus, the lower the number of rows, the less time it takes to refresh all the rows. One feature of the present invention is that the molecular memory device can be configured to exhibit significantly longer data retention than typical capacitors, in the order of tens, seconds, tens of seconds, or effectively unlimited seconds. Thus, the refresh cycle may be performed on a very low frequency scale or may be omitted altogether. Thus, considerations for refreshing that actually affect the physical layout of the memory array can be mitigated, and arrays of various shapes can be implemented. For example, the memory array can be easily fabricated with a larger number of word lines, thereby making each word line shorter. As a result, the word line driver circuit can be smaller or eliminated, because less current is needed to drive the word line at high speed. Alternatively or additionally, shorter word lines may be driven faster, thus improving the read / write access time. Still yet another alternative, each row of memory locations may have a plurality of word lines to provide a mechanism for storing multiple states of information in each memory location.

A sense amplifier is coupled to each bit line and is activated to detect a signal on bit line 109 that indicates the state of the memory element coupled to that bit line, thereby amplifying the state to a suitable logic level signal. In one embodiment, the sense amplifier is implemented in a substantially conventional design so that the conventional design will operate to detect and amplify the signal from the molecular memory device. Alternatively, unlike conventional capacitors, some molecular storage devices provide a highly distinct signal indicative of their condition. This distinct signal can reduce the need for conventional sense amplifier logic because the status signal from the molecular storage device is more easily and reliably latched into the buffer of the read / write logic than the signal stored in conventional capacitors ). That is, the present invention can provide a device large enough to eliminate the need for a sense amplifier.

The read / write logic includes a circuit diagram for placing the memory device in a read or write state. In the read state, data from the array of molecules is placed on the bit line (with or without activation of the sense amplifiers) and is collected by the buffer / latch in the read / write logic. The column address decoder will select which bit line is active in a particular read operation. In a write operation, the read / write logic drives the data signal on the selected bit line, causing the data to overwrite any data already stored in the addressed memory element (s) when the word line is activated.

The refresh operation is substantially similar to the read operation, while the word line is driven by a refresh circuit diagram (not shown) rather than by an address applied from the outside. In a refresh operation, when a sense amplifier is used, it drives the bit line to a signal level that indicates the current state of the memory device, and the value is automatically written back to the memory device. Unlike the read operation, the state of the bit line is not coupled to the read / write logic during refresh. This operation is only needed if the charge retention time of the molecule used is less than the operating life of the device used, for example about 10 years for a flash memory.

In an exemplary embedded system that includes a central processing unit and a molecular memory, the memory bus couples the CPU and the molecular memory device to exchange address, data, and control signals. Optionally, the embedded system may also include conventional memory coupled to the memory bus. Typical memories may include random access memory (e.g., DRAM, SRAM, SDRAM, etc.), or read only memory (e.g., ROM, EPROM, EEPROM, etc.). These other types of memory may be useful for caching a data molecular memory device, storing an operating system or a BIOS file, and the like. Embedded systems may include one or more input / output (I / O) interfaces that enable communication between the CPU and external devices and systems. The I / O interface can be implemented by serial ports, parallel ports, radio frequency ports, optical ports, infrared ports, and the like. Moreover, the interface may be configured to communicate using any available protocol including a packet-based protocol.

battery

Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited for electrolytes for battery applications. In one embodiment, the anode; cathode; A separator between the anode and the cathode; And an electrolyte. The electrolyte is comprised of an ionic liquid composition or a salt dissolved in one or more ionic liquids or solvents, wherein the one or more ionic liquids or salts comprise one or more phosphonium cations of the following general formula: And one or more anions;

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In one embodiment, the electrolyte is comprised of an ionic liquid having one or more phosphonium-based cations and one or more anions, wherein the ionic liquid composition has a thermodynamic stability of up to 375 ^° C, a liquidus of greater than 400 ^° C ), And an ionic conductivity of at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm at room temperature. In another embodiment, the electrolyte is comprised of at least one phosphonium-based cation and at least one salt having at least one anion dissolved in a solvent, wherein the electrolyte composition is at least 5 mS / cm or at least 10 mS / cm, or at least 15 mS / cm, or at least 20 mS / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm.

A cell comprising an electrolyte composition according to an embodiment of the present invention is described further in co-pending US patent application Ser. No. __________________________________________________________________________________________________________________________________________________________ (Attorney Docket No. 057472-060), the entire disclosure of which is incorporated herein by reference Which is incorporated herein by reference.

In some embodiments, the electrolyte composition comprises but is not limited to one or more of the following solvents: acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate ), Diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate VC), vinylethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (GBL) and gamma-valerolactone (GVL).

In some embodiments, the electrolyte composition comprises at least one lithium salt having at least one anion selected from the group consisting of: PF ₆ , (CF ₃ ) ₃ PF ₃ , (CF ₃ ) ₄ PF ₂ , (CF _{3 CF 2) 4 PF 2, (} CF 3 CF 2 CF 2) 4 PF 2, (-OCOCOO-) PF 4, (-OCOCOO -) (CF 3) 3 PF, (-OCOCOO-) 3 P, BF 4, _{CF 3 BF 3, (CF 3} ) 2 BF 2, (CF 3) 3 BF, (CF 3) 4 B, (-OCOCOO-) BF 2, (-OCOCOO-) BF (CF 3), (-OCOCOO- _{) (CF 3) 2 B,} (-OSOCH 2 SOO-) BF 2, (-OSOCF 2 SOO-) BF 2, (-OSOCH 2 SOO-) BF (CF 3), (-OSOCF 2 SOO-) BF ( _{CF 3), (-OSOCH 2 SOO-} ) B (CF 3) 2, (-OSOCF 2 SOO-) B (CF 3) 2, CF 3 SO 3, (CF 3 SO 2) 2 N, (-OCOCOO- _{) 2 PF 2, (CF 3} CF 2) 3 PF 3, (CF 3 CF 2 CF 2) 3 PF 3, (-OCOCOO-) 2 B, (-OCO (CH 2) n COO-) BF (CF 3 _{), (-OCOCR 2 COO-) BF} (CF 3), (-OCOCR 2 COO-) B (CF 3) 2, (-OCOCR 2 COO-) 2 B, CF 3 BF (-OOR) 2, CF 3 _{B (-OOR) 3, CF 3} B (-OOR) F 2, (-OCOCOCOO-) BF (CF 3), (-OCOCOCOO-) B (CF 3) 2, (-OCOCOCOO-) 2 B, (- OCOCR ¹ R ² CR ¹ R ² COO-) BF (CF ₃ ), and (-O COCR ¹ R ² CR ¹ R ² COO-) B (CF ₃ ) ₂ ; Here, R, R ¹ and R ² are each independently H or F.

In further embodiments, the electrolyte composition comprises, but is not limited to, one or more of the following lithium salts: lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), Lithium hexafluoroarsenate (LiAsF ₆ ), lithium trifluoromethanesulfonate or lithium triflate (LiCF ₃ SO ₃ ), lithium bis (trifluoromethanesulfonyl) imide (Li (CF ₃ SO _{2) 2} N or LiIm) and lithium bis (methanesulfonyl pentafluorophenyl) imide _{(Li (CF 3 CF 2 SO} 2) 2 N or LiBETI).

In a further aspect, the phosphonium electrolyte has reduced flammability, thereby improving the stability of battery operation. In a further aspect, a phosphonium ionic liquid or salt may be used as an additive to promote the formation of a solid electrolyte interphase (SEI) layer or electrode protection layer. The SEI layer broadens the electrochemical stability range, inhibiting degradation or decomposition reactions of the cell, thereby helping to improve the cycle life of the cell.

The phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes for various batteries, such as lithium primary batteries and lithium secondary batteries, including lithium ion batteries and rechargeable lithium metal batteries Sometimes collectively referred to herein as a "lithium battery"). Examples of lithium primary cells, but is not including, the following limitation: lithium / manganese dioxide (Li / MnO _2), lithium / day fluorocarbon (Li / CFx), a lithium / silver vanadium oxide (Li / Ag ₂ V ₄ O ₁₁ ), Li- (CF) _x , lithium / iron disulfide (Li / FeS ₂ ), and lithium / copper oxide (Li / CuO). Examples of lithium ion batteries (LIB) include, but are not limited to: carbon, graphite, graphene, silicon (Si), tin (Sn), Si / Co doped carbon, and metal oxides, (LiCoO ₂ ), lithium manganese oxide (LMO) (LiMn ₂ O ₄ ), lithium iron phosphate (LFP) (LiFePO ₄ ), lithium nickel manganese cobalt (Ni (NiMnCo) O ₂ ), lithium nickel cobalt aluminum oxide (NCA) (Li (NiCoAl) O ₂ ), lithium nickel manganese oxide (LNMO) (Li ₂ NiMn ₃ O ₈ ), and lithium vanadium oxide (LVO). Examples of rechargeable lithium metal batteries include, but are not limited to, lithium metal anodes and lithium cobalt oxide (LCO) (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium iron phosphate (LFP) LiFePO _4), lithium nickel manganese cobalt oxide (NMC) (Li (NiMnCo) O 2), lithium nickel cobalt aluminum oxide (NCA) (Li (NiCoAl) O 2), lithium nickel-manganese oxide (LNMO) (Li ₂ NiMn ₃ O ₈ ), a lithium / sulfur battery and a lithium / air battery

In a further embodiment, the approach to energy storage may be combined with electrochemical double layer capacitors (EDLCs) to form a hybrid energy storage system comprising an array of cells and EDLC.

Electrochemical Double layer  Capacitor

Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes in electrochemical bi-layer capacitors (EDLC), also referred to as electrochemical capacitors or supercapacitors or ultracapacitors. EDLC is an energy storage device capable of storing more energy than conventional capacitors and discharging this energy at a higher rate than secondary cells. In addition, the cycle life of electrochemical capacitors must far exceed the lifetime of the battery system. EDLC is attractive in dislocation applications among promising technologies that require pulsed power. Examples of such applications include digital communication devices that require pulse power in the millisecond range and traction power systems in electric vehicles where high power demands can last from seconds to minutes. Battery performance and cycle life are significantly degraded as power demand increases. A capacitor-cell combination has been proposed wherein the capacitor processes the peak power and the battery provides a continuous load between the pulses. Such a hybrid power system can improve the overall power performance and increase the battery cycle life without increasing the size or weight of the system.

EDLC is basically the same as a battery in terms of general design, and differs in that the nature of charge storage in the electrode active material is capacitive; That is, the charging and discharging process involves only the movement of the electronic charge through the solid electronic phase and the ionic movement through the electrolyte phase. Compared with batteries, higher power density and longer cycle life can be achieved because no rate-limiting and life-limited phase transformation occurs at the electrode / electrolyte interface in the EDLC device.

The dominant EDLC technology is based on the double layer type of charging at high surface area carbon electrodes where the capacitor is electronically charged with a counter-ion in the solution phase moving the carbon surface to the carbon surface, , Which is to balance the charge. Other techniques are based on the charging of the pseudocapacitance type at the electrodes of conductive polymers and certain metal oxides. Conductive polymers have been studied for use in EDLC. Higher energy densities can be achieved because the charge only occurs through the volume of active polymer material rather than the outer surface. Metal oxides have also been studied for use in EDLC. Charging in these active materials occurs through the volume of the material and, consequently, the observed charge and energy density are reported to be comparable or even higher than those obtained from the conductive polymer.

In one embodiment of the invention, the EDLC device comprises a single cell. 1, there is shown a schematic cross-sectional view of a single-cell EDLC 10, which includes a pair of electrodes 12, 12 'coupled to current collector plates 14, 14' An embedded separator film or membrane 16 and an electrolytic solution 18 (not shown) that permeates and fills the pores of the separator and the at least one electrode.

2A and 2B, the capacitor electrode is a bipolar array 20 in which two electrodes 22, 24 are attached on both sides of a "bipolar" current collector 26 Can be produced. A multi-cell EDLC can be fabricated by arranging a large number of single cells in a bipolar stack to provide the higher voltage (and power) needed. An exemplary multi-cell EDLC 30 is shown in Figure 2B, wherein the bipolar stack consists of four unit cells 32-38. Each cell has the same structure as that of the single cell 10 in Fig. In the bipolar stack, each cell is separated from a neighboring cell by a single current collector plate, which also serves as an ionic wall between the cells. This design optimizes the current path through the cell, reduces ohmic losses between cells, and minimizes packaging weight due to current collection. As a result, the capacitors have higher energy and power densities.

In some embodiments, the EDLC is formed with a flat or flat structure of electrode / separator / electrode assemblies. In other embodiments, the EDLC is formed with an electrode / separator / electrode assembly having a wound spiral structure, such as a cylindrical and prismatic structure.

In some embodiments, the electrodes are made of high surface area active material micro- or nanoparticles, which are bonded together by a binder material to form a porous structure. In addition to the compressed powder with the binder, the active material can be made in other forms such as fibers, woven fibers, felt, foam, cloth, arogel and mesobead. Examples of the active material include, but are not limited to, carbon species such as carbon black, graphite, and graphene; Carbon-metal complex; Conductive polymers such as polyaniline, polypyrrole, and polythiophene; Oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides of lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium; And combinations thereof.

In some embodiments, the electrode binder material is selected from one or more of the following: polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber ( SBR), polyacrylonitrile (PAN), polyacrylate, acrylate copolymer (ACM), carboxymethylcellulose (CMC), polyacrylic acid (PAA), polyamide, polyimide, polyurethane, polyvinyl ether PVE) or a combination thereof.

In some embodiments, the separator material is selected from one or more of the following, including but not limited to: films or membranes of microporous polyolefins such as polyethylene (PE) and polypropylene (PP), polyvinylidene fluoride (PVdF), PVdF coated polyolefin, polytetrafluoroethylene (PTFE), polyvinyl chloride, resorcinol formaldehyde polymer, cellulose paper, nonwoven polystyrene cloth, acrylic resin fiber, nonwoven polyester film, poly A carbonate film and a fiber glass paper or a combination thereof.

In one embodiment, the electrolyte is comprised of an ionic liquid composition or a salt dissolved in one or more ionic liquids or solvents, which comprises a phosphonium-based cation of one or more of the following general formulas: And one or more anions;

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ^3, and R ⁴ are each independently a substituent, for example, but not limited to, an alkyl group as described below. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group consisting of 1 to 6 carbon atoms, more typically 1 to 4 carbon atoms. Any one or more of the salts may be liquid or solid at a temperature of 100 ^o C or lower. In some embodiments, the salt consists of one cation and one anion pair. In another embodiment, the salt consists of one cation and a number of anions. In another embodiment, the salt consists of one anion and a plurality of cations. In a further embodiment, the salt consists of a plurality of cations and a plurality of anions.

In one embodiment, the electrolyte being composed of an ionic liquid having at least one phosphonate nyumgye cations and one or more anions, wherein the ionic liquid composition is thermodynamically stable, the liquidus range of 400 ^o C in excess of up to 375 ^o C , And at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm at room temperature. In another embodiment, the electrolyte is comprised of one or more salts having one or more phosphonium-based cations and one or more anions dissolved in a solvent, wherein the electrolyte composition is at least 5 mS / cm, or at least 10 mS / cm , Or at least 15 mS / cm, or at least 20 mS / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm.

In another embodiment, the electrolyte composition further comprises one or more conventional non-phosphonium salts. In some embodiments, the electrolyte composition can be composed of conventional salts, wherein the phosphonium ionic liquids or salts disclosed herein are additives. In some embodiments, the electrolyte composition is comprised of a phosphonium ionic liquid or salt and one or more conventional salts, and the phosphonium ionic liquid or salt: a conventional salt is in the range of 1: 100 to 1: 1 Mol (or molar) ratio. Conventional salts _{example, (CH 3 CH 2) 4} N +, (CH 3 CH 2) 3 (CH 3) N +, (CH 3 CH 2) 2 (CH 3) 2 N +, (CH 3 CH 2 ^{_{) (CH 3) 3 N +}} , (CH 3) 4 N + and tetraalkylammonium, already as imidazolium, pyrazolium, pyridinium, avoid large titanium, pyrimidinyl titanium, flutes Dodge titanium and the group consisting of pyrrolidine pyridinium At least one cation selected from: And ^{_{ClO 4 -, BF 4 -,}} CF 3 SO 3 -, PF 6 -, AsF 6 -, SbF 6 -, (CF 3 SO 2) 2 N -, (CF3CF 2 SO 2) 2 N - and (CF ₃ SO ₂ ) ₃ C ^- . In another embodiment of the present invention, In some embodiments, one or more conventional salts include, but are not limited to, tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), 1- Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-ethyl-1-methylpyrrolidinium tetrafluoroborate (EMPBF ₄ ) Romero tansul sulfonyl) imide (EMIIm), and phosphate (EMIPF ₆₎ as imidazolium hexafluoro-1-ethyl-3-methyl. In some embodiments, one or more conventional salts include, but are not limited to, the following lithium-based salts: lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium trifluoromethanesulfonate or lithium triflate (LiCF ₃ SO ₃ ), lithium bis (trifluoromethanesulfonyl) imide (Li ₃ SO ₂ ) ₂ N or LiIm) and lithium bis (pentafluoromethanesulfonyl) imide (Li (CF ₃ CF ₂ SO ₂ ) ₂ N or LiBETI).

In some embodiments, the electrolyte composition further comprises, but is not limited to, one or more of the following solvents: acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (VC), vinylethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran Lactone (GBL), and gamma-valerolactone (GVL).

In one embodiment, the phosphonium electrolyte compositions disclosed herein can be applied onto a porous electrode and a separator prior to cell assembly by any suitable means such as, for example, soaking, spraying, screen printing, have. In other embodiments, the phosphonium electrolyte compositions disclosed herein can be applied onto the porous electrode and the separator after cell assembly by using any suitable means, for example, a vacuum injection apparatus. In another embodiment, the phosphonium electrolyte composition disclosed herein may be in the form of a polymer gel electrolyte film or membrane. Alternatively, the polymer gel electrolyte can be applied directly to the electrode. Electrodes coated with free-standing gel electrolyte films or gel electrolytes are particularly suitable for high volume and high throughput manufacturing processes, for example, roll-to-roll winding processes. Another advantage of such an electrolyte film is that it can function not only as an electrolyte but also as a separator. Such an electrolyte film can also be used as an electrolyte carrier to precisely control the amount and distribution of electrolyte, thereby improving cell assembly consistency and increasing product yield. In some embodiments, the electrolyte film comprises a membrane as disclosed in co-pending patent application number 12 / 027,924, filed February 7, 2008, the entire disclosure of which is incorporated herein by reference in its entirety Lt; / RTI >

In some embodiments, the current collector may include, but is not limited to, an aluminum plate or foil or film, carbon coated aluminum, stainless steel, carbon coated stainless steel, gold, platinum, silver, Doped plastic, or a combination thereof.

In one embodiment, both electrodes 12 and 12 'of the single cell EDLC 10 may be fabricated from the same type of active material to provide a symmetrical electrode configuration. Alternatively, the EDLC may have an asymmetric electrode configuration, where each electrode is in the form of a different type of active material. In a preferred embodiment, the symmetric EDLC is easier to manufacture than the asymmetric EDLC. In addition, the symmetric EDLC is capable of reversing the polarity of the two electrodes, which enables the advantage of continuous high performance during long-term charge cycling. However, the asymmetric EDLC is selected from electrode materials whose selection is determined by cost and performance.

In an exemplary embodiment, the EDLC device comprises a pair of porous electrodes made from activated carbon bonded to an aluminum current collector, an NKK cellulose separator sandwiched between the two electrodes, and a pore of the separator and the electrodes , And the filling includes the phosphonium electrolyte disclosed in this specification.

In another exemplary embodiment, the EDLC is fabricated as a stack of cell components. As shown in FIGS. 2A and 2B, the electrode active material and the binder of activated carbon particles may be attached to one side of the current collector to form a single-sided electrode or attached to both sides of the "bipolar & Thereby forming a double-sided electrode. In the multi-cell stack, a first NKK cellulosic separator is disposed on the first cross-section electrode, a first bipolar electrode is disposed on the first separator, a second separator is disposed on the first bipolar electrode, A second bipolar electrode is disposed on the second separator, a third separator is disposed on the second bipolar electrode, a third bipolar electrode is disposed on the third separator, and a fourth separator is disposed on the third bipolar electrode And the second cross-sectional electrode is disposed on the fourth separator to form four cell stacks. An EDLC containing more cells may be fabricated to form the first multi-cell module as described above. The module may then be stacked on top of another module until a desired number of modules is achieved. The periphery of the edge of the electrode / separator / electrode assembly is partially sealed. Before the edges are completely sealed, a sufficient amount of the phosphonium electrolyte described herein is added to the assembly to fill the pores of the separator and the electrodes.

In another exemplary embodiment, spirally wound EDLC is formed. The electrode active material and the binder of the activated carbon particles adhere to both sides of the current collector to form a double-sided electrode similar in structure to that shown in Figs. 2A and 2B. The electrode / separator stack or assembly includes a first electrode disposed on the first Celgard® polypropylene / polyethylene separator, a second separator disposed on the first electrode, a second electrode disposed on the second separator, . The stack is wound around a round spiral tight cell center to form a cylindrical structure or is wound around a flat, helical, dense cell center to form a prismatic structure. Thereafter, the stack is partially sealed or disposed in the can. Prior to final sealing, a sufficient amount of any of the electrolytes described herein is added to the pores of the separator and electrodes of the stack.

In another exemplary embodiment, an EDLC device may be fabricated using a conductive polymer as an electrode active material for the phosphonium electrolyte composition and one electrode or both disclosed herein, which may reduce the total storage density of the device . The conductive polymer may be selected from any of the conductive organic material classes including polyaniline, polypyrrole and polythiophene. Polythiophenes, such as poly (3- (4-fluorophenyl) thiophene) (PFPT), are particularly interesting because they have excellent stability to electrochemical cycling and are known to be readily processable.

In a further illustrative embodiment, the EDLC device comprises an anode (negative electrode) made of graphite, a cathode made of a high surface area activated carbon (positive electrode) and lithium ion intercalated graphite, . ≪ / RTI > The EDLC formed is an asymmetric hybrid capacitor referred to as a lithium ion capacitor (LIC).

An important requirement for enhanced energy cycle efficiency and maximum power delivery is equivalent cell series equivalent series resistance (ESR). Thus, for EDLC electrolytes it is useful to have a high conductivity for ion transport. Surprisingly, when the phosphonium electrolyte compositions described herein replace conventional electrolytes, as described above, or when phosphonium salts are used as additives with conventional electrolytes, ionic conductivity is significantly increased and EDLC The performance stability of the device is greatly improved as can be seen from the following examples.

In an exemplary embodiment, the solventless pure phosphonium ionic liquid (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ has an ionic conductivity of 15.2 mS / cm .

In another exemplary embodiment, when the phosphonium ionic liquid (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ is mixed in a solvent of acetonitrile (ACN) And an ionic conductivity of 75 mS / cm at an ACN / ionic liquid volume ratio of 1.5 to 2.0.

In another exemplary embodiment, when the phosphonium ionic liquid (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ is mixed into the solvent of propylene carbonate (PC) And an ion conductivity of 22 mS / cm at a PC / ionic liquid volume ratio of 0.75 to 1.25.

In another exemplary embodiment, various phosphonium salts were dissolved at a concentration of 1.0 M in acetonitrile (ACN) solvent. The resulting electrolyte exhibited ionic conductivities of greater than about 28 mS / cm, or greater than about 34 mS / cm, or greater than about 41 mS / cm, or greater than about 55 mS / cm, or greater than about 61 mS / cm at room temperature .

In another exemplary embodiment, a typical (but not exclusive) solution of 1.0 M LiPF ₆ in a solvent (EC: DEC = 1: 1) mixed in a weight ratio of EC (ethylene carbonate) (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ is added in an amount of 10% by weight to the phosphorous electrolytic solution. The ionic conductivity of the electrolyte increases up to about 25% at -30 ° C at 109%, + 20 ° C, and + 60 ° C with the addition of a phosphonium additive. Generally, the ionic conductivity of conventional electrolytes increases by at least 25% as a result of the phosphonium additive.

In a further exemplary embodiment, a solvent (EC: DEC: EMC 1: 1: 1) mixed in a weight ratio of EC (ethylene carbonate) mentioned search) to a conventional electrolyte solution of LiPF ₆ in the 1.0 M of, phosphonium salts _{(CH 3 CH 2 CH 2)} (CH 3 CH 2) (CH 3) 2 PCF 3 BF 3 is added to 10 w% as. The ionic conductivity of the electrolyte increases by 36% at 20 DEG C, 26% at 60 DEG C, and 38% at 90 DEG C with the addition of the phosphonium additive. Generally, the ionic conductivity of conventional electrolytes increases by at least 25% as a result of the phosphonium additive.

The separator was found to be the largest single source of cell ESR. Therefore, a suitable separator has a high ionic conductivity when immersed in an electrolyte and needs to have a minimum thickness. In one embodiment, the separator is less than about 100 μm thick. In another embodiment, the separator is less than about 50 탆 thick. In another embodiment, the separator is less than about 30 탆 thick. In another embodiment, the separator is less than about 10 탆 thick.

Another important advantage of the novel phosphonium electrolyte compositions disclosed herein, which use phosphonium salts as replacements for conventional electrolytes or as additives, is that they exhibit a wider electrochemical voltage stability range over conventional electrolytes.

In some exemplary embodiments, various phosphonium salts are dissolved in an acetonitrile (ACN) solvent to form an electrolyte at a concentration of 1.0 M. The electrochemical voltage range is measured in a cell having a Pt working electrode, a Pt counter electrode and an Ag / Ag + reference electrode. In one arrangement, the stable voltage range is about -3.0 V to +2.4 V. In another arrangement, the voltage range is about -3.2 V to +2.4 V. In another arrangement, the voltage range is about -2.4 V to +2.5 V. In another arrangement, the voltage range is about -1.9V to +3.0V.

In further exemplary embodiments, the single cell EDLC is composed of two carbon electrodes, a cellulose separator sandwiched between the two electrodes, and an electrolyte of various phosphonium salts dissolved in a 1.0 M concentration in a propylene carbonate (PC) solvent . In one arrangement, the EDLC can be charged and discharged from 0 V to 3.9 V. In another arrangement, the EDLC can be charged and discharged from 0 V to 3.6V. In another arrangement, the EDLC can be charged and discharged from 0 V to 3.3 V. In an additional arrangement of EDLCs configured in a symmetric structure, the EDLC may be operated at -3.9 V to +3.9 V, or -3.6 V to +3.6 V, or -3.3 V to +3.3 V.

Another important advantage of the use of the phosphonium electrolyte compositions disclosed herein, either as a replacement for conventional ELDC electrolytes or using phosphonium salts as additives, is that they exhibit reduced vapor pressure and thus reduced flammability compared to conventional electrolytes , Thus improving the stability of EDLC operation. In one aspect of the present invention, when a phosphonium salt is used as an additive with a conventional electrolyte (containing a conventional, non-phosphonium salt), the phosphonium salt and the conventional salt are used in an amount of from 1/100 to 1 / 1 < / RTI > of the phosphonium salt / conventional salt. Examples of typical salts include, but are not limited to, tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF _4), 1- ethyl-3-methylimidazolium bis (methanesulfonyl trifluoromethanesulfonyl) imide (EMIIm), including phosphate (EMIPF _6), 1- ethyl-3-methyl imidazolium hexafluoro in do.

In an exemplary embodiment, the electrolyte is a phosphonium salt - (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF _{3 in} a concentration of 1.0 M in a solvent of acetonitrile (ACN) Is dissolved. The vapor pressure of ACN is reduced to about 39% at 25 ° C and to 38% at 105 ° C. Significant inhibition of the vapor pressure by the phosphonium salt has the advantage of reducing the flammability of the electrolyte, thus improving the safety of the device operation.

In another exemplary embodiment, a conventional electrolyte solution of 1.0 M LiPF ₆ in a solvent in which EC (ethylene carbonate) and DEC (diethyl carbonate) are mixed in a weight ratio of 1: 1, is supplied by Novolyte Technologies (a subsidiary of BASF group) Lt; / RTI > A phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was added to the standard electrolyte at 20 wt%. The self-extinguishing time was reduced by 53% by adding the phosphonium additive to the conventional electrolyte. This indicates that the stability and reliability of the energy storage device can be substantially improved by using phosphonium salts as additives in conventional electrolytes.

An additional significant advantage of EDLC formed in accordance with the present invention, compared to the prior art, is their broad temperature range. As can be seen in the following examples, the EDLC made with the novel phosphonium electrolytes disclosed herein has a pH of from about -50 ^° C to +120 ^° C, or from about -40 ^° C to + 105 ^° C, 20 ^° C to + 85 ^° C, or -10 ^° C to +65 ^° C. Thus, with the materials and structures disclosed herein, it is now possible to produce EDLC that can function in the extended temperature range. This makes it possible to implement such a device in a wide range of applications that experience a wide temperature range during manufacture and / or operation.

In some preferred embodiments, the EDLC is designed to operate at various voltage and temperature combinations. In one arrangement, the EDLC is comprised of 2.5 V and 120 < RTI ID = 0.0 > ^o Can be operated in C In another arrangement, the EDLC is 2.7 V and 105 < RTI ID = 0.0 > ^o Can be operated in C In another arrangement, the EDLC is 2.8 V and 85 < RTI ID = 0.0 > ^o Can be operated in C In another arrangement, the EDLC is comprised of 3.0 V and 70 < RTI ID = 0.0 > ^o Can be operated in C In a further arrangement, the EDLC can be operated at 3.5 V and 60 ^o C.

In a further embodiment, the approach to energy storage may be combined with a cell to form a capacitor-cell hybrid energy storage system comprising an array of cells and an EDL.

Electrolytic capacitor

Phosphonium ionic liquids, salts, and compositions in accordance with embodiments of the present invention are well suited to electrolytes of electrolytic capacitors. In one embodiment, the anode (cathode); Cathode (anode); A separator between the anode and the cathode; And an electrolytic solution is provided. The electrolyte is comprised of an ionic liquid composition or a salt dissolved in one or more ionic liquids or solvents, wherein the one or more ionic liquids or salts comprise one or more phosphonium cations of the following general formula: And one or more anions;

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In one embodiment, the electrolyte is comprised of an ionic liquid having one or more phosphonium-based cations and one or more anions, wherein the ionic liquid composition has a thermodynamic stability of up to 375 ^° C, a liquidus line range of greater than 400 ^° C, And at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm at room temperature. In another embodiment, the electrolyte is comprised of one or more salts having one or more phosphonium-based cations and one or more anions dissolved in a solvent, wherein the electrolyte composition is at least 5 mS / cm, or at least 10 mS / cm , Or at least 15 mS / cm, or at least 20 mS / cm, or at least 30 mS / cm, or at least 40 mS / cm, or at least 50 mS / cm, or at least 60 mS / cm. In some embodiments, the electrolyte composition comprises but is not limited to one or more of the following solvents: acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate ), Diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate VC), vinylethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (GBL), and gamma -valerolactone (GVL). In one embodiment, the anode-anode is typically an aluminum oxide or an aluminum foil having an oxide thin film formed by anodization. Although aluminum is the preferred metal for the anode, other metals such as tantalum, magnesium, titanium, niobium, zirconium and zinc may also be used. The cathode-cathode is usually an aluminum foil etched. In a further aspect, the phosphonium electrolyte exhibits reduced flammability compared to conventional electrolytes, thus enhancing the stability of electrolytic capacitor operation.

Dye-sensitized solar cell

The phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited for electrolytes of dye sensitized solar cells (DSSCs). In one embodiment, there is provided a DSSC comprising a dye molecule attached anode, an electrolyte comprising a redox system, and a cathode. The electrolyte is comprised of an ionic liquid composition or a salt dissolved in one or more ionic liquids or solvents, wherein the one or more ionic liquids or salts comprise one or more phosphonium cations of the following general formula: And one or more anions;

R ¹ R ² R ³ R ⁴ P

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a substituent. In another embodiment, the electrolyte has at least one phosphonium-based cation and at least one anion wherein the electrolyte composition has at least two of thermodynamic stability, low volatility, broad liquid line range, ionic conductivity, chemical stability, and electrochemical stability Or more. In another embodiment, the electrolyte has at least one phosphonium-based cation and at least one anion, wherein the electrolyte composition has a thermodynamic stability of at least about 375 ^o C and a conductivity of at least 5 mS / cm, or at least 10 mS / cm , Or at least 15 mS / cm.

Electrolytic film

Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytic or electrolyte films. In one embodiment, there is provided an electrolytic film comprising a phosphonium ionic liquid composition applied to a substrate. In another embodiment, there is provided an electrolytic film comprising at least one phosphonium ionic liquid applied to a substrate or a salt dissolved in a solvent. In one embodiment, the at least one phosphonium ionic liquid or salt is dissolved in the solvent to form a coating solution. The coating solution is applied to the substrate in any suitable manner, for example, by spraying, spin coating, or the like. Then, the substrate is heated to partially or wholly remove the solvent to form an electrolyte or an ion conductive film. In another embodiment, a solution of the ionic liquid, salt and polymer dissolved in a suitable solvent is coated onto the substrate, for example by spray or spin coating, and then the solvent is partially or fully evaporated. Thereby, an ion conductive polymer gel / film is formed. Such films are particularly suitable as batteries, EDLC, and electrolytes of DSSC, and fuel cell membranes.

Heat transfer medium

The high thermodynamic stability, low volatility, and desirable properties of the wide liquid line range of the phosphonium ionic liquids of the present invention are well suited as heat transfer media. Some embodiments of the present invention include an ionic liquid composition as a heat transfer medium or at least one salt dissolved in a solvent, wherein at least one salt comprises at least one phosphonium-based cation and at least one anion, wherein the heat transfer medium has a maximum approximately it provides the heat transfer medium that represents the liquidus range of thermodynamic stability and 400 ^o C in excess of the temperature of 375 ^o C. In some embodiments, the heat transfer medium of the present invention is a high temperature reaction medium. In another embodiment, the heat transfer medium of the present invention is a heat extraction medium.

Other applications

The phosphonium ionic liquids of the present invention find use in further applications. In one exemplary embodiment, embedded capacitors are verified. In one embodiment, the buried capacitor is comprised of a dielectric disposed between two electrodes, and the dielectric is comprised of an electrolytic film of a phosphonium ionic composition as described above. Embedded capacitors of the present invention may be embedded in an integrated circuit package. Additional implementations include "on-board" capacitor placement.

The above description is meant to be exemplary, and the application of such phosphonium ionic liquid electrolyte compositions is not limited to the listed applications or processes.

Example

Embodiments of the present invention will be described in more detail with reference to the following specific embodiments. The embodiments provided below are intended for illustrative purposes only and are not intended to limit the scope and / or teaching of the invention.

Generally, the phosphonium ionic liquid is reacted with metathesis reactions with a suitably substituted phosphonium salt and a suitably substituted metal salt, or with an appropriately substituted phosphine precursor and an appropriately substituted anion precursor . ≪ / RTI > Figures 3-6 illustrate reaction schemes for preparing four exemplary embodiments of the phosphonium ionic liquids of the present invention.

Example  One

A phosphonium ionic liquid was prepared. AgSO ₃ CF ₃ was filled into a 50 ml round bottom (Rb) flask and assembled into a 3 cm swivel frit. The flask was evacuated and brought into a glove box. In the glove box, di-n-propylethylmethylphosphonium iodide was added and the flask was reassembled, brought to a vacuum line, emptied, and anhydrous THF was transferred in vacuo. The flask was allowed to warm to room temperature and then heated to 40 [deg.] C for 2 hours. As a result, a pale green bead-like solid was formed. The solid was filtered off. This gave a milky white solution like pearls. The volatiles were removed under high vacuum with heating using a hot bath at 30 占 폚. As a result, a white crystalline material having a yield of 0.470 g was produced. The material was subjected to thermogravimetric analysis (TGA) and the results are shown in FIG.

Example  2

Additional phosphonium ionic liquids were prepared. Di-n-propylethyl methylphosphonium iodide was added to a 100 ml Rb flask in a glove box and then separated and dissolved in 50 ml DI H ₂ O. To this solution, AgO ₂ CCF ₃ was added and immediately a yellow bead-like precipitate was obtained. After stirring for 2 hours, AgI was separated by filtration and the cake was washed three times with 5 ml DI H ₂ O each. Most of the water was removed on a rotary evaporator. Thereby, a clear, low viscosity liquid was obtained, which was then dried under high vacuum with heating and stirring. This resulted in solidification of the material. In warm baths, a gentle warming of the white solid produced a liquid, which appeared to melt just above room temperature. This experiment yielded 0.410 g of material. The above reaction formula is shown in Fig. Thermogravimetric analysis (TGA) and evolved gas analysis (EGA) tests were performed on the material and the results are shown in Figures 8b and 8c, respectively.

Example  3

In this example, di-n-propylethyl methylphosphonium iodide was added to a 100 ml Rb flask in a glove box, which was then taken out of the fume hood and dissolved in 70 ml MeOH. Next, AgO ₂ CCF ₂ CF ₂ CF ₃ was added and immediately a yellow slurry was obtained. After stirring for 3 hours, the solids were separated by filtration, most of the MeOH was removed by rotary evaporation and the remaining residue was dried under high vacuum. Thus, a yellow gel-like slush material was obtained. It was observed that a "liquid" type of crystals were formed on the sides of the Rb flask, which was then "melted" by scraping the flask. This experiment yielded 0.618 g of material. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in Figure 9a. The product gas analysis (EGA) was also performed and the results are shown in FIG. 9b.

Example  4

A pressure flask was brought into the glove box and filled with 0.100 g of P (CH ₂ OH) ₃ followed by 5 mL of THF-d8. Once the solids dissolved, Me ₂ SO ₄ was added. Next, the flask was sealed and removed from the glove box. It was heated in a 110 ° C oil bath for 10 minutes, then cooled, brought back into the glove box and 1 mL of aliquot was separated for ¹ H NMR. The above reaction scheme is illustrated in FIG. 10A. ¹ H NMR is shown in FIG.

Example  5

In this experiment, 1-ethyl-1-methylphosphoranium nitrate was added to a 100 ml 14/20 Rb flask in a glovebox. Here, KC (CN) ₃ was added, and then Rb was assembled into a 3 cm swivel frit. The frit was removed from the line and CHCl ₃ was vacuum transferred into it. The flask was stirred for about 12 hours. Gooey brown material was observed on the bottom of the flask. The solution was filtered to give a milky white filtrate, from which the brown oil was separated. The brown oil was washed twice with recycled CHCl ₃ , resulting in a whiter and more granular form. All volatile components were removed under high vacuum, resulting in a low viscosity brown oil. This experiment yielded 1.52 g of material. The above reaction scheme is shown in FIG. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in FIG. 11b.

Example  6

In this example, 1-ethyl-1-methylphosphorinanium iodide was added to a 100 ml Rb flask in a glovebox, which was then removed from the fume hood and dissolved in 70 ml MeOH. Next, AgO ₂ CCF ₂ CF ₂ CF ₃ was added, and a yellow precipitate was immediately obtained. The flask was stirred for 18 hours, and then the solid was removed by filtration. Most of the MeOH was removed by rotary evaporation and the residue was dried under high vacuum. By this procedure, an off-white, yellow-colored solid was obtained. This experiment yielded 0.620 g of material. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in FIG.

Example  7

In another experiment, 1-butyl-1-ethylphosphoranium iodide was added to the Rb flask in a fume hood, which was then dissolved in water and stirred. AgO ₃ SCF ₃ was added and a yellow precipitate formed immediately. The flask was stirred for 2 hours and then vacuum filtered. The solution was bubbled through filtration and the milky material was observed after filtration. The material was rotary evaporated and the residue was dried under vacuum on an oil bath on which the solid was melted. This experiment yielded 0.490 g of material. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in FIG.

Example  8

In a further experiment, 1-butyl-1-ethylphosphoranium iodide was added to the flask in a fume hood. MeOH was added, and then the flask was stirred for 15 minutes. Was added p-toluenesulfonate. The flask was stirred for 4 hours. A yellow precipitate formed. The material was gravity filtered and then rotary evaporated. The material was dried under vacuum to give a liquid. This experiment yielded 0.253 g of material. The above reaction formula is shown in Fig. 14A. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in FIG. 14B.

Example  9

In another experiment, 250 mg (0.96 mmol) triethyl methylphosphine iodide was added to 15 mL deionized water, followed by 163 mg (0.96 mmol) silver nitrate pre-dissolved in 5.0 mL deionized water. The reaction was stirred for 10 minutes, at which time the white to yellow precipitate was filtered off. Next, the solid was washed with 5.0 mL deionized water and the aqueous fractions were mixed. The water was removed under vacuum on a rotary evaporator to leave a white solid residue which was recrystallized from a 3: 1 mixture of ethyl acetate and acetonitrile to give triethylmethylphosphonium nitrate. Yield: 176 mg, 94%. The above phosphonium nitrate (176 mg, 0.90 mmol) was dissolved in 5 mL of anhydrous acetonitrile. 113 mg (0.90 mmol) of potassium tetrafluoroborate dissolved in 5 mL anhydrous acetonitrile was added to the phosphonium salt and after 5 minutes of stirring the solids were separated by filtration. The solvent was removed on a rotary evaporator, yielding an analytically pure triethylmethylphosphonium tetrafluoroborate by obtaining an off-white solid which was recrystallized from hot 2-propanol. Yield: 161 mg, 81%. The composition was confirmed by the ¹ H NMR spectrum shown in Fig. 15A and the ³¹ P NMR shown in Fig. 15B. The material was subjected to thermogravimetric analysis (TGA) and the results are shown in Fig.

Example  10

In another experiment, 250 mg (1.04 mmol) of triethylpropylphosphonium bromide and 135 mg (1.06 mmol) of potassium tetrafluoroborate were mixed in 10 mL of acetonitrile. A fine white precipitate of KBr began to form immediately. The mixture was stirred for 1 hour, it was filtered and the solvent was removed on a rotary evaporator to give a white solid. Yield: 218 mg, 85%. This crude product was recrystallized from 2-propanol to give the analytically pure material. The composition was confirmed by the ¹ H NMR spectrum shown in Fig. 17A and the ³¹ P NMR shown in Fig. 17B. Thermogravimetric analysis (TGA) was performed on the material and the results are shown in FIG.

Example  11

For further work, the reaction was carried out in a glovebox under a nitrogen atmosphere. Triethylpropylphosphonium iodide (1.00 g, 3.47 mmol) was dissolved in 20 mL of anhydrous acetonitrile. To this solution, 877 mg (3.47 mmol) of silver hexafluorophosphate was added with continued stirring. A white precipitate of iodide was formed immediately and the reaction was stirred for 5 minutes. The precipitate was filtered off and washed several times with anhydrous CH ₃ CN. The precipitate was taken out from the glove box and evaporated to give a white solid. The crude material was dissolved in hot isopropanol and passed through a 0.2 탆 PTFE membrane. The filtrate was cooled to obtain white crystals collected by filtration. Yield: 744 mg, 70%. The composition was confirmed by the ¹ H NMR spectrum shown in Fig. 19A and the ³¹ P NMR shown in Fig. 19B. The material was subjected to thermogravimetric analysis (TGA) and the results are shown in Fig.

Example  12

In this embodiment, the 1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 PCF 3 BF 3 / (CH 3 CH 2 CH 2) (CH 3 CH 2) (CH 3) 2 _{P CF 3 BF 3 / (CH} 3 CH 2 CH 2) (CH 3 CH 2) 2 (CH 3) a third component phosphonium ionic liquid composition comprising a _{P CF 3 BF 3 (CH 3} CH 2 CH 2) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P CF ₃ BF ₃ . The material was subjected to differential scanning calorimetry (DSC) and the results are shown in Figure 21a for a single component composition and Figure 21b for a three component composition. As shown in FIGS. 21A and 21B, the ternary composition exhibits the advantage of a lower cooling temperature and hence greater liquidus line coverage as compared to a single component composition.

Example  13

In another experiment, a phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was prepared. When measured in an electrochemical cell having a Pt working electrode, a Pt counter electrode and an Ag / Ag ⁺ reference electrode, the salt had a low viscosity of 19.5 cP at 25 캜, a melting point of -10.0 캜, an onset decomposition temperature of 396.1 캜, A liquid range of 407 DEG C, an ionic conductivity of 15.2 mS / cm, and an electrochemical voltage range of -1.5 < -5 > The results are summarized in Table 14 below.

[Table 14]

Example  14

In another experiment, a phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was prepared. The salt was dissolved in a solvent of acetonitrile (ACN) to have an ACN / salt volume ratio in the range of 0-4. The ion conductivity of the resulting electrolyte was measured at room temperature, and the results are shown in FIG. As shown in Fig. 22, the ionic conductivity increased from 13.2 mS / cm to a peak value of 75 mS / cm at a ratio of 1.5 to 2.0 in a 0 ratio (pure ionic liquid) with an increase in ACN / salt ratio.

Example  15

In another experiment, a phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was prepared. The salt was dissolved in a solvent of propylene carbonate (PC) so that the PC / salt volume ratio was in the range of 0 to 2.3. The ion conductivity of the produced electrolyte was measured at room temperature, and the results are shown in FIG. As shown in Fig. 23, the ionic conductivity increased from 13.9 mS / cm to a peak value of 22 mS / cm at a ratio of 0.75 to 1.25 in a 0 ratio (pure ionic liquid) with an increase in PC / salt ratio.

Example  16-35

In further experiments, various phosphonium salts were prepared. The salt was dissolved in a solvent of acetonitrile (ACN) to form an electrolyte at a concentration of 1.0M. The ion conductivity of the resulting electrolyte was measured at room temperature. The electrochemically stable voltage range was measured in an electrochemical cell with Pt working electrode, Pt counter electrode and Ag / Ag + reference electrode. The results are summarized in Table 15. The electrolyte exhibited ionic conductivities of greater than about 28 mS / cm, or greater than about 34 mS / cm, or greater than about 41 mS / cm, or greater than about 55 mS / cm, or greater than about 61 mS / cm at room temperature. In one batch, the electrochemical voltage range was about -3.2 V to +2.4 V. In another arrangement, the electrochemical voltage range was about -3.0 V to + 2.4 V. In another arrangement, the electrochemical voltage range was about -2.0 V to +2.4 V.

[Table 15]

Example  36-41

In a further experiment, various phosphonium salts were prepared and compared to ammonium salts as controls. The salt was dissolved in a solvent of propylene carbonate (PC) to form an electrolyte at a concentration of 1.0M. The ion conductivity of the resulting electrolyte was measured at room temperature. The electrochemical voltage range was measured in an electrochemical cell having a Pt working electrode, a Pt counter electrode and an Ag / Ag + reference electrode. The results are summarized in Table 16, demonstrating that the phosphonium salt exhibits a higher conductivity and wider electrochemical voltage stability range than the control-ammonium analog. In one batch, the electrochemical range was about -2.4 V to +2.5 V. In another arrangement, the electrochemical range was about -1.9 V to +3.0 V

[Table 16]

Example  42-45

In a further experiment, various phosphonium salts were prepared and compared to ammonium salts as controls. The salt was dissolved in a solvent of propylene carbonate (PC) to form an electrolyte at a concentration ranging from 0.6 M to 5.4 M. The ion conductivity of the resulting electrolytic solution was measured at room temperature, and the results are shown in Fig. Concentration values of the 2.0 M concentration are shown in Table 17, demonstrating that the phosphonium salt exhibits a higher conductivity than the control-ammonium analog.

[Table 17]

Example  46

In another experiment, a phosphonium salt- (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was prepared and used as a control for the ammonium salt (CH ₃ CH ₂ ) ₃ (CH ₃ ) compared with NBF ₄ . The salt was dissolved in an acetonitrile (ACN) solvent to form an electrolyte at a concentration of 1.0M. The vapor pressure of the solution was measured at 25 to 105 DEG C by differential scanning calorimetry (DSC). The ion conductivity of the resulting electrolyte was measured at room temperature. As shown in Fig. 25, the vapor pressure of ACN is higher by 39% in case of having a phosphonium salt than in 27% in the case of having an ammonium salt at 25 ° C and higher than 13% of having in case of having an ammonium salt at 105 ° C, If salt is present, it is lowered to 38%. Significant inhibition of the vapor pressure by the phosphonium salts is beneficial in reducing the flammability of the electrolyte and thus in improving the stability of the EDLC operation.

Example  47-50

In another experiment, phosphonium salts were used as additives in conventional electrolytes of lithium batteries. In one embodiment of the present invention, 1.0 M LiPF ₆ in a mixed solvent (referred to as EC: DEC 1: 1) in which EC (ethylene carbonate) and DEC (diethyl carbonate) are mixed in a weight ratio of 1: Conventional electrolytes were supplied by Novolyte Technologies (a subsidiary of the BASF group). The phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was added to the conventional electrolytic solution at 20 wt%. In another embodiment of the present invention, a solvent (EC: DEC: EMC 1: 1: 1) mixed in a weight ratio of EC (ethylene carbonate), DEC (diethyl carbonate) referred to as 1) was provided a conventional electrolytic solution of 1.0 M of LiPF ₆ in the in Novolyte Technologies (of BASF group of companies). The phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was added to the conventional electrolytic solution at 10 wt%. To perform the self-extinguishing test, a sample of 1 g of the electrolyte was poured into a glass dish, the sample was burnt, and the time required for the flame to be digested was recorded. The self-extinguishing time (SET) was normalized to the mass of the sample. The results are summarized in Table 18 below. The phosphonium additive at concentrations between 10 and 20 w% reduced the self-extinguishing time from 33 to 53%. This indicates that the stability and reliability of a lithium ion battery can be substantially improved by using a phosphonium salt as an additive to a conventional lithium ion electrolyte.

[Table 18]

Example  51

In another experimental example, a phosphonium salt was used as an additive for a standard lithium battery electrolyte. In one embodiment of the present invention, 1.0 M LiPF ₆ in a mixed solvent (referred to as EC: DEC 1: 1) in which EC (ethylene carbonate) and DEC (diethyl carbonate) are mixed in a weight ratio of 1: Standard electrolytes were supplied by Novolyte Technologies (a subsidiary of the BASF group). The phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was added to the standard electrolyte at 10 wt%. The ionic conductivity of both the standard electrolyte solution and the solution having the phosphonium additive was measured at various temperatures of -30 to 60 캜. As shown in Fig. 26, the phosphonium additive improved the ion conductivity of the electrolyte solution over a wide temperature range. At -30 캜, the ionic conductivity increased to 109% as a result of the phosphonium additive. At + 20 < 0 > C, ionic conductivity increased to 23% as a result of the phosphonium additive. At + 60 < 0 > C, ionic conductivity increased to about 25% as a result of the phosphonium additive. Generally, the ionic conductivity of the standard electrolyte has increased by at least 25% as a result of the phosphonium additive.

Example  52

In another experiment, a phosphonium salt was used as an additive for a lithium battery standard electrolyte solution. In one embodiment of the present invention, a solvent (EC: DEC: EMC 1: 1: 1) mixed in a weight ratio of EC (ethylene carbonate), DEC (diethyl carbonate) referred to as 1) was provided a standard electrolyte of 1.0 M of LiPF ₆ in the in Novolyte Technologies (of BASF group of companies). The phosphonium salt CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was added to the standard electrolyte at 10 wt%. The ionic conductivity of both the standard electrolyte solution and the solution having the phosphonium additive was measured at various temperatures of 20 to 90 占 폚. As shown in Fig. 27, the phosphonium additive improved the ion conductivity of the electrolyte solution over a wide temperature range. At 20 캜, the ion conductivity increased to 36% as a result of the phosphonium additive. At 60 캜, ionic conductivity increased to about 26% as a result of the phosphonium additive. At < RTI ID = 0.0 > 90 C, < / RTI > the ionic conductivity increased to about 38% as a result of the phosphonium additive. Generally, the ionic conductivity of the standard electrolyte has increased by at least 25% as a result of the phosphonium additive.

Example  53

In a further experiment, the coin cell as shown in Fig. 28 is composed of two carbon electrodes of 14 mm diameter in the form of a disk, a 19 mm diameter separator sandwiched between two electrodes and an impregnating electrolyte. In one embodiment of the present invention, activated carbon (Kuraray YP-50F, 1500 - 1800 m ² / g) was mixed with a binder to prepare two carbon electrodes each having a thickness of 100 μm, Thick aluminum housing. The above separator was prepared from 35 mu m NKK cellulose separator (TF40-35). Both the carbon electrode and the separator were impregnated with an electrolytic solution containing 1.0 M phosphonium salt in acetonitrile or propylene carbonate. The assembly was placed in a 2032 coin cell case and sealed by applying a suitable pressure using a crimper. The finished cell had a diameter of 20 mm and a thickness of 3.2 mm. The entire assembly process was carried out in a glove box filled with nitrogen. The completed cells were characterized by CHI constant voltage (potentiostat) by charging and discharging at a constant current. FIG. 29 shows the charge-discharge curves of these coin cells with 1.0 M (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in the propylene carbonate electrolyte. The cell was first charged from 0 V to 2.5 V at 10 mA and then discharged to 1.0 V. [ The cell capacitance was measured to be 0.55F.

Example  54-57

In further experiments, the pouch cell as shown in Figures 30A and 30B consists of two carbon electrodes 15 mm x 15 mm, a 20 mm x 20 mm separator sandwiched between the two electrodes, and an immersion electrolyte . Optionally, the pouch cell comprises a third electrode-reference electrode, for example a silver electrode, so that the potential at each carbon electrode can be measured. In one embodiment of the present invention, ^two 100 μm thick carbon electrodes were prepared by mixing active carbon (Kuraray YP-50F, 1500 - 1800 m ² / g) with a binder, each having a thickness of 30 μm Lt; / RTI > The above separator was prepared from 35 mu m NKK cellulose separator (TF40-35). Both the carbon electrode and the separator were impregnated with an electrolytic solution containing 1.0 M phosphonium salt in acetonitrile or propylene carbonate. The assemblies were arranged side by side and then the two current collecting tabs were bonded together using a hot melt adhesive tape to prevent leakage around the tabs. The assembly was then vacuum sealed in an aluminum laminate pouch bag. The finished cell had a size of 70 mm x 30 mm and a thickness of 0.3 mm. The entire assembly process was carried out in a glove box filled with nitrogen. The completed cells were characterized by CHI constant voltage by charging and discharging at a constant current. 31A shows the charge-discharge curve of a pouch cell having 1.0 M (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in propylene carbonate. The cell was charged and discharged from 0 to 2.7 V at 10 mA. FIG. 31B shows the carbon positive electrode measured as a silver reference electrode and the separated electrode potential in a carbon negative electrode. In some cases, the pouch cell could be fully charged to a high voltage up to 3.9 volts. The results are summarized in Table 19 below. In one arrangement, the EDLC can be charged and discharged from 0 V to 3.9 V. In another arrangement, the EDLC can be charged and discharged from 0 V to 3.6 V. In another arrangement, the EDLC can be charged and discharged from 0 V to 3.3 V.

[Table 19]

Example  58

In a further experiment, the cylindrical cell as shown in Fig. 32 had a first separator strip of 6 cm x 50 cm, a first carbon electrode strip of 5.8 cm x 50 cm disposed above the first separator, A second separator strip of 6 cm x 50 cm disposed on top of one carbon electrode strip, and a second carbon electrode strip of 5.8 cm x 50 cm disposed on top of the second separator. The electrode / separator assembly was wound in a jellyroll fashion around a tight cell center. In one embodiment of the present invention, a carbon electrode having a thickness of 100 μm is prepared by mixing active carbon (Kuraray YP-50F, 1500 to 1800 m ² / g) with a binder, Bonded to both sides to create a double-sided electrode structure. The separator was prepared from an NKK cellulose separator (TF 40-35) having a thickness of 35 μm. The center of the jelly roll was placed in a 18650 cylindrical cell case. An electrolytic solution containing 1.0 M phosphonium salt in acetonitrile or propylene carbonate was added using a vacuum injector to ensure that the electrolyte permeates and completely fills the pores of the separator and the carbon electrodes. After filling the electrolyte, a cap was placed to seal the cell. The finished cylindrical cell had a diameter of 18 mm and a length of 65 mm. The entire assembly process was carried out in a dry room or in a nitrogen filled glove box. The completed cell was characterized by constant voltage of PAR VersaSTAT 4-200 by charging and discharging at a constant current. FIG. 33 shows the charge-discharge curves of such a cylindrical cell having an electrolyte of 1.0 M (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in propylene carbonate. The cell was first charged from 1.0 to 2.5 V at 600 mA, held at 2.5 V for 300 seconds, and then discharged to 2.5 V. [ The cell capacitance was measured to be 132F.

Example  59-61

In further experiments, for a pouch cell containing 1.0 M phosphonium salt in propylene carbonate, as compared to the ammonium salt as a control, 2.7 V and 70 < RTI ID = 0.0 > ^o Accelerated stress testing at C was performed. Cell performance stability was measured with initial capacitance retention. The result is shown in Fig. At 80 hours, the numerical values of the capacitance retention are shown in Table 20, which shows that cells with phosphonium salts exhibit a higher retention rate than cells with ammonium salts.

[Table 20]

Example  62

In further experiments, for a pouch cell containing an electrolyte of 1.0 M phosphonium salt- (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ , ammonium salt- (CH ₃ CH ₂ ) ₃ (CH ₃ ) NBF ₄ , it was found that -40 ^o C was to test the performance of the cell at various temperatures from +80 ^o C. 25 ^The cell performance stability was measured by the capacitance retention rate at C ^° . As shown in Figure 35, a cell with a phosphonium salt exhibits a higher retention at a temperature below 0 ^° C compared to a cell with an ammonium salt. As can be seen, EDLC made with the novel phosphonium electrolytes disclosed herein can be operated at a temperature range of -40 ^° C to + 80 ^° C. It is contemplated that the EDLC with the phosphonium electrolyte described herein can be operated in a temperature range of about -50 ^° C to +120 ^° C. Thus, with the materials and structures disclosed herein, it is now possible to produce EDLC that can function in the extended temperature range. This makes it possible to implement such a device in a wide range of applications that experience a wide temperature range during manufacture and / or operation.

It is not intended to limit the scope of the invention to the specific embodiments disclosed in the intended embodiments as examples of some aspects of the invention, and any implementations that are functionally equivalent are within the scope of the present invention. Indeed, various modifications of the invention, other than that shown and described herein, will be apparent to those of ordinary skill in the art, which is intended to be within the scope of the appended claims.

Several references are cited, the entire disclosures of which are incorporated herein by reference.

Claims (45)

As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the first electrode and the second electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
The electrolyte composition comprises at least one phosphonium ionic liquid or at least one phosphonium salt dissolved in a solvent,
Wherein the at least one phosphonium ionic liquid or phosphonium salt comprises at least one phosphonium cation of the formula: And at least one anion; an electrochemical double layer capacitor:
R ¹ R ² R ³ R ⁴ P
Here, R ¹ , R ² , R ^3, and R ⁴ are each independently an alkyl group. The method according to claim 1,
R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 4 carbon atoms. The method according to claim 1,
R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group consisting of 1 to 4 carbon atoms, at least two of the R groups are the same and all R groups are free of oxygen. The method according to claim 1,
Wherein at least one of the at least one R groups is substituted with fluorine. The method according to claim 1,
Any one or more of the above phosphonium salts may be liquid or solid at a temperature of 100 < ⁰ > C or less. The method according to claim 1,
Wherein at least one of said phosphonium ionic liquid or said phosphonium salt is composed of one cation and one anion pair. The method according to claim 1,
Wherein the at least one phosphonium ionic liquid or the phosphonium salt is composed of one anion and a plurality of cations. The method according to claim 1,
Wherein the at least one phosphonium ionic liquid or the phosphonium salt is composed of one cation and a plurality of anions. The method according to claim 1,
Wherein the at least one phosphonium ionic liquid or phosphonium salt comprises a plurality of cations and a plurality of anions. The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2 CH 2)} 2 (CH 3 CH 2) (CH 3) P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2 CH 2)} (CH 3 CH 2) (CH 3) 2 P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2) 3 (} CH 3) P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2 CH 2)} (CH 3 CH 2) 3 P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2) 4 P} + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2 CH 2)} 3 (CH 3) P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
_{(CH 3 CH 2 CH 2)} 3 (CH 3 CH 2) P + The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
(CF ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₃ P ⁺ The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
(CF ₃ CH ₂ CH ₂ ) ₃ (CH ₃ CH ₂ ) P ⁺ The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
(CF ₃ CH ₂ CH ₂ ) ₃ (CH ₃ ) P ⁺ The method according to claim 1,
Wherein the phosphonium-based cation is composed of an electrochemical double layer capacitor:
(CF ₃ CH ₂ CH ₂ ) ₄ P ⁺ The method according to claim 1,
The electrolyte composition comprises the phosphonium-based cation, and
_{PF 6, (CF 3) 3} PF 3, (CF 3) 4 PF 2, (CF 3 CF 2) 4 PF 2, (CF 3 CF 2 CF 2) 4 PF 2, (-OCOCOO-) PF 4, ( _{-OCOCOO -) (CF 3) 3} PF, (-OCOCOO-) 3 P, BF 4, CF 3 BF 3, (CF 3) 2 BF 2, (CF 3) 3 BF, (CF 3) 4 B, ( _{-OCOCOO-) BF 2, (-OCOCOO-)} BF (CF 3), (-OCOCOO -) (CF 3) 2 B, (-OSOCH 2 SOO-) BF 2, (-OSOCF 2 SOO-) BF 2, _{(-OSOCH 2 SOO-) BF (CF} 3), (-OSOCF 2 SOO-) BF (CF 3), (-OSOCH 2 SOO-) B (CF 3) 2, (-OSOCF 2 SOO-) B (CF ₃ ) ₂ , CF ₃ SO ₃ , (CF ₃ SO ₂ ) ₂ N, (-OCOCOO-) ₂ PF ₂ , (CF ₃ CF ₂ ) ₃ PF ₃ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ , _{-OCOCOO-) 2 B, (-OCO (} CH 2) n COO-) BF (CF 3), (-OCOCR 2 COO-) BF (CF 3), (-OCOCR 2 COO-) B (CF 3) 2 _{, (-OCOCR 2 COO-) 2 B} , CF 3 BF (-OOR) 2, CF 3 B (-OOR) 3, CF 3 B (-OOR) F 2, (-OCOCOCOO-) BF (CF 3), _{(-OCOCOCOO-) B (CF 3)} 2, (-OCOCOCOO-) 2 B, (-OCOCR 1 R 2 CR 1 R 2 COO-) BF (CF 3) and ^{(-OCOCR 1 R 2 CR 1 R} 2 COO -) B (CF ₃ ) ₂ wherein R, R ¹ and R ² are each independently H or F, , Electrochemical double layer capacitors. The method according to claim 1,
The one or more anions are _{^{- O 3 SCF 3, - O}} 2 CCF 3, - O 2 CCF 2 CF 2 CF 3, CF 3 BF 3 -, C (CN) 3 -, PF 6 -, NO 3 -, - O ^{_{3 SCH 3, BF 4 -,}} - O 3 SCF 2 CF 2 CF 3, - O 2 CCF 2 CF 3, - O 2 CH, - O 2 CC 6 H 5, - OCN, CO 3 2 -, (-OCOCOO ^{_{-) BF 2 -, (-OCOCOO}} -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, (CF 3 SO 2) 2 N -, (CF 3) 2 BF 2 -, (CF 3 ) ₃ BF ^- , CF ₃ CF ₂ BF ₃ ^- or ^- N (CN) ₂ . The method according to claim 1,
Wherein the electrolyte composition comprises an electrochemical double layer capacitor comprising the phosphonium salt and one or more of the following solvents:
(EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinylethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate Diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), gamma -butyrolactone (GBL), gamma -valerolactone (GVL) or mixtures thereof. The method according to claim 1,
Wherein the electrolyte composition comprises the phosphonium salt, wherein the phosphonium salt is a cation of the formula (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P ⁺ ; And
Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or any combination thereof. The method according to claim 1,
The electrolyte composition comprises the phosphonium salts, including the phosphonium salt of the formula _{(CH 3) (CH 3 CH} 2) ₃ P cations; And
Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- or any combination thereof. The method according to claim 1,
Wherein the electrolyte composition comprises the phosphonium salt, wherein the phosphonium salt is a cation of the formula (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₃ P ⁺ ; And
Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO-) 2 B -, (-OCOCOO -) (CF 3) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or combinations thereof. The method according to claim 1,
Wherein the electrolyte composition comprises the phosphonium salt, wherein the phosphonium salt is a cation of the formula (CH ₃ CH ₂ ) ₄ P ⁺ ; And
Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or combinations thereof. The method according to claim 1,
The positive electrode active material and the negative electrode active material may be carbon black, graphite, graphene, Carbon-metal complex; Polyaniline, polypyrrole, polythiophene; Oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides of lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium; Or a combination thereof. ≪ Desc / Clms Page number 24 > The method according to claim 1,
Wherein the positive electrode active material and the negative electrode active material are the same. The method according to claim 1,
Wherein the positive electrode active material and the negative electrode active material are different from each other. The method according to claim 1,
Wherein the electrolyte composition further comprises one or more conventional non-phosphonium salts. 32. The method of claim 31,
The phosphonium ionic liquid or the phosphonium salt and the conventional salt may be added to the electrolyte composition in the range of 1: 100 to 1: 1 in the phosphonium ionic liquid or the phosphonium salt: Lt; RTI ID = 0.0 > electrochemical < / RTI > 32. The method of claim 31,
The at least one conventional salt is selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ) Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIIm) and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF ₆ ) Electrochemical double layer capacitors. As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
The electrolyte composition comprises at least one phosphonium ionic liquid, or at least one phosphonium salt dissolved in a solvent,
Wherein the at least one phosphonium ionic liquid or phosphonium salt comprises at least one cation of the formula:
_{P (CH 3 CH 2 CH 2} ) y (CH 3 CH 2) x (CH 3) 4-xy ( where, x, y = 0 to 4; x + y = 4) ; And
At least one anion of the formula:
_{(CF 3) x BF 4 -x} ( where, x = 0 to 4)
(CF ₃ (CF ₂ ) _n ) _x PF _{6 -x} (where n = 0 to 2; x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _{2 -x} (where n = 0 to 2; x = 0 to 2)
(-OCO (CH ₂ ) _n COO-) ₂ B (where n = 0 to 2)
(-OSOCH ₂ SOO -) (CF ₃ ) _x BF _{2 -x} (where x = 0 to 2)
_{(-OCOCOO-) x (CF 3)} y PF 6 -2x-y (x = 1 to 3; y = 0 to 4; 2x + y = 6) ;, electrochemical double layer capacitor comprising a. As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
The electrolyte composition comprises at least one phosphonium ionic liquid, or at least one phosphonium salt dissolved in a solvent,
Wherein said at least one phosphonium ionic liquid or said phosphonium salt comprises at least one cation of the formula:
_{P (-CH 2 CH 2 CH 2} CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy ( where, x, y = 0 to 2; x + y = 2)
_{P (-CH 2 CH 2 CH 2} CH 2 CH 2 -) (CH 3 CH 2 CH 2) y (CH 3 CH 2) x (CH 3) 2-xy ( where, x, y = 0 to 2; x + y = 2); And
At least one anion of the formula:
_{(CF 3) x BF 4 -x} ( where, x = 0 to 4)
(CF ₃ (CF ₂ ) _n ) _x PF _{6 -x} (where n = 0 to 2; x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _{2 -x} (where n = 0 to 2; x = 0 to 2)
(-OCO (CH ₂ ) _n COO-) ₂ B (where n = 0 to 2)
(-OSOCH ₂ SOO -) (CF ₃ ) _x BF _{2 -x} (where x = 0 to 2)
_{(-OCOCOO-) x (CF 3)} y PF 6 -2x-y (x = 1 to 3; y = 0 to 4; 2x + y = 6) ;, electrochemical double layer capacitor comprising a. 35. The method of claim 34,
Wherein at least one hydrogen atom of the at least one cation or anion is substituted with fluorine. 36. The method of claim 35,
Wherein at least one hydrogen atom of the at least one cation or anion is substituted with fluorine. As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
Wherein the electrolyte composition comprises a phosphonium salt dissolved in a solvent, wherein the phosphonium salt is an electrochemical double layer capacitor comprising:
1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 P / (CH 3 CH 2 CH 2) (CH 3 CH 2) (CH 3) 2 P / (CH 3 CH 2 CH 2 ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P; And
Formula _{^{BF 4 -, PF 6 -,}} CF 3 BF 3 -, (-OCOCOO-) BF 2 -, (-OCOCOO -) (CF 3) 2 B -, (-OCOCOO-) 2 B -, CF 3 SO 3 ^- , C (CN) ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^-, or a combination thereof. 39. The method of claim 38,
Wherein the anion is composed of a mixture of BF ₄ ^- and CF ₃ BF ₃ ^- and the molar ratio of the [BF ₄ ^- ]: [CF ₃ BF ₃ ^- ] concentration ranges from 100/1 to 1/1. 39. The method of claim 38,
Wherein the anion is composed of a mixture of PF ₆ ^- and CF ₃ BF ₃ ^- and the molar ratio of [PF ₆ ^- ]: [CF ₃ BF ₃ ^- ] concentration is in the range of 100/1 to 1/1, . 39. The method of claim 38,
The anions are PF ₆ ^- and BF ₄ ^- consists of a mixture ^{_{of, [PF 6 -]: [}} BF 4 -] molar ratio of the concentration in the range of 100/1 to 1/1, an electrochemical double layer capacitor. As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
Wherein the electrolyte composition comprises a phosphonium salt dissolved in a solvent, wherein the phosphonium salt comprises an electrochemical double layer capacitor:
1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 P / (CH 3 CH 2 CH 2) (CH 3 CH 2) (CH 3) 2 P / (CH 3 CH 2 CH 2 ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P; And
Anion composed of CF ₃ BF ₃ ^- . As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
Wherein the electrolyte composition comprises a phosphonium salt dissolved in a phosphonium solvent, the salt comprising an electrochemical double layer capacitor:
1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 P / (CH 3 CH 2 CH 2) (CH 3 CH 2) (CH 3) 2 P / (CH 3 CH 2 CH 2 ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P; And
Anion composed of BF ₄ ^- . As an electrochemical double layer capacitor (EDLC)
Positive electrode;
Negative electrode;
A separator between the positive electrode and the negative electrode; And
And an electrolyte composition in contact with the positive electrode, the negative electrode and the separator,
Wherein the electrolyte composition comprises a phosphonium salt dissolved in a solvent, wherein the phosphonium salt comprises an electrochemical double layer capacitor:
1: 3: 1 molar ratio of _{(CH 3 CH 2 CH 2)} (CH 3) 3 P / (CH 3 CH 2 CH 2) (CH 3 CH 2) (CH 3) 2 P / (CH 3 CH 2 CH 2 ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P; And
Anion composed of PF ₆ ^- . A hybrid energy storage system comprising an array of electrochemical bi-layer capacitors according to claim 1 and an array of cells.

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