JP2016507888A - Electrolyte composition and electrochemical double layer capacitor formed therefrom - Google Patents

Abstract

The present invention generally encompasses phosphonium ionic liquids, salts, compositions and their use in many applications, among other applications electronic devices such as memory devices including static memory, permanent memory and dynamic random access memory. As an electrolyte for batteries, as an electrolyte for energy storage devices such as batteries, electrochemical double layer capacitors (EDLC) or supercapacitors or ultracapacitors, as electrolytic capacitors, as electrolytes for dye-sensitized solar cells (DSSC), as electrolytes for fuel cells Examples of the heat transfer medium include, but are not limited to. In particular, the present invention generally relates to phosphonium ionic liquids, salts, compositions, which have excellent thermodynamic stability, low volatility, wide liquid phase range, ionic conductivity, and electrochemical stability. Indicates a combination. The invention further encompasses methods of making such phosphonium ionic liquids, salts, and compositions, and operating devices and systems comprising the same.

Description

  The present invention generally encompasses phosphnium ionic liquids, salts, composition-based electrolyte compositions and their use in many applications, among others, static memory, fixed memory. As an electrolyte for electronic devices such as memory devices including dynamic random access memories, as dyes for energy storage devices such as batteries, electrochemical double layer capacitors (EDLC) or supercapacitors or ultracapacitors, electrolytic capacitors Solar cell (DSSC) electrolytes include, but are not limited to, fuel cell electrolytes as heat transfer media, high temperature reactions and / or extraction media. In particular, the present invention relates to phosphonium ionic liquids, salts, compositions and molecules possessing structural characteristics, which compositions have thermodynamic stability, low volatility, wide liquidus range, and ions. A desired combination of at least two or more of the conductivity is indicated. The invention further encompasses methods for making such phosphonium ionic liquids, salts, compositions and molecules, and operating devices and systems comprising the same.

  Ionic liquids have received considerable attention in part because of their wide range of uses and applications. The term “ionic liquid” is commonly used for salts with a relatively low melting point (100 ° C. or less). Salts that are liquid at room temperature are commonly referred to as room temperature ionic liquids. Early researchers utilized dialkylimidazolium salt-based ionic liquids. For example, Wilkes et al. Developed a dialkyl imidazolium salt-based ionic liquid for use in aluminum metal anodes and chlorine cathodes with the goal of making batteries. J. Wilkes, J. Levisky, R. Wilson, C. Hussey, Inorg. Chem, 21, 1263 (1982).

  Some of the most widely studied and commonly used ionic liquids are based on pyridinium salts, and important uses of N-alkylpyridinium and N, N′-dialkylimidazoliums have been found. Pyridinium-based ionic liquids, including N-alkyl-pyridinium and N, N-dialkylimidazoliums, as well as nitrogen-based ionic liquids generally possess thermodynamic stability limited to 300 ° C or less and are easily It is distillable and tends to have a measurable vapor pressure at temperatures well below 200 ° C. Such properties limit their usefulness as well as their use. For example, such an ionic liquid is liable to be decomposed during heat treatment in a post process (BEOL). Furthermore, such ionic liquids also decompose during other heat transfer steps that subject the ionic liquids to continuous thermal cycling to temperatures often above 300 ° C.

  The various properties of ionic liquids are continuously investigated and further uses of ionic liquids are envisioned. For example, electrochemical methods and applications require electrolytes that increase conductivity in various devices and applications. Recent work has been done in the area of room temperature ionic liquids as a possible alternative to conventional solvent-based electrolytes.

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J. Wilkes, J. Levisky, R. Wilson, C. Hussey, Inorg. Chem, 21, 1263 (1982) Yang et al. (1999) J. Porphyrins Phthalocyanines, 3: 117-147. 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. (1997) J. Mater. Chem., 7: 1245-1262. Strachan et al. (1998) Inorg. Chem., 37: 1191-1201 Yang et al. (1999) J. Am. Chem. Soc., 121: 4008-4018 Handbook of Electrochemistry of the Elements Roth et al. (2000) Vac. Sci. Technol. B 18: 2359-2364 Roth et al. (2003) J. Am. Chem. Soc. 125: 505-517 Advanced Inorganic Chemistry, 5th edition, Cotton & Wilkinson, John Wiley & Sons, 1988, Chapter 26 Organometallics, A Concise Introduction, Elschenbroich et al., 2nd edition, 1992, VCH Comprehensive Organometallic Chemistry II, A Review of the Literature 1982-1994, edited by Abel et al., 7, 7, 8, 10 and 11, Pergamon Press Robins et al., J. Am. Chem. Soc. 104: 1882-1893 (1982) Gassman et al., J. Am. Chem. Soc. 108: 4228-4229 (1986) Connelly et al., Chem. Rev. 96: 877-910 (1996) Geiger et al., Advances in Organometallic Chemistry 23: 1-93 Geiger et al., Advances in Organometallic Chemistry 24:87 Ng and Jiang (1997) Chemical Society Reviews 26: 433-442 Jiang et al. (1999) J. Porphyrins Phthalocyanines 3: 322-328 Arnold et al. (1999) Chemistry Letters 483-484 Cotton and Wilkenson, Advanced Organic Chemistry, 5th edition, John Wiley & Sons, 1988 Rai-Choudhury (1997) The Handbook of Microlithography, Micromachining, and Microfabrication, SPIE Optical Engineering Press Bard & Faulkner (1997) Fundamentals of Microfabrication

  While development has been underway, the need for new developments in ionic liquids, salts, and electrolyte compositions, and electrolytes are electrochemical double layer capacitors, lithium metal and lithium ion batteries, fuel cells, dye-sensitized solar Clearly, there is a continuing need for materials and uses that are available for use in batteries and molecular memory devices.

  The present invention broadly encompasses phosphonium ionic liquids, salts, compositions and their use in many applications, among other applications, memory devices including static memory, fixed memory and dynamic random access memory, etc. As an electrolyte of an electronic device, as an electrolyte of an energy storage device such as a battery, an electrochemical double layer capacitor (EDLC) or a supercapacitor or ultracapacitor, an electrolytic capacitor, a fuel cell as an electrolyte of a dye-sensitized solar cell (DSSC) Examples of the electrolyte include, but are not limited to, a heat transfer medium, a high-temperature reaction, and / or an extraction medium. In particular, the present invention relates to phosphonium ionic liquids, salts, compositions and molecules that have structural features, the composition of thermodynamic stability, low volatility, wide liquid phase range, and ionic conductivity. At least two or more desired combinations are shown.

In one aspect, an ionic liquid composition is provided, the ionic liquid composition having the general formula:
R ¹ R ² R ³ R ⁴ P
One or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are optionally and each independently a substituent including. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently a different alkyl group composed of 2-14 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 phosphorane, pentamethylene phosphorinane, tetramethynyl phosphor, phospholane, or phosphorinane. In another embodiment, R ² , R ³ and R ⁴ are the same and are composed of phospholane, phosphorinane or phosphole.

  In another embodiment, an ionic liquid composition comprising one or more phosphonium-based cations and one or more anions is provided, the ionic liquid composition having a thermodynamic stability above 375 ° C. It exhibits a liquid phase range wider than 400 ° C. and an ionic conductivity of 10 mS / cm or less at room temperature.

  In another aspect, the invention includes an electrolyte composition comprised of a phosphonium-based cation with a suitable anion. In some embodiments, the term “electrolyte” or “electrolyte solution” or “electrolyte composition” or “ion electrolyte” or “ion conductive electrolyte” or “ion conductive composition” or “ionic composition” As used herein, the term is defined as any one or more of the following: (a) an ionic liquid, (b) a room temperature ionic liquid, (c) in at least one solvent. And (d) one or more salts that form a gel electrolyte by dissolving with at least one polymer in at least one solvent. Further, the one or more salts are defined to include: (a) one or more salts that are solid at a temperature of 100 ° C. or lower, and (b) at a temperature of 100 ° C. or lower. One or more salts that are liquids.

In another embodiment, an electrolyte composition is provided, the electrolyte composition being composed of one or more salts dissolved in a solvent, the one or more salts having the general formula:
R ¹ R ² R ³ R ⁴ P (1)
One or more of the formulas wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent such as, but not limited to, an alkyl group as described below A phosphonium-based cation and one or more anions. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. It is. Any one or more of the salts may be liquid or solid at a temperature of 100 ° C. or lower. In some embodiments, the salt is composed of one cation and one anion pair. In other embodiments, the salt is composed of one cation and multiple anions. In other embodiments, the salt is composed of one anion and multiple cations. In a further embodiment, the salt is composed of multiple cations and multiple anions.

In another embodiment, the electrolyte composition further comprises one or more conventional, non-phosphonium salts. In some embodiments, the electrolyte composition may be composed of conventional salts, in which case the phosphonium-based ionic liquids or salts disclosed herein are additives. In some embodiments, the electrolyte composition is comprised of a phosphonium-based ionic liquid or salt and one or more conventional salts, which are phosphonium-based ionic liquids or salts: moles of conventional salts (or (Molar concentration) ratio exists in the range of 1: 100 to 1: 1. Examples of conventional salts include, but are not limited to, tetraalkylammonium, such as (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 ⁺ etc., from the group consisting of imidazolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, pyridazinium, pyrrolidinium One or more selected cations and ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ And a salt composed of one or more anions selected from the group consisting of CF ₂ SO ₂ ) ₂ N ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ . In some embodiments, one or more conventional salts include, but are not limited to, tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), tetrafluoroboric acid 1-ethyl-3-methylimidazolium (EMIBF ₄ ), 1-ethyl-1-methylpyrrolidinium tetrafluoroborate (EMPBF ₄ ), 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ( EMIIm) and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF ₆ ). In some embodiments, one or more conventional salts include, but are not limited to, 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) imido (Li (CF ₃ SO ₂ ) ₂ N or LiIm), And bis (pentafluoromethanesulfonyl) imide lithium (Li (CF ₃ CF ₂ SO ₂ ) ₂ N or LiBETI).

A further aspect of the present invention provides a battery comprising an anode, a cathode, a separator between the anode and cathode, and an electrolyte. The electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
An ion comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent Consists of one or more salts dissolved in a liquid composition or solvent. In one embodiment, the electrolyte is composed of an ionic liquid having one or more phosphonium-based cations and one or more anions, the ionic liquid composition having a thermodynamic stability up to 375 ° C. A liquidus range wider 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 one or more salts dissolved in a solvent having one or more phosphonium-based cations and one or more anions, the electrolyte composition comprising: At room temperature, 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 The ionic conductivity of is shown. In a further aspect, the phosphonium electrolyte exhibits lower flammability compared to conventional electrolytes, thus improving battery operation safety. In a further aspect, phosphonium ionic liquids or salts can be used as additives to facilitate the formation of a solid electrolyte interphase (SEI) layer or electrode protection layer. The SEI layer can widen the electrochemical stability window, suppress battery degradation or decomposition reactions, and thus improve battery cycle life.

A further aspect of the invention provides an electrochemical double layer capacitor (EDLC), which includes an anode, a cathode, a separator between the anode and cathode, and an electrolyte. The electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
An ion comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent Consists of one or more salts dissolved in a liquid composition or solvent. In one embodiment, the electrolyte is composed of an ionic liquid having one or more phosphonium-based cations and one or more anions, the ionic liquid composition having a thermodynamic stability up to 375 ° C. Exhibit a liquidus range 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 one or more salts dissolved in a solvent having one or more phosphonium-based cations and one or more anions, the electrolyte composition comprising: At room temperature, 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 The ionic conductivity of is shown. In a further embodiment, the phosphonium electrolyte exhibits lower flammability compared to conventional electrolytes, thus improving the safety of EDLC operation. In a further aspect, phosphonium ionic liquids or salts can be used as additives to facilitate the formation of a solid electrolyte interphase (SEI) layer or electrode protection layer. Without being bound by any particular theory, we believe that the protective layer acts to expand the electrochemical stability window, inhibit EDLC degradation or degradation reactions, and thus improve EDLC cycle life. thinking.

  Embodiments of the present invention provide a heat transfer medium comprising one or more salts dissolved in an ionic liquid composition or solvent comprising one or more phosphonium-based cations and one or more anions. Further provided, this heat transfer medium exhibits thermodynamic stability at temperatures in excess of 375 ° C., a liquid phase range greater than 400 ° C.

Phosphonium ionic liquid compositions and salts are useful in forming a variety of hybrid electrical devices. For example, in one embodiment, the first electrode, the second electrode, and the general formula:
R ¹ R ² R ³ R ⁴ P
An ionic liquid composition comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent And an electrolyte composed of one or more salts dissolved in a solvent or solvent, wherein the electrolyte is electrically coupled to at least one of the first and second electrodes. It's ringing. In some embodiments, the first electrode is composed of a redox active molecule (ReAM).

  In another embodiment, a molecular storage device comprising a working electrode and a counter electrode configured to provide electrical capacitance, and an ion conductive composition comprising one or more phosphonium-based cations of the above general formula Provided, the ionically conductive composition is electrically coupled to at least the working electrode and the counter electrode.

  In another embodiment, the present invention encompasses a molecular memory element comprising a switching device, bit lines and word lines coupled to the switching device, and a molecular storage device accessible via the switching device. The molecular storage device can be placed in two or more distinct states, where the molecular storage device is placed in one of the distinct states by signals applied to the bit and word lines. The molecular storage device includes a first electrode, a second electrode, and a phosphonium-based cation and a suitable anion electrolyte between the first and second electrodes.

  Another embodiment includes a molecular memory array that includes a plurality of molecular storage elements that can place each molecular storage element in two or more distinct states. The plurality of bit lines and word lines are coupled to the plurality of molecular storage elements such that each molecular storage element is coupled to and addressable by at least one bit line and at least one word line. .

  Other aspects, embodiments and advantages of the present invention will become apparent upon reading the detailed description of the invention and the appended claims provided below, and upon reference to the following drawings.

1 is a cross-sectional view of an electrochemical double layer capacitor (EDLC) according to an embodiment of the present invention. 1 is a cross-sectional view of a bipolar electrode of an EDLC according to an embodiment of the present invention. 1 is a cross-sectional view of a multi-cell stack structure of an EDLC according to an embodiment of the present invention. FIG. 2 illustrates one reaction scheme for forming a phosphonium ionic liquid according to some embodiments of the present invention. FIG. 4 shows another reaction scheme for forming another embodiment of the phosphonium ionic liquid of the present invention. FIG. 3 shows another reaction scheme for forming a phosphonium ionic liquid according to another embodiment of the present invention. FIG. 4 shows another reaction scheme for forming a phosphonium ionic liquid according to a further embodiment of the present invention. 2 is a thermogravimetric analysis (TGA) graph performed on an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 1. FIG. 2 shows a reaction scheme for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 2. FIG. 2 is a graph illustrating thermogravimetric analysis (TGA) for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 2. FIG. 2 is a graph illustrating evolved gas analysis (EGA) for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 2. 4 is a graph illustrating thermogravimetric analysis (TGA) for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 3. FIG. 4 is a graph illustrating evolved gas analysis (EGA) for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 3. FIG. FIG. 5 shows a reaction scheme for an exemplary embodiment of a phosphonium ionic liquid prepared as described in FIG. 4 and Example 4. FIG. 5 shows a ¹ H NMR spectrum for an exemplary embodiment of a phosphonium ionic liquid prepared as described in FIG. 4 and Example 4. FIG. 6 shows a reaction scheme for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 5. 6 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 5. FIG. 6 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 6. 6 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 7. FIG. FIG. 4 shows a reaction scheme for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 8. 6 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 8. FIG. 10 shows a ¹ H NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 9. FIG. 10 shows a ³¹ P NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 9. 6 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium salt prepared according to Example 9. FIG. 5 shows a ¹ H NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 10. FIG. 10 shows a ³¹ P NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 10. 2 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium salt prepared according to Example 10. FIG. FIG. 6 shows a ¹ H NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 11. FIG. 10 shows a ³¹ P NMR spectrum for an exemplary embodiment of a phosphonium salt prepared as described in Example 11. 2 is a graph showing thermogravimetric analysis (TGA) results for an exemplary embodiment of a phosphonium salt prepared according to Example 11. FIG. FIG. 6 is a graph showing differential scanning calorimetry (DSC) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 12. FIG. FIG. 6 is a graph showing differential scanning calorimetry (DSC) results for an exemplary embodiment of a phosphonium ionic liquid prepared according to Example 12. FIG. Of the volume ratio of ACN / salt to phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ in acetonitrile (ACN) as described in Example 14. It is a graph which shows ion conductivity as a function. Volume ratio of PC / salt to phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) _{3 in} propylene carbonate (PC) as described in Example 15. Is a graph showing ionic conductivity as a function of FIG. 5 is a graph showing ionic conductivity as a function of molar concentration of phosphonium salt compared to ammonium salt in propylene carbonate as described in Examples 42-45. FIG. 4 is a graph showing vapor pressure as a function of temperature for acetonitrile, acetonitrile with 1.0 M ammonium salt and acetonitrile with 1.0 M phosphonium salt as described in Example 46. FIG. Phosphonium salt (CH ₃ CH ₂ CH ₂ ) for ionic conductivity of 1.0 M LiPF _{6 in} EC: DEC 1: 1 at different temperatures from -30 to 60 ° C. as described in Example 51 ₃ is a graph showing the influence of CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ . Phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₂ ) for ionic conductivity of 1.0M LiPF _{6 in} EC: DEC 1: 1 at different temperatures of 20-90 ° C. as described in Example 52. ₃ CH ₂ ) (CH ₃ ) ₂ is a graph showing the influence of PCF ₃ BF ₃ . FIG. 46 is a cross-sectional view of an EDLC coin cell according to one embodiment of the present invention as described in Example 53. Charge and discharge curves for coin cells with 1.0 M phosphonium salt- (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in propylene carbonate as described in Example 53. It is the graph shown. FIG. 5 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. 5 illustrates a fabrication process for an EDLC pouch cell according to one embodiment of the present invention as described in Examples 54-57. Phosphonium salt in propylene carbonate 1.0M as described in Example _{54~57 - (CH 3 CH 2 CH} 2) (CH 3 CH 2) (CH 3) charging of the pouch cell having ₂ CF ₃ F ₃ - It is a graph which shows a discharge curve. Figure 5 is a graph showing the resolved electrode potential at the carbon anode and cathode as measured with a silver reference electrode as described in Examples 54-57. FIG. 6 is an exploded view of an EDLC cylindrical cell according to one embodiment of the invention as described in Example 58. Charging a cylindrical cell with 1.0 M phosphonium salt in propylene carbonate as described in Example 58-(CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F _3- It is a graph which shows a discharge curve. FIG. 5 shows the capacitance retention at 2.7 V and 70 ° C. of pouch cells with 1.0 M phosphonium salt compared to ammonium salt in propylene carbonate as described in Examples 59-61. FIG. 5 shows the capacitance retention at different temperatures of pouch cells with 1.0M phosphonium salt as described in Example 62 compared to ammonium salt in propylene carbonate.

Overview The present invention is generally directed to phosphonium ionic liquids, salts, and compositions and their use in many applications.

General Description The present invention encompasses novel phosphonium ionic liquids, salts, compositions and their use in many applications, including electronic devices such as memory devices including static memory, fixed memory and dynamic random access memory. Examples of the electrolyte include, but are not limited to, batteries, electrochemical double layer capacitors, electrolytic capacitors, fuel cells, dye-sensitized solar cells, and electrochromic device applications. Further applications include the use as heat transfer media, high temperature reactions and / or extraction media, among other applications. In particular, the present invention relates to phosphonium ionic liquids, salts, compositions and molecules possessing structural characteristics, which compositions have thermodynamic stability, low volatility, wide liquid phase range, ionic conductivity, and electrical properties. A desirable combination of at least two of the chemical stability is indicated. The invention further encompasses methods for making such phosphonium ionic liquids, compositions and molecules, and operating devices and systems comprising the same.

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

  Phosphonium ionic liquid compositions, due to their advantageous properties, make them particularly suitable for use as electrolytes in electronic devices, batteries, EDLCs, fuel cells, dye-sensitized solar cells (DSSCs), and electrochromic devices. Become.

  In a further aspect of the present invention there is provided a heat transfer medium composed of one or more salts dissolved in a phosphonium ionic liquid composition or solvent. The advantageous properties of the compositions of the present invention are well suited for heat transfer media, making the heat transfer media useful in processes and systems utilized, for example, in heat extraction processes and high temperature reactions.

Definitions As used herein and unless otherwise stated, “electrolyte” or “electrolyte solution” or “electrolyte composition” or “ionic electrolyte” or “ionic conductive electrolyte” or “ionic conductive composition” Or the term “ionic composition” is used, which is defined herein as any one or more of: (a) an ionic liquid, (b) a room temperature ionic liquid (C) one or more salts dissolved in at least one solvent, and (d) one or more forming a gel electrolyte by dissolving with at least one polymer in at least one solvent. Salt. Further, the one or more salts are defined to include: (a) one or more salts that are solid at a temperature of 100 ° C. or lower, and (b) at a temperature of 100 ° C. or lower. One or more salts that are liquids.

  As used herein and unless otherwise stated, the term “acyl” refers to OH of this carboxyl group as a number of other substituents (RCO—), such as “R” substituents. It refers to organic acid groups that can be replaced with those described in the book. Examples include but are not limited to halo, acetyl, and benzoyl.

  As used herein and unless otherwise stated, the term “alkoxy group” means an —O-alkyl group, where alkyl is as defined herein. An alkoxy group can be unsubstituted or substituted with one, two or three suitable substituents. Preferably, the alkyl chain of the alkoxy group is 1-6 carbon atoms in length, referred to herein as, for example, “(C1-C6) alkoxy”.

  As used herein and unless otherwise stated, “alkyl” by itself or as part of another substituent is a single hydrogen from a single carbon atom of the parent alkane, alkene, or alkyne. Saturated or unsaturated, branched, linear or cyclic monovalent hydrocarbon group obtained by removing atoms. Also included within the definition of alkyl groups are cycloalkyl groups such as C5, C6 or other rings, and heterocyclic rings having nitrogen, oxygen, sulfur or phosphorus (heterocycloalkyl). Alkyl also includes heteroalkyl having the heteroatoms sulfur, oxygen, nitrogen, phosphorus, and silicon, which have found particular use in certain embodiments. The alkyl group can be optionally substituted with R groups independently selected at each position, as described below.

  Examples of alkyl groups include, but are not limited to, (C1-C6) alkyl groups such as methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl- 1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl- 1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2- Examples include ethyl-1-butyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, and hexyl, and longer alkyl groups such as heptyl and octyl.

  The term “alkyl” refers to groups having any degree or level of saturation, ie, groups having exclusively carbon-carbon single bonds, groups having one or more carbon-carbon double bonds, one or more It is specifically intended to include groups having a carbon-carbon triple bond as well as groups having a mixture of single, double and triple carbon-carbon bonds. Where a specific level of saturation is intended, the expressions “alkanyl”, “alkenyl” and “alkynyl” are used.

  “Alkanyl” by itself or as part of another substituent is a saturated, branched, linear or ring obtained by removing one hydrogen atom from a single carbon atom of a parent alkane. Refers to an alkyl group of the formula. “Heteroalkanyl” is included as described above.

  “Alkenyl” by itself or as part of another substituent has at least one carbon-carbon double bond obtained by removing one hydrogen atom from a single carbon atom of a parent alkene. Refers to an unsaturated branched, straight chain or cyclic alkyl group. This group may be in either cis or trans configuration relative to the double bond. 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-butenyl. 4- (2-methyl-3-butene) -pentenyl and the like. An alkenyl group can be unsubstituted or substituted with one or more independently selected R groups.

  An `` alkynyl '' is a non-alkyl having itself at least one carbon-carbon triple bond obtained by removing one hydrogen atom from a single carbon atom of the parent alkyne, as part of another substituent. Saturated branched, straight-chain or cyclic alkyl group.

  Also included within the definition of “alkyl” are “substituted alkyl”. “Substituted” is commonly designated herein as “R” and refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituents. R substituents include, but are not limited to, hydrogen, halogen, alkyl (including substituted alkyl (alkylthio, alkylamino, alkoxy, etc.), cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, and substituted cycloheteroalkyl), aryl (Including substituted aryl, heteroaryl or substituted heteroaryl), carbonyl, alcohol, amino, amide, nitro, ether, ester, aldehyde, sulfonyl, sulfoxyl, carbamoyl, acyl, cyano, thiocyanato, silicon moiety, halogen, sulfur-containing moiety , And can be selected independently from the phosphorus-containing portion and the like. In some embodiments, the R substituent comprises a redox active moiety (ReAM) as described herein. In some embodiments, optionally R and R ′, together with the atoms to which they are attached, include cycloalkyl (including cycloheteroalkyl) and / or cycloaryl (including cycloheteroaryl). These can be further substituted if desired. In the structures depicted herein, R is hydrogen when the position is unsubstituted. Note that some positions may allow 2 or 3 substituents, R, R ′, and R ″, in which case the R, R ′, and R ″ groups may be the same or different. Should.

  In some embodiments, the R group (subunit) is used to adjust the redox potential of the subject compound. Thus, as described more fully below and in the references cited herein, an R group, such as a redox active subunit, can be used to change its redox potential, particularly macrocyclic molecules, particularly porphyrins. Can be added to macrocycles. Certain preferred substituents include, but are not limited to, 4-chlorophenyl, 3-acetamidophenyl, 2,4-dichloro-4-trifluoromethyl, and ferrocene (including ferrocene derivatives). When substituents are used to change the redox potential, preferred substituents provide a redox 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 depicted in the figures and text of US Provisional Patent Application No. 60 / 687,464, incorporated herein by reference. Some suitable proligands and complexes, and suitable substituents are described in U.S. Patent 6,212,093; U.S. Patent 6,728,129; U.S. Patent 6,451,942; U.S. Patent 6,777,516; U.S. Patent 6,381,169; U.S. Patent 6,657,884; U.S. Patent 6,272,038; U.S. Patent 6,484,394; and U.S. Patent Application No. 10 / 040,059; U.S. Patent Application No. 10 / 682,868; U.S. Patent Application No. 10 / 445,977; Outlined in patent application 10 / 834,630; U.S. patent application 10 / 135,220; U.S. patent application 10 / 723,315; U.S. patent application 10 / 456,321; U.S. patent application 10 / 376,865. All of these, especially those structures and descriptions depicted therein, are expressly incorporated by reference, thereby allowing certain macrocycles with substituents depicted therein, and further Substituent embodiments for both substituted derivatives It is expressly incorporated.

  “Aryl” or grammatical equivalents herein refer to aromatic monocyclic or polycyclic hydrocarbon moieties generally having from 5 to 14 carbon atoms (but larger polycyclic ring structures And any carbocyclic ketone, imine, or thioketone derivative thereof, and a carbon atom having a free valence is a member of an aromatic ring. Aromatic groups include arylene groups and aromatic groups from which more than two atoms have been removed. For the purposes of this application, aryl includes heteroaryl. “Heteroaryl” means an aromatic group in which 1 to 5 of the carbon atoms are replaced with a heteroatom selected from nitrogen, oxygen, sulfur, phosphorus, boron and silicon, and the free valence Are members of an aromatic ring and any of its heterocyclic ketone and thioketone derivatives. Thus, heterocycles include both monocyclic and polycyclic systems such as thienyl, furyl, pyrrolyl, pyrimidinyl, indolyl, purinyl, quinolyl, isoquinolyl, thiazolyl, imidazolyl, naphthalene, phenanthroline, and the like. Also included within the definition of aryl are substituted aryls having one or more substituents “R” as defined herein and outlined above and herein. For example, “perfluoroaryl” is included, which refers to an aryl group in which all hydrogen atoms are replaced with fluorine atoms. Also included is oxalyl.

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

The term “nitro” refers to the —NO ₂ group.

“Amino group” or grammatical equivalents herein means a —NH ₂ , —NHR and NRR ′ group, where R and R ′ are independently as defined herein. is there.

  As used herein, the term “pyridyl” refers to an aryl group in which one CH unit is replaced with 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.

  The term `` sulfoxyl '' includes alkyl (cycloalkyl, perfluoroalkyl, etc.) or aryl (e.g., a perfluoroaryl group) composition RS (O)-, where R is defined herein. Which is a substituent as defined). Examples include, but are not limited to, methylsulfoxyl, phenylsulfoxyl, and the like.

The term “sulfonyl” is a composition RSO ₂ — (wherein R is defined herein) having an alkyl, aryl, (including cycloalkyl, perfluoroalkyl, or perfluoroaryl group). Which is a normal substituent). Examples include, but are not limited to, methylsulfonyl, phenylsulfonyl, p-toluenesulfonyl, and the like.

  The term “carbamoyl” refers to a group of the composition R (R ′) NC (O) —, where R and R ′ are as defined herein. Examples include, but are not limited to, N-ethylcarbamoyl, N, N-dimethylcarbamoyl, and the like.

The term “amido” refers to a group of the composition R ₁ CONR ₂ —, where R ₁ and R ₂ are substituents as defined herein. Examples include, but are not limited to, acetamide, N-ethylbenzamide, and the like.

  The term “imine” refers to ═NR.

In certain embodiments, if a metal is designated, for example, as “M” or “M _n ” (where n is an integer), it is recognized that the metal can be accompanied by a counter ion. .

  As used herein and unless otherwise stated, the term “current measuring device” measures the current generated in an electrochemical cell as a result of applying a specific electric field potential (“voltage”). Is a device that can.

  As used herein and unless otherwise stated, the term “aryloxy group” means an —O-aryl group, where aryl is as defined herein. . An aryloxy group can be unsubstituted or substituted with one or two suitable substituents. Preferably, the aryl ring of the aryloxy group is a monocyclic ring, which contains 6 carbon atoms and is referred to herein as “(C6) aryloxy”.

As used herein and unless otherwise indicated, the term “benzyl” means —CH ₂ -phenyl.

  As used herein and unless otherwise indicated, the term “carbonyl” group is a divalent group of formula —C (O) —.

  As used herein and unless otherwise stated, the term “coulometric device” measures the net charge generated while applying a potential field to an electrochemical cell (“voltage”). Is a device that can.

  As used herein and unless otherwise indicated, the term “cyano” refers to a —CN group.

  As used herein and unless otherwise stated, the term “different and distinguishable” refers to an entity (atom, molecule, aggregate, subunit, etc.) when referring to two or more oxidation states. ) Means that the effective charge can exist in two different states. If the difference between these states exceeds the thermal energy at room temperature, these states are said to be “distinguishable”.

As used herein and unless otherwise stated, the term “E _1/2 ” refers to E = E ₀ + (RT / nF) 1n (D _ox / D _red ) where R is a gas is a constant, T is temperature in K (Kelvin), n is the number of electrons involved in the process, F is the Faraday constant (96,485Coulomb / mol), D _ox is the diffusion rate of the oxidizing species _Where D _red is the diffusivity of the reducing species) and refers to a practical definition of the apparent potential (E ₀ ) of the redox process.

  As used herein and unless otherwise stated, the term “electrically coupled” means that when used with respect to storage molecules and / or storage media and electrodes, electrons are stored from the storage media / molecules to the electrodes. Refers to a bond between the storage medium or molecule and the electrode, such as moving to or from the electrode to the storage medium / molecule, thereby changing the oxidation state of the storage medium / molecule. As electrical coupling, direct covalent coupling between storage medium / molecule and electrode, indirect covalent coupling (e.g. via a linker), direct or between storage medium / molecule and electrode Mention may be made of indirect ionic bonds or other bonds (eg hydrophobic bonds). Furthermore, the actual binding may not be necessary and the storage medium / molecule may simply be in contact with the electrode surface. Similarly, if the electrode is sufficiently close to the storage medium / molecule so that electron tunneling between the medium / molecule and the electrode is possible, the contact between the electrode and the storage medium / molecule is It is not always necessary.

  As used herein and unless otherwise stated, the term `` electrochemical cell '' includes, at a minimum, a reference electrode, a working electrode, a redox active medium (e.g., a storage medium), as appropriate, It consists of some means (eg, a dielectric) for providing electrical conductivity between the electrodes and / or between the electrode and the medium. In some embodiments, the dielectric is a component of the storage medium.

  As used herein and unless otherwise stated, the term `` electrode '' refers to any medium capable of transporting charge (e.g., electrons) to and / or from a storage molecule. . Preferred electrodes are metals or conductive organic molecules. The electrodes can be fabricated into almost any two-dimensional or three-dimensional shape (eg, discontinuous lines, pads, planes, spheres, cylinders).

  As used herein and unless otherwise stated, the term “fixed electrode” reflects the fact that the electrode is inherently stable and cannot be moved relative to the storage medium. Intended. That is, the electrode and the storage medium are arranged in a geometric relationship that is essentially fixed to each other. It is naturally recognized that this relationship changes somewhat due to expansion and contraction of the medium due to thermal changes or due to changes in the configuration of the molecules that make up the electrodes and / or storage medium. Nevertheless, the overall spatial arrangement remains essentially unchanged.

  As used herein and unless otherwise stated, the term “linker” refers to two different molecules, two subunits of a molecule, or a molecule used to couple a molecule to a substrate. It is.

  Many of the compounds described herein utilize a substituent that is generally depicted herein as “R”. Suitable R groups include, but are not limited to, hydrogen, alkyl, alcohol, aryl, amino, amide, nitro, ether, ester, aldehyde, sulfonyl, silicon moiety, halogen, cyano, acyl, sulfur-containing moiety, phosphorus-containing moiety , Sb, imide, carbamoyl, linker, addition moiety, ReAM and other subunits. Some positions may allow two substituents, R and R ′, in which case the R and R ′ groups may be the same or different, and one of the substituents may be hydrogen. It should be noted that it is generally preferred. In some embodiments, the R group is as defined and shown in US figures and text. Some suitable proligands and complexes, and suitable substituents are described in U.S. Patent 6,212,093; U.S. Patent 6,728,129; U.S. Patent 6,451,942; U.S. Patent 6,777,516; U.S. Patent 6,381,169; U.S. Patent 6,657,884; U.S. Patent 6,272,038; U.S. Patent 6,484,394; and U.S. Patent Application No. 10 / 040,059; U.S. Patent Application No. 10 / 682,868; U.S. Patent Application No. 10 / 445,977; Outlined in patent application 10 / 834,630; U.S. patent application 10 / 135,220; U.S. patent application 10 / 723,315; U.S. patent application 10 / 456,321; U.S. patent application 10 / 376,865. All of these, especially those structures and descriptions depicted therein, are expressly incorporated by reference, thereby allowing certain macrocycles with substituents depicted therein, and further Substituent embodiments for both substituted derivatives It is expressly incorporated.

  As used herein and unless otherwise noted, the term “subunit” refers to the redox active portion of a molecule.

Phosphonium Ionic Liquids, Salts, and Compositions of the Invention As described in detail herein, the novel phosphonium ionic liquids, salts, and composition embodiments of the present invention have desirable properties and particularly high heat. Shows a combination of at least two or more of mechanical stability, low volatility, wide liquid phase range, high ionic conductivity, and wide electrochemical stability window. Combinations up to the desired level within one composition, and in some embodiments, all combinations of these properties at the desired level are unexpected, unexpected, known ions It provides significant advantages over the composition. Embodiments of the phosphonium compositions of the present invention that exhibit such properties enable applications and devices that were not previously available.

  In some embodiments, the phosphonium ionic liquids of the present invention comprise a phosphonium cation having a selected molecular weight and substitution pattern coupled with a selected anion, thereby providing thermodynamic stability, ionic conductivity, An ionic liquid is formed having an adjustable combination of liquid phase range and low volatility properties.

  In some embodiments, “ionic liquid” herein means a salt that is liquid at 100 ° C. or lower. A “room temperature” ionic liquid is further defined herein as being liquid at or below room temperature.

  In other embodiments, the term “electrolyte” or “electrolyte solution” or “electrolyte composition” or “ion electrolyte” or “ion conductive electrolyte” or “ion conductive composition” or “ionic composition” is used. The term is defined herein as any one or more of the following: (a) an ionic liquid, (b) a room temperature ionic liquid, (c) in at least one solvent. One or more salts dissolved, and (d) one or more salts forming a gel electrolyte by dissolving with at least one polymer in at least one solvent. Further, the one or more salts are defined to include: (a) one or more salts that are solid at a temperature of 100 ° C. or lower, and (b) at a temperature of 100 ° C. or lower. One or more salts that are liquids.

  In some embodiments, the present invention includes phosphonium ionic liquids and phosphonium electrolytes that exhibit thermodynamic stability up to a temperature of about 400 ° C., more usually up to a temperature of about 375 ° C. Showing thermal stability to such high temperatures is an important development and allows the use of the phosphonium ionic liquids of the present invention in a wide range of applications. Embodiments of the phosphonium ionic liquids and phosphonium electrolytes of the present invention are at least 1 mS / cm, or 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 / at room temperature. It further exhibits an ionic conductivity of 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 volatility that is about 20% lower compared to these nitrogen-based analogs. This combination of high thermal stability, high ionic conductivity, wide liquid phase range, and low volatility was highly desirable and unexpected. In the prior art, it has generally been found that the thermal stability and ionic conductivity of ionic liquids exhibit an inverse correlation.

  In some embodiments, the phosphonium ionic liquid and phosphonium electrolyte are composed of cations having a molecular weight of 500 Daltons or less. In other embodiments, the phosphonium ionic liquid and phosphonium electrolyte are composed of cations having a molecular weight in the range of 200-500 Daltons relative to the ionic liquid in the lower thermal stability region.

The phosphonium ion composition of the present invention has the general formula:
R ¹ R ² R ³ R ⁴ P (1)
(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent). In some embodiments, the cation is composed of open chains.

In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group. In one embodiment, at least one of the alkyl groups is different from the other two. In one embodiment, none of the alkyl groups are methyl. In some embodiments, the alkyl group consists of 2 to 7 carbon atoms, more usually 1 to 6 carbon atoms. In some embodiments, R ¹ , R ² , R ^3, and R ⁴ are each independently a different alkyl group composed of 2-14 carbon atoms. In some embodiments, the alkyl group has no branches. In one embodiment, R ¹ = R ² in the aliphatic, heterocyclic moiety. Alternatively, R ¹ = R ² in the aromatic or heterocyclic moiety.

In some embodiments, R ¹ or R ² is composed of phenyl or substituted alkylphenyl. In some embodiments, R ¹ and R ² are the same and are composed of tetramethylene (phosphorane) or pentamethylene (phosphorinane). Alternatively, R ¹ and R ² are the same and are composed of tetramethynyl (phosphole). In a further embodiment, R ¹ and R ² are the same and are composed of phospholane or phosphorinane. In yet another embodiment, R ² , R ³ and R ⁴ are the same and are composed of phospholane, phosphorinane or phosphole.

In some embodiments, at least one, more than, or all of R ¹ , R ² , R ³ and R ⁴ have a functional group that reacts with a redox active molecule (ReAM) as described below. Each is chosen not to have. 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 1-7 carbon atoms. In another embodiment, the total number of carbon atoms in all alkyl groups is 12 or less. In still other embodiments, each alkyl group is independently composed of 1-6 carbon atoms, more usually 1-5 carbon atoms.

In another embodiment, a phosphonium ion composition is provided, the phosphonium ion composition being composed of one or more salts dissolved in a solvent, the one or more salts having the general formula:
R ¹ R ² R ³ R ⁴ P (1)
One or more of the formulas wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent such as, but not limited to, an alkyl group as described below A phosphonium-based cation and one or more anions. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. It is. In some embodiments, one or more of the hydrogen atoms in one or more of the R groups are substituted with fluorine. Any one or more of the salts may be liquid or solid at a temperature of 100 ° C. or lower. In some embodiments, the salt is composed of one cation and one anion. In other embodiments, the salt is composed of one cation and multiple anions. In other embodiments, the salt is composed of one anion and multiple cations. In a further embodiment, the salt is composed of multiple cations and multiple anions. Exemplary embodiments of suitable solvents include, but are not limited to, one or more of the following: acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), Vinyl ethylene carbonate (VEC), phenyl ethylene carbonate (PhEC), propyl methyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL), and γ-valero Lactone (GVL).

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

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

  Another exemplary embodiment provides a phosphonium cation composed of the following formula:

  Further provided are phosphonium cations composed of the following 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-butylethylphosphonium, and the like. .

  In other embodiments, examples of suitable phosphonium cations include, but are not limited to, ethylphosphorane; n-propylphosphorane; n-butylphosphorane; n-hexylphosphorane; and phenylphosphorane.

  In further embodiments, examples of suitable phosphonium cations include, but are not limited to, ethyl phosphole; n-propyl phosphole; n-butyl phosphole; n-hexyl phosphole; and phenyl phosphole.

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

The phosphonium ionic liquid or salt of the present invention is composed of a cation and an anion. There will be a wide variety of possible cation and anion combinations, as will be appreciated by those skilled in the art. The phosphonium ionic liquid or salt of the present invention comprises a cation as described above having the general formula:
C ⁺ A ^-
(Wherein C ⁺ is a cation and A ⁺ is an anion) with an anion generally selected from compounds that are readily ion exchanged with reagents or solvents. In the case of organic solvents, C ⁺ is preferably Li ⁺ , K ⁺ , Na ⁺ , NH ₄ ⁺ or Ag ⁺ . In the case of an aqueous solvent, C ⁺ is preferably Ag ⁺ .

Many anions can be selected. In one preferred embodiment, the anion is bis-perfluoromethylsulfonylimide. Exemplary embodiments of suitable anions include, but are not limited to, any one or more of the following: 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 SCF 2 CF 2 CF 3, SO 4 2-, - O 2 CCF 3, - O 2 CCF 2 CF 2 CF 3, or ^- N (CN) ₂ .

  In some embodiments, the phosphonium ionic liquids or salts of the invention are composed of a single cation-anion pair. Alternatively, two or more phosphonium ionic liquids or salts can be used to form a common binary system, a mixed binary system, a common ternary system, a mixed ternary system, and the like. Composition ranges for binary, ternary, etc. include from 1 ppm to 999,999 ppm for each component cation and each component 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 is composed of a single cation-anion pair. In other embodiments, the salt is composed of one cation and multiple anions. In other embodiments, the salt is composed of one anion and multiple cations. In still other embodiments, the salt is composed of multiple cations and multiple anions.

An electrolyte composition according to some embodiments of the present invention is filed concurrently with the present specification and is a co-pending US patent application number, the entire disclosure of which is incorporated herein by reference. (Attorney Docket No. 057472-058).

  In a preferred embodiment, the phosphonium ionic liquid composition is composed of a combination of cations and anions as shown in Table 1A and Table 1B below (Tables 1 and 2). In another preferred embodiment, the phosphonium electrolyte is composed of a combination of cations and anions as shown in Table 1C, Table 1D, Table 1E and Table 1F (Table 3, Table 4 and Table 5) below. For clarity, the sign of the charge is omitted in the formula.

  Table 1A illustrates an example of an anionic binary system with a common cation:

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

  In another embodiment, the phosphonium electrolyte is composed of salts with cations as shown in Table 1C-1 to Table 1C-3 (Table 3) below:

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

  In a further embodiment, the phosphonium electrolyte composition is comprised of a salt having a combination of cations and anions as shown in Table 1E-1 to Table 1E-4 below (Table 5):

In some embodiments, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising one or more cations of the following formula:
P (CH ₃ CH ₂ CH ₂ ) _y (CH ₃ CH ₂ ) _x (CH ₃ ) _4-xy (x, y = 0 to 4 and 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 and 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 = 0-2, 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 = 0-2, x (+ y ≦ 2)
And one or more anions of the following formula:
(CF ₃ ) _x BR _4-x (x = 0 ~ 4)
(CF ₃ (CF ₂ ) _n ) _x PF _6-x (n = 0-2, x = 0-4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (n = 0-2, x = 0-2)
(-OCO (CF ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (n = 0-2, x = 0-2)
(-OCO (CH ₂ ) _n COO-) ₂ B (n = 0-2)
(-OCO (CF ₂ ) _n COO-) ₂ B (n = 0-2)
(-OOR) _x (CF ₃ ) BF _3-x (where x = 0 to 3)
(-OCOCOCOO-) (CF ₃ ) _x BF _2-x (x = 0 ~ 2)
(-OCOCOCOO-) ₂ B
(-OSOCH ₂ SOO-) (CF ₃ ) _x BF _2-x (x = 0 ~ ₂ )
(-OSOCF ₂ SOO-) (CF ₃ ) _x BF _2-x (where x = 0 to 2)
(-OCOCOO-) _x (CF ₃ ) _y PF _6-2x-y (x = 1-3, y = 0-4, 2x + y ≦ 6)
Consists of.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt having 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 and x + y ≦ 4)
One or more cations and 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 and x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (where n = 0 to 2 and 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 = 1-3, y = 0-4, 2x + y ≦ 6)
Of one or more anions.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt having 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 Yes, x + y ≦ 2)
One or more cations and 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 and x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (where n = 0 to 2 and 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 = 1-3, y = 0-4, 2x + y ≦ 6)
Of one or more anions.

In one embodiment, the phosphonium electrolyte is composed of a salt dissolved in a solvent, which is 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 one or more anions selected from the group consisting of H or F.

In one embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of the formula: (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P ⁺ and the 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 - consists of or any one or more anions of these combinations.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of formula (CH ₃ ) (CH ₃ CH ₂ ) ₃ P ⁺ and a 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 -, It is composed of (CF ₃ SO ₂ ) ₂ N ^- or any one or more anions of these combinations.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of 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 -) (CF 3) 2 B -, (- OCOCOO-) 2 B -, CF 3 SO 3 -, C (CN ) ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ or a combination of any one or more anions thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of formula (CH ₃ CH ₂ CH ₂ ) ₃ (CH ₃ ) P ⁺ and a 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 of any one or more anions thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of formula (CH ₃ CH ₂ CH ₂ ) ₃ (CH ₃ CH ₂ ) P ⁺ and a 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 of any one or more anions thereof.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of formula (CH ₃ CH ₂ CH ₂ ) ₂ (CH ₃ CH ₂ ) (CH ₃ ) P ⁺ and a 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, and any one or more anions.

In another embodiment, the phosphonium electrolyte is comprised of a salt dissolved in a solvent, the salt comprising a cation of formula (CH ₃ CH ₂ ) ₄ P ⁺ and a 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 ) It is composed of one or more anions of ₂ N ^- or combinations thereof.

In a further embodiment, the phosphonium electrolyte consists of a salt dissolved in a solvent, which salt has the formula (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 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 of any one or more anions thereof.

In some embodiments, the anion is a mixture of BF ₄ ⁻ and CF ₃ BF ₃ ⁻ at a concentration ratio of [BF ₄ ⁻ ]: [CF ₃ BF ₃ ⁻ ] ranging from 100/1 to 1/1. Composed. In another embodiment, the anion is composed of a mixture of PF ₆ ⁻ and CF ₃ BF ₃ ⁻ at a concentration ratio of [PF ₆ ⁻ ]: [CF ₃ BF ₃ ⁻ ] ranging from 100/1 to 1/1. Is done. In yet a further embodiment, the anion is comprised of a mixture of PF ₆ ⁻ and BF ₄ ⁻ at a concentration ratio of [PF ₆ ⁻ ]: [BF ₄ ⁻ ] ranging from 100/1 to 1/1.

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

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

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

  In still further preferred embodiments, the phosphonium ionic liquid composition is composed of a combination of cations and anions as shown in Table 5 below:

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

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

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

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

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

  Further preferred embodiments include phosphonium ionic liquid compositions composed of combinations of cations and anions as shown in Table 11 below:

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

  Another preferred exemplary embodiment includes a phosphonium ionic liquid composition composed of a combination of cations and anions as shown in Table 13 below:

  In some embodiments, additional examples of suitable phosphonium ionic liquid compositions include, but are not limited to, di-n-propylethylmethylphosphonium bis- (trifluoromethylsulfonyl) imide; n-butyl n-propyl And ethylmethylphosphonium 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-methylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphoranium bis- (tri Fluoromethylsulfonyl) imide; n-butylmethylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-hexylmethylphosphoranium bis- (trifluoromethylsulfonyl) imide; and phenylmethylphosphoranium bis- (tri Further examples include fluoromethylsulfonyl) imide.

  In another embodiment, examples of suitable phosphonium ionic liquid compositions include, but are not limited to, 1-ethyl-1-methylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphoranium Bis- (trifluoromethylsulfonyl) imide; n-butylmethylphosphoranium bis- (trifluoromethylsulfonyl) imide; n-hexylmethylphosphoranium bis- (trifluoromethylsulfonyl) imide; and phenylmethylphosphoranium Bis- (trifluoromethylsulfonyl) imide is mentioned.

  Further exemplary embodiments of suitable phosphonium ionic liquid compositions include, but are not limited to, 1-ethyl-1-methylphosphacyclohexanebis- (trifluoromethylsulfonyl) imide; n-propylmethylphosphacyclohexanebis -(Trifluoromethylsulfonyl) imide; n-butylmethylphosphacyclohexanebis- (trifluoromethylsulfonyl) imide; n-hexylmethylphosphacyclohexanebis- (trifluoromethylsulfonyl) imide; and phenylmethylphosphacyclohexanebis -(Trifluoromethylsulfonyl) imide is mentioned.

  The phosphonium ionic liquids of the present invention may also form eutectics from one or more solids, or solids and liquids, according to some embodiments. In this case, the term “ionic liquid” is further defined to include ionic liquids that are ionic solids or eutectics originating from ionic liquids and ionic solids, such as binary, ternary, etc.

Redox Active Molecules The phosphonium ionic liquids of the present invention described herein can be utilized to synthesize a wide range of hybrid components and / or devices, such as memory devices and elements. In exemplary embodiments, the phosphonium ionic liquids herein are used to form molecular memory devices in which information is stored in redox active information storage molecules.

  As used herein, the term “redox active molecule (ReAM)” is intended to refer to a molecule or component of a molecule that can be oxidized or reduced, eg, by applying an appropriate voltage. As described below, ReAM can include macrocycles, including but not limited to porphyrins and porphyrin derivatives, and non-macrocyclic compounds, including sandwich compounds such as those described herein. And the like. In certain embodiments, the ReAM can include multiple subunits, such as in the case of a dyad or triad. Examples of ReAM include ferrocene, Bipy, PAH, and viologen. In general, as described below, there are several types of ReAM useful in the present invention, all based on multidentate proligands, including macrocyclic and non-macrocyclic moieties. Some suitable proligands and complexes, and suitable substituents are described in U.S. Patent No. 6,212,093; U.S. Patent No. 6,728,129; U.S. Patent No. 6,451,942; U.S. Patent No. 6,777,516; U.S. Patent No. 6,381,169; U.S. Patent No. 6,381,169; U.S. Patent No. 6,657,884; U.S. Patent No. 6,272,038; U.S. Patent No. 6,484,394; and U.S. Patent Application No. 10 / 040,059; U.S. Patent Application No. 10 / 682,868; U.S. Patent Application No. 10 / 445,977; Outlined in patent application 10 / 834,630; U.S. patent application 10 / 135,220; U.S. patent application 10 / 723,315; U.S. patent application 10 / 456,321; U.S. patent application 10 / 376,865. All of these, and particularly their structure and description depicted therein, are expressly incorporated by reference.

  Suitable proligands fall into two categories: ligands that use nitrogen, oxygen, sulfur, carbon, or phosphorus atoms (depending on the metal ion) as coordination atoms (in the literature, sigma (σ) donors and generally And organometallic ligands such as metallocene ligands (commonly referred to in the literature as pi (π) donors and depicted herein as Lm).

  In addition, a single ReAM can have more than one redox activity. For example, FIG. 13A of US Patent Application Publication No. 2007/0108438 shows two redox active subunits, porphyrin (shown in the absence of metal), and ferrocene. Similarly, a sandwich coordination compound is considered a single ReAM. This is distinguished from the case where these ReAMs are polymerized as monomers. Furthermore, the metal ions / complexes of the present invention may be accompanied by counter ions not generally shown herein.

Macrocyclic Ligand In one embodiment, ReAM is a macrocyclic ligand, which includes both macrocyclic proligands and macrocyclic complexes. As used herein, "macrocyclic proligands" contain donor atoms (sometimes referred to herein as "coordination atoms") that are oriented so that they can bind to a metal ion and surround the metal atoms. Means a cyclic compound having a sufficient size. Generally, the donor atom is a heteroatom including, but not limited to, nitrogen, oxygen and sulfur, with nitrogen being particularly preferred. However, as will be appreciated by those skilled in the art, different metal ions preferentially bind to different heteroatoms, and thus the heteroatoms used can vary depending on the desired metal ion. Further, in some embodiments, a single macrocycle can contain different types of heteroatoms.

  A “macrocyclic complex” is a macrocyclic proligand having at least one metal ion, and in some embodiments, the macrocyclic complex comprises a single metal ion, but is described below. As such, multinuclear complexes including polynuclear macrocyclic complexes are also envisioned.

  A wide variety of macrocyclic ligands have found use in the present invention, including those that are electronically conjugated and those that may not, but the macrocyclic ligands of the present invention are preferably Has at least one, preferably two or more oxidation states, with 4, 6 and 8 oxidation states being particularly significant.

A rough schematic of a suitable macrocyclic ligand is shown and described in FIGS. 11 and 14 of US Patent Application Publication No. 2007/0108438, all in addition to FIGS. It is incorporated in the description. In this embodiment, which is largely based on porphyrin, a 16-membered ring (either the carbon or heteroatom if the -X- moiety contains a single atom), a 17-membered ring (two of the -X- moieties are two ), 18-membered ring (when two of the -X- moieties contain two skeleton atoms), 19-membered ring (three of the -X- moieties contain two skeletal atoms) ) Or 20-membered rings (when all four of the -X- moieties contain two skeletal atoms) are all envisioned. Each -X- group is independently selected. The -Q- moiety, together with the backbone -C-heteroatom-C (which has either a single bond or a double bond that independently connects the carbon and heteroatom), is one or two ( In the case of a 5-membered ring) or one, two or three (in the case of a 6-membered ring) form a 5- or 6-membered ring optionally substituted with independently selected R ² groups. In some embodiments, the rings, bonds, and substituents are chosen such that the compound is electronically conjugated as a result and has at least two oxidation states.

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

Porphyrins A particularly preferred subset of macrocycles suitable in the present invention are porphyrins including porphyrin derivatives. Such derivatives include porphyrins having an additional ring ortho-fused or ortho-perifused to the porphyrin nucleus, or porphyrins in which one or more carbon atoms of the porphyrin ring are replaced by atoms of another element (skeleton substitution) Derivatives in which the nitrogen atom of the porphyrin ring is replaced by an atom of another element (nitrogen skeletal substitution), Derivatives in which substituents other than hydrogen are located in the peripheral atoms of the porphyrin (meso-, β- or nuclear atoms, porphyrin One or more of the derivatives having a saturation of one or more bonds (e.g. hydroporphyrin, e.g., chlorin, bacteriochlorin, isobacteriochlorin, decahydroporphyrin, colfin, pyrocorphine, etc.), a pyrrole unit and a pyromethenyl unit A derivative in which multiple atoms are inserted into the porphyrin ring (extended Phyllins), derivatives in which one or more groups have been removed from the porphyrin ring (reduced porphyrins such as choline, corrole) and combinations of the aforementioned derivatives (such as phthalocyanines, subphthalocyanines and porphyrin isomers). Suitable porphyrin derivatives include, but are not limited to, etiophyllin, pyroporphyrin, rhodoporphyrin, philoporphyrin, chlorophyll groups including phyloerythrin, chlorophyll a and b, and deuteroporphyrin, deuterohemin, Hemoglobin groups including hemin, hematin, protoporphyrin, mesohemin, hematoporphyrin, mesoporphyrin, coproporphyrin, uruporphyrin and turacin, and tetraarylazadipi A series of lomethin can be mentioned.

  As is the case for the compounds outlined herein, and as will be appreciated by those skilled in the art, each unsaturation position is defined herein as either a carbon or a heteroatom. One or more such substituents may be included depending on the desired valence of the system.

  In a preferred embodiment, the redox active molecule can be a metallocene, which can be substituted at any suitable position using the R group independently selected herein. Metallocenes that find particular use 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 a redox potential range of less than about 2 volts.

  It is understood that the oxidation potential of these series members can be varied as usual by changing the metal (M) or substituent.

  Another example of a redox active molecule composed of a porphyrin is shown in FIG. 12H of U.S. Patent Application Publication No. 2007/018438 (where F is a redox active subunit (e.g., ferrocene, substituted ferrocene, metalloporphyrin, or metallochlorin). J1 is a linker, M is a metal (for example, Zn, Mg, Cd, Hg, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Mn, B, Al, Ga, Pb and Sn, etc.), and S1 and S2 are independently aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, Selected from the group of alkylamino, acyl, sulfoxyl, sulfonyl, imide, amide, and carbamoyl, wherein the substituent has 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 a substrate, coupling to the substrate And selected from the group of reaction sites that can be ion-coupled to the substrate). In preferred embodiments, X or L-X may be an alcohol or thiol. In some embodiments, L-X can be eliminated and replaced with a substituent independently selected from the same group as S1 or S2.

  The control over the hole accumulation and hole hopping characteristics of the redox active unit of the redox active molecule used in the memory device of the present invention allows fine control over the architecture of the memory device.

  Such control is executed by synthetic design. The hole storage characteristics depend on the oxidation potential of the redox active unit or subunit that is itself the storage medium used in the device of the present invention or that is used to assemble this storage medium. The hole accumulation properties and redox potential can be precisely adjusted by the choice of the base molecule, the metal to be bound and the peripheral substituents (Yang et al. (1999) J. Porphyrins Phthalocyanines, 3: 117-147), the disclosure of which This reference is incorporated herein by reference.

  For example, in the case of porphyrins, Mg porphyrins are more easily oxidized than Zn porphyrins, and electron-withdrawing or electron-emitting aryl groups can adjust their oxidation properties as expected. Hole hopping occurs between isoenergetic porphyrins in the nanostructure and is mediated through covalent linkers linking the 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. (1997) J. Am. Mater. Chem., 7: 1245-1262, Strachan et al. (1998) Inorg. Chem., 37: 191-11201, Yang et al. (1999) J. Am. Chem. Soc., 121: 4008-4018) These disclosures are specifically incorporated herein by reference in their entirety.

  The design of compounds with predicted redox potentials is well known to those skilled in the art. In general, the oxidation potential of redox active units or subunits is well known to those skilled in the art and can be examined (see, eg, Handbook of Electrochemistry of the Elements). Furthermore, 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, in particular the oxidation potential of the information storage molecule or information storage medium, can be measured according to standard methods. Usually, the oxidation potential is predicted by comparing the experimentally determined oxidation potential of a basic molecule with the oxidation potential of a basic molecule with one substituent and determining the potential shift due to that particular substituent. Is done. The predicted oxidation potential is then obtained from the sum of such substituent-dependent potential shifts for each substituent.

  The suitability of a particular redox active molecule for use in the methods of the present invention can be readily determined. In accordance with the method of the present invention, the molecule of interest is simply polymerized and coupled to a surface (eg, a hydrogen passivated surface). (E.g., herein or in U.S. Pat.No. 6,272,038; U.S. Pat.No. 6,212,093; and U.S. Pat.No. 6,208,553, WO 01/03126, or (Roth et al. (2000) Vac. Sci. 18: 2359-2364; Roth et al. (2003) J. Am. Chem. Soc. 125: 505-517)) to evaluate the following by performing sinusoidal voltammetry): 1) whether the molecule is coupled to the surface, 2) degree of coverage, 3) whether the molecule degrades during the coupling procedure, and 4) multiple read / write operations Stability of the molecule against.

  Also included within the definition of “porphyrin” is a porphyrin complex comprising a porphyrin proligand and at least one metal ion. Suitable metals for porphyrin compounds will vary with the heteroatoms used as coordination atoms, but are generally selected from transition metal ions. The term “transition metal” as used herein generally refers to 38 elements in groups 3-12 of the periodic table. Usually, transition metals say that these valence electrons, or the electrons they use to combine with other elements, are present in multiple shells, often resulting in some common oxidation state. Characterized by facts. In certain embodiments, transition metals of the present invention include, but are not limited to, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, Ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, ruzafodium, and / or their oxides and / or nitrides, and / or alloys, and One or more of the mixtures may be mentioned.

Other macrocycles There are several macrocycles based on cyclene derivatives. FIGS. 17 and 13C of U.S. Patent Application Publication No. 2007/0108438 show several examples based on cyclene / cyclam derivatives that can include skeletal expansion by inclusion of independently selected carbon or heteroatoms. The macrocyclic proligand is shown. In some embodiments, at least one R group is a redox active subunit, preferably electronically conjugated to a metal. In some embodiments, two or more adjacent R ² groups form a ring or an aryl group, including when at least one R group is a redox active subunit.

  Further, in some embodiments, macrocyclic complexes that rely on organometallic ligands are used. In addition to pure organic compounds for use as redox moieties, and various transition metal coordination complexes with δ-bonded organic ligands having donor atoms as heterocyclic or exocyclic substituents, π-bonded organic ligands A wide variety of transition metal organometallic compounds are available (Advanced Inorganic Chemistry, 5th Edition, Cotton & Wilkinson, John Wiley & Sons, 1988, Chapter 26; Organometallics, A Concise Introduction, Elschenbroich et al., 2nd Edition 1992, VCH; and Comprehensive Organometallic Chemistry II, A Review of the Literature 1982-1994, edited by Abel et al., 7, 7, 8, 10 and 11, Pergamon Press, which are hereby incorporated by reference. Explicitly incorporated by). Such organometallic ligands include cyclic aromatic compounds such as cyclopentadienide ion [C5H5 (-1)], as well as indenides (classes of metallocenes) that form a class of bis (cyclopentadienyl) metal compounds (ie, metallocenes). indenylide) (-1) ions, etc., including various ring-substituted and ring-fused derivatives, eg, incorporated by reference, 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, ferrocene [(C5H5) 2Fe] and its derivatives are a wide variety of chemicals (Connelly et al., Chem. Rev. 96: 877-910 (1996) incorporated by reference) and electrochemical ( Geiger et al., Advances in Organometallic Chemistry 23: 1-93 and Geiger et al., Advances in Organometallic Chemistry 24:87, incorporated by reference), are typical examples that have been used for electron transfer or "redox" reactions. . A variety of first, second and third period transition metal metallocene derivatives are useful as redox moieties (and redox subunits). Other potentially suitable organometallic ligands include cyclic arenes, such as benzene, and their ring substituted and fused derivatives to produce bis (arene) metal compounds, among 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 can be combined with other π-bonded and δ-bonded ligands. Together, it constitutes a general class of organometallic compounds in which a metal carbon bond is present. Electrochemical studies of various dimers and oligomers of such compounds with crosslinked organic ligands and additional non-crosslinked ligands and with and without metal-metal bonds are all useful.

  When the one or more co-ligands are organometallic ligands, the ligand is generally attached via one of the carbon atoms of the organometallic ligand, provided that The addition may be through other atoms to the heterocyclic ligand. Preferred organometallic ligands include metallocene ligands including substituted derivatives and metallocene neophanes (see Cotton and Wilkenson, supra, page 1174). For example, a derivative of a metallocene ligand, such as methylcyclopentadienyl, preferably has a plurality of methyl groups such as pentamethylcyclopentadienyl. By using this, the stability of metallocene is increased. be able to. In some embodiments, the metallocene is derivatized with one or more substituents as outlined herein, particularly to alter the redox potential of the subunit or portion thereof.

  Any combination of ligands can be used as described herein. Preferred combinations include: a) all ligands are nitrogen donor 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 formula L-Mn-L, wherein each L is a heterocyclic ligand (as described below) and each M Is a metal, n is 2 or more, most preferably 2 or 3, and each metal is located between a pair of ligands and (depending on the oxidation state of the metal) one or each in each ligand A plurality of heteroatoms (usually bonded to a plurality of heteroatoms, eg, 2, 3, 4, 5 etc.). Therefore, sandwich coordination compounds are not organometallic compounds such as ferrocene, in which the metal is bonded to a carbon atom. The ligands in the sandwich coordination compound are generally arranged in a stacking direction (i.e., generally coplanarly oriented and axially aligned with each other, provided that they are relative to each other, It may or may not be rotated about its axis) (see, eg, Ng and Jiang (1997) Chemical Society Reviews 26: 433-442, incorporated by reference). 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 detail in U.S. Patent No. 6,212,093; U.S. Patent No. 6,451,942; U.S. Patent No. 6,777,516, and the polymerization of these molecules is described in U.S. Patent Application Publication No. 2007/0123618. All of these, especially the individual substituents found to be used in both sandwich complexes and “single macrocycle” complexes, are included herein.

  The term “double-decker sandwich coordination compound” refers to a sandwich coordination compound where n is 2, as described above, and thus the formula L′-M′-LZ, wherein each of L ′ and LZ is the same (E.g., Jiang et al. (1999) J. Porphyrins Phthalocyanines 3: 322-328 and U.S. Pat.No. 6,212,093; U.S. Pat.No. 6,451,942; U.S. Pat.No. 6,777,516). The polymerization of these molecules is described in US Patent Application Publication No. 2007/0123618, which is hereby incorporated by reference in its entirety.

  The term “triple-decker sandwich coordination compound” refers to a sandwich coordination compound where n is 3, as described above, and thus the formula L′-M′LZ-MZ-L3 (where L ′, LZ and Refers to sandwich coordination compounds having each of L3, which may be the same or different, and M ′ and MZ may be the same or different (see, for example, Arnold et al. (1999) Chemistry Letters 483-484 and US Pat. No. 6,212,093; U.S. Pat.No. 6,451,942; U.S. Pat.No. 6,777,516) .The polymerization of these molecules is described in U.S. Patent Application Publication No. 2007/0123618, which is incorporated herein by reference in its entirety. In the issue.

  In addition, polymers of these sandwich compounds are also useful, including “dyads” and “triads” as described in US Pat. No. 6,212,093; US Pat. No. 6,451,942; US Pat. No. 6,777,516. The polymerization of these molecules, which are included, is described in US Patent Publication No. 2007/0123618, which is incorporated by reference.

Non-macrocyclic proligands and complexes As a general rule, ReAM containing a non-macrocyclic chelator forms a non-macrocyclic chelate by binding to a metal ion, because of the presence of the metal, This is because a plurality of oxidation states can be obtained by binding a plurality of proligands together.

In some embodiments, a nitrogen donating proligand is used. Suitable nitrogen donating proligands are well known in the art and include, but are not limited to, NH ₂ ; NHR; NRR ′; pyridine; pyrazine; isonicotinamide; imidazole; substituted derivatives of bipyridine and bipyridine; terpyridine and substituted derivatives Phenanthroline, especially 1,10-phenanthroline (short for phen) and substituted derivatives of phenanthroline such as 4,7-dimethylphenanthroline and dipyridol [3,2-a: 2 ', 3'-c] phenazine ( Dipyridphenazine; 1,4,5,8,9,12-hexaazatriphenylene (shortened hat); 9,10-phenanthrenequinone diimine (shortened phi); 1 1,4,5,8-tetraazaphenanthrene (abbreviated tap); 1,4,8,11-tetra-azacyclotetradecane (abbreviated cyclam) and isocyanide. Substituted derivatives including fused derivatives can also be used. It should be noted that macrocyclic ligands that do not coordinately saturate metal ions and require the addition of another proligand are considered non-macrocyclic for this purpose. As those skilled in the art will appreciate, it is possible to form a coordinately saturated compound by covalently adding several “non-macrocyclic” ligands, but Lack of formula skeleton.

  Suitable sigma donating ligands using carbon, oxygen, sulfur and phosphorus are known in the art. For example, suitable sigma carbon donors can be found in Cotton and Wilkenson, Advanced Organic Chemistry, 5th edition, John Wiley & Sons, 1988 (see, e.g., page 38), incorporated herein by reference. Found. Similarly, suitable oxygen ligands include crown ethers, water and others known in the art. Phosphine and substituted phosphines are also suitable, see Cotton and Wilkenson, page 38.

  Oxygen, sulfur, phosphorus and nitrogen donor ligands are added in such a way as to allow the heteroatom to function as a coordination atom.

Multinucleated proligands and complexes Further, some embodiments utilize multidentate ligands that are multinucleated ligands, eg, these multidentate ligands can bind multiple metal ions. These multidentate ligands may be macrocyclic or non-macrocyclic.

  Some suitable proligands and complexes, and suitable substituents are described in U.S. Patent No. 6,212,093; U.S. Patent No. 6,728,129; U.S. Patent No. 6,451,942; U.S. Patent No. 6,777,516; U.S. Patent No. 6,381,169; U.S. Patent No. 6,381,169; U.S. Patent No. 6,657,884; U.S. Patent No. 6,272,038; U.S. Patent No. 6,484,394; and U.S. Patent Application No. 10 / 040,059; U.S. Patent Application No. 10 / 682,868; U.S. Patent Application No. 10 / 445,977; Outlined in patent application 10 / 834,630; U.S. patent application 10 / 135,220; U.S. patent application 10 / 723,315; U.S. patent application 10 / 456,321; U.S. patent application 10 / 376,865. All of these, and in particular their structure and description shown therein, are expressly incorporated by reference.

Applications and Uses of Phosphonium Ionic Liquids or Salts As used herein and unless otherwise noted, the terms “memory element”, “memory cell” or “memory cell” are used to store information. Refers to an electrochemical cell that can. A preferred “storage cell” is a discontinuous region of the storage medium addressed by at least one, preferably two electrodes (eg, working electrode and reference electrode). A memory cell can be individually addressed (eg, a unique electrode is associated with each memory element), or multiple memory elements can be a single electrode, particularly if the oxidation states of different memory elements can be distinguished. Can be addressed. The memory element can optionally include a dielectric (eg, a dielectric impregnated with counter ions).

  As used herein, the term “electrode” refers to any medium capable of transporting charge (eg, electrons) to and / or from a storage molecule. Preferred electrodes include, but are not limited to, Group III elements (including doped and oxidized Group III elements), Group IV elements (including doped and oxidized Group IV elements), Group V elements (doped And oxidized organic group V elements) and transition metals (including transition metal oxides and transition metal nitrides) and metals and conductive organic molecules. The electrodes can be fabricated into almost any two-dimensional or three-dimensional shape (eg, discontinuous lines, pads, planes, spheres, cylinders).

  As used herein and unless otherwise stated, the term “plural oxidation states” means more than one oxidation state. In preferred embodiments, the oxidation state may reflect an increase in electrons (reduction) or a loss of electrons (oxidation).

  As used herein and unless otherwise stated, the term “multiporphyrin array” refers to a macrocycle of porphyrins linked by a discrete number of two or more covalent bonds. The multiporphyrin array may be linear, cyclic, or branched.

  As used herein and unless otherwise stated, the term “output of an integrated circuit” refers to a voltage generated by one or more integrated circuits and / or one or more integrated circuit components. Or it refers to a signal.

  As used herein and unless otherwise stated, the term `` existing on a single plane '' when used in connection with the memory device of the present invention is the subject component ( Refers to the fact that the storage media, electrodes, etc.) are on the same physical plane of the device (eg, on a single sheet). Components that lie on the same plane can usually be fabricated simultaneously, eg, in a single operation. Thus, for example, all electrodes on a single plane can typically be applied in a single (eg, sputtering) step (assuming they all consist of the same material).

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

As used herein and unless otherwise stated, the term “oxidation” refers to the loss of one or more electrons in an element, compound, or chemical substituent / subunit. In the oxidation reaction, electrons are lost by the atoms of the elements involved in the reaction. The charge on these atoms should then be more positive. The electrons are lost from the species undergoing oxidation, and thus the electrons appear as products in the oxidation reaction. Oxidation occurs in the reaction Fe ²⁺ (aqueous) → Fe ³⁺ (aqueous) + e ⁻ , because the electrons are clearly generated as “free” entities in the oxidation reaction. This is because electrons are lost from the Fe ²⁺ (aqueous) species. Conversely, the term reduction refers to the increase of one or more electrons by an element, compound, or chemical substituent / subunit.

  As used herein and unless otherwise stated, the term “oxidation state” refers to the state of an electron in an electrically neutral state or element, compound, or chemical substituent / subunit. It refers to a state created by an increase or loss. In a preferred embodiment, the term “oxidation state” refers to a state including a neutral state and any state other than a neutral state caused by an increase or loss (reduction or oxidation) of electrons.

  As used herein and unless otherwise stated, the terms `` read out '' or `` question '' refer to determining the oxidation state of one or more molecules (e.g., molecules that make up a storage medium). .

  As used herein and unless otherwise stated, the term “redox active unit” or “redox active subunit” refers to a molecule or molecule that can be oxidized or reduced by applying an appropriate voltage. Refers to the ingredients.

  As used herein and unless otherwise stated, the term “refresh”, when used in connection with a storage molecule or storage medium, applies the voltage to the storage molecule or storage medium by applying a voltage to the storage molecule or storage medium. Alternatively, it refers to resetting the oxidation state of the storage medium to a predetermined state (eg, the oxidation state in which the storage molecule or storage medium was placed immediately before reading).

  As used herein and unless otherwise stated, the term `` reference electrode '' refers to one or more electrodes that provide a measurement reference (e.g., a specific reference voltage) recorded from the working electrode. Used to point. In a preferred embodiment, the reference electrodes of the memory device of the present invention are at the same potential, although this is not necessarily the case in some embodiments.

  As used herein and unless otherwise noted, a “sinusoidal voltammeter” is a voltammetric device capable of determining the frequency domain characteristics of an electrochemical cell.

  As used herein and unless otherwise stated, the term “memory density” refers to the number of bits per volume and / or the number of bits per molecule that can be stored. If the storage medium is said to have a storage density of more than 1 bit per molecule, this preferably means that the storage medium contains molecules that allow a single molecule to store at least 1 bit of information. Refers to the fact that

  As used herein and unless otherwise noted, the term “storage location” refers to a discrete area or area in which a storage medium is located. When addressed with one or more electrodes, the storage location may form a storage cell. However, if two storage locations contain the same storage medium and have essentially the same oxidation state and both storage locations are commonly addressed, they can form a functional storage cell .

  As used herein and unless otherwise stated, the term “storage medium” refers to a composition comprising a memory molecule of the invention, preferably a memory molecule of the invention bound to a substrate.

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

  As used herein and unless otherwise stated, the term “voltammetric device” is capable of measuring the current generated in an electrochemical cell as a result of applying a voltage or changing a voltage. It is a device.

  As used herein and unless otherwise noted, a voltage source is any source (eg, molecule, device, circuit, etc.) that can apply a voltage to a target (eg, an electrode).

  As used herein and unless otherwise noted, the term “working electrode” refers to one or more electrodes used to set or read the state of a storage medium and / or storage molecule. Used for.

Devices 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, a device is provided that includes a first electrode, a second electrode, and an electrolyte comprised of an ionic liquid composition, the ionic liquid composition having the general formula:
R ¹ R ² R ³ R ⁴ P
Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent group, and one or more anions. An electrolyte is electrically coupled to at least one of the first and second electrodes. In some embodiments, the first electrode is composed of a redox active molecule (ReAM) as described in detail above.

  In another embodiment, a molecular storage device comprising a working electrode and a counter electrode configured to provide electrical capacitance, and an ion conductive composition comprising one or more phosphonium-based cations of the above general formula Provided, the ionically conductive composition is electrically coupled to at least the working electrode and the counter electrode.

  In another embodiment, the present invention encompasses a molecular memory element comprising a switching device, bit lines and word lines coupled to the switching device, and a molecular storage device accessible via the switching device. The molecular storage device can be placed in two or more distinct states, where the molecular storage device is placed in one of the distinct states by signals applied to the bit and word lines. The molecular storage device includes a first electrode, a second electrode, and a phosphonium-based cation and a suitable anion electrolyte between the first and second electrodes. Another embodiment includes a molecular memory array that includes a plurality of molecular storage elements that can place each molecular storage element in two or more distinct states. The plurality of bit lines and word lines are coupled to the plurality of molecular storage elements such that each molecular storage element is coupled to and addressable by at least one bit line and at least one word line. .

  A molecular memory device may include an addressable array of molecular storage elements. The address decoder receives the coded address and creates a word line signal corresponding to the coded address. The word line driver is coupled with the address decoder and generates an amplified word line signal. The amplified word line signal controls a switch that selectively couples a member of the array of molecular storage elements to the bit line. Read / write logic coupled to the bit line determines whether the molecular memory device is in read or write mode. In the read mode, the sense amplifier coupled to each bit line detects the electronic state of the selectively coupled molecular memory element and outputs a data signal indicating the electronic state of the selectively coupled molecular memory element on the bit line. To generate. In write mode, read / write logic carries data signals onto the bit lines and selectively coupled molecular storage elements.

  Another embodiment includes devices that include logic integrated with an embedded molecular memory device, such as application specific integrated circuit (ASIC) and system on chip (SOC) devices. Such an implementation includes one or more functional components formed monolithically with a molecular memory device and interconnected to the molecular memory device. Functional components may include solid state electronic devices and / or molecular electronic devices.

  In certain embodiments, the molecular storage device is implemented as a stacked structure formed subsequent to and on a semiconductor substrate having an active device formed therein. In other embodiments, 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 the semiconductor substrates. Molecular storage devices include, for example, an electrochemical cell having two or more electrode surfaces separated by an electrolyte (eg, a ceramic or solid electrolyte). A storage molecule (eg, a molecule having one or more oxidation states that can be used for information to be stored) is coupled to an electrode surface within the electrochemical cell.

  Other embodiments of the invention include transistor switching devices including field effect transistors; row decoders coupled to word lines; column decoders coupled to bit lines; current preamplifiers connected to bit lines; connected to bit lines Sense amplifier, an address decoder that receives a coded address and generates a word line signal corresponding to the coded address, a line driver coupled to the address decoder (the line driver generates an amplified word line signal ( In some cases, the amplified word line signal controls a switch that selectively couples a member of the array of molecular storage elements to the bit line)), and the read / write logic coupled to the bit line (the read / write logic is , Molecular memory Sense amplifier coupled to each bit line (if the device is in read mode, the sense amplifier coupled to each bit line is a selectively coupled numerator). Detects the electronic state of the storage element and generates a data signal on the bit line indicating the electronic state of the selectively coupled molecular storage element (if the device is in write mode, the read / write logic will bit the data signal Including the use of components selected independently from lines and selectively coupled molecular memory elements))); electrolyte layers; and combinations thereof.

  Further embodiments include a second electrode coupled to the ground and bit and word lines that are either vertical or parallel.

  Further embodiments have the memory array of the present invention including volatile memory such as DRAM or SRAM, or non-volatile memory such as flash or ferroelectric memory.

  In a further embodiment, the molecular storage device includes an additional layer formed on the first electrode, the additional layer includes an opening, the molecular material is in the opening, and the first layer is formed on the additional layer. An array is provided that is electronically coupled to the two electrode layers and the electrolyte layer.

  Another embodiment includes a monolithically integrated device that includes a logic device configured to perform a particular function and an implantable molecular memory device of the present invention coupled to the logic device. The device may optionally include an application specific integrated circuit (ASIC), system on chip (SOC), solid state electronic device or molecular electronic device.

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

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

  The memory device operates by receiving an N-bit row address in the row address decoder and an M-bit column address in the column address decoder. The row address decoder generates a signal on one word line. The word line may include a word line driver circuit that carries a high current signal on the word line. Because wordlines tend to be long and thin conductors that extend over most of the chip surface, a significant amount of current and a large power switch are required to carry the wordline signal. As a result, line driver circuits often include a power supply in addition to a power supply circuit (not shown) that provides operating power to other logic. Therefore, word line drivers tend to include large components, and high current fast switching tends to create noise, squeeze the limits of power supplies and power regulators, and squeeze isolated structures.

  A conventional storage array has more columns (bit lines) than rows (word lines) because each word line becomes active during a refresh operation and is coupled to that word line. This is because all of the storage elements that have been refreshed are refreshed. Thus, the smaller the number of rows, the less time is required to refresh all of the rows. One feature of the present invention is that molecular memory devices have data retention on the order of 10 seconds, 100 seconds, 1000 seconds, or effectively an unlimited number of seconds, much longer than normal capacitors. It can be configured to show. Thus, the refresh cycle can be carried out with a frequency that is several orders of magnitude lower or can be omitted altogether. Thus, the refresh considerations that actually affect the physical layout of the memory array can be relaxed and various shaped arrays can be implemented. For example, a memory array can be easily manufactured with a larger number of word lines, which makes each word line shorter. As a result, less current is required to drive each word line at high speed, and the word line driver circuit can be reduced or eliminated. Alternatively or additionally, read / write access time can be improved by driving shorter word lines faster. As yet another alternative, a mechanism for storing multiple states of information in each memory location can be obtained by providing each row of memory locations with multiple word lines.

  The sense amplifier is coupled to each bit line and operates to detect a signal on the bit line 109 that indicates the state of the memory element coupled to that bit line and amplifies the state to a signal of an appropriate logic level. To do. In one embodiment, the sense amplifier may be implemented with a substantially conventional design because such a conventional design operates to detect and amplify signals from molecular memory devices. Because it becomes. Alternatively, unlike conventional capacitors, some molecular memory elements provide highly characteristic signals that indicate these states. These characteristic signals can be more easily and reliably latched by the read / write logic buffer than the state signal from the molecular storage device is stored in the conventional capacitor, so that conventional sense amplifier logic The need for can be reduced. That is, the present invention can provide a device that is large enough to eliminate the need for a sense amplifier.

  The read / write logic includes circuitry for placing the memory device in a read or write state. In the read state, data from the molecular array is placed on the bit line (with or without the activation of the sense amplifier) and captured by the read / write logic buffer / latch. The column address decoder will select which bit line is active in a particular read operation. In a write operation, the read / write logic causes the data signal on the selected bit line to overwrite any data already stored in the memory element that the data addressed when the word line becomes active. carry.

  The refresh operation is substantially similar to the read operation, but the word line is driven by a refresh circuit (not shown) rather than an externally applied address. In a refresh operation, if a sense amplifier is used, it drives the bit line to a signal level that indicates the current state of the memory element, and its value is automatically rewritten to the memory element. Unlike the read operation, the bit line state is not coupled to the read / write logic during the refresh. This operation is required only when the charge retention time of the molecules used is shorter than the operating life of the device used (eg, about 10 years for flash memory).

  In an exemplary embedded system that includes a central processing unit and molecular memory, the memory bus exchanges address, data, and control signals by coupling with the CPU and molecular memory devices. In some cases, the embedded system may also include a conventional memory coupled to a memory bus. Conventional memory may include random access memory (eg, DRAM, SRAM, SDRAM, etc.) or read only memory (eg, ROM, EPROM, EEPROM, etc.). These other types of memory can be useful for caching data molecular memory devices, storing operating system or BIOS files, and so on. The embedded system may include one or more input / output (I / O) interfaces that allow the CPU to communicate with external devices and systems. The I / O interface may be implemented by a serial port, a parallel port, a radio frequency port, an optical port, an infrared port, or the like. Further, the interface may be configured to communicate using any available protocol, including packet-based protocols.

Batteries The phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited for electrolytes for battery applications. In one embodiment, a battery is provided that includes an anode, a cathode, a separator between the anode and cathode, and an electrolyte. The electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
An ion comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent Consists of one or more ionic liquids or salts dissolved in a liquid composition or solvent. In one embodiment, the electrolyte is comprised of an ionic liquid having one or more phosphonium-based cations and one or more anions, the ionic liquid composition having a thermodynamic stability of 375 ° C. or less. A liquidus range wider 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 one or more salts dissolved in a solvent having one or more phosphonium-based cations and one or more anions, the electrolyte composition comprising: At room temperature, 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 The ionic conductivity of is shown.

Batteries comprising electrolyte compositions according to embodiments of the present invention are filed concurrently with this specification and are hereby incorporated by reference in their entirety. (Attorney Docket No. 057472-060).

  In some embodiments, the electrolyte composition is further comprised of, but 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) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene Carbonate (VC), vinyl ethylene carbonate (VEC), phenyl ethylene carbonate (PhEC), propyl methyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL) , And γ-valerolactone (GVL).

In some embodiments, the electrolyte composition comprises 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), and is composed of one or more lithium salts having one or more anions selected from the group consisting of.

In further embodiments, the electrolyte composition is composed of, but 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 bis (pentafluorophenyl) imide lithium _{(Li (CF 3 CF 2 SO} 2) 2 N or LiBETI).

  In a further aspect, the phosphonium electrolyte has lower flammability and thus improves the safety of battery operation. In a further aspect, the phosphonium ionic liquid or salt can be used as an additive to facilitate the formation of a solid electrolyte interphase (SEI) layer or electrode protection layer. The SEI layer helps to widen the electrochemical stability window, suppress battery degradation or decomposition reactions and thus improve battery cycle life.

Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention can vary, including lithium ion batteries and rechargeable lithium metal batteries (sometimes referred to herein collectively as “lithium batteries”). Are well suited for electrolytes such as lithium primary batteries and lithium secondary batteries. Examples of lithium primary batteries include, but are not limited to: lithium / manganese dioxide (Li / MnO ₂ ), lithium / carbon monofluoride (Li / CFx), 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 such as Anode such as lithium titanium oxide (LTO), as well as lithium cobalt oxide (LCO) (LiCoO ₂ ), lithium manganese oxide (LMO) (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 ) and a cathode of lithium vanadium oxide (LVO). Examples of rechargeable lithium metal batteries include, but are not limited to: lithium cobalt oxide (LCO) (LiCoO ₂ ), lithium manganese oxide (LMO) (Li / Mn ₂ O ₄ ), phosphoric acid Iron Lithium (LFP) (LiFePO ₄ ), Lithium Nickel Manganese Cobalt (NMC) (Li (NiMnCo) O ₂ ), Lithium Nickel Cobalt Aluminum (NCA) (Li (NiCoAl) O ₂ ), Lithium Nickel Manganese Oxide (LNMO) (Li ₂ NiMn ₃ O ₈ ) cathode and lithium metal anode, lithium / sulfur battery, and lithium / air battery.

  In a further embodiment, the above approach to energy storage can be combined with an electrochemical double layer capacitor (EDLC) to form a hybrid energy storage system including an array of batteries and EDLC.

Electrochemical Double Layer Capacitors Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are very suitable for electrochemical double layer capacitor (EDLC) electrolytes, also called electrochemical capacitors or supercapacitors or ultracapacitors. . An EDLC is an energy storage device that can store more energy than a conventional capacitor and release this energy at a higher rate than a rechargeable battery. In addition, the cycle life of the electrochemical capacitor should far exceed the cycle life of the battery system. EDLC is interesting for potential applications in the state of the art that require power in the form of pulses. Examples of such applications include digital communication devices that require power pulses in the millisecond range, and traction power systems for electric transport equipment where high power demand can persist from seconds to minutes. Battery performance and cycle life are severely degraded as power demand increases. Capacitor battery combinations have been proposed in which the capacitor handles peak power and the battery provides a support load between pulses. Such a hybrid power system can improve overall power performance and extend battery cycle life without increasing the size or mass of the system.

  EDLC is basically the same as a battery in terms of overall design, except that the charge storage nature of the electrode active material is capacitive, that is, the charge and discharge processes are via a solid electronic phase. Only the movement of the electronic charge and the movement of ions through the electrolyte solution phase. Higher power density and longer cycle life can be achieved compared to batteries because no phase transformations that determine speed and limit life occur at the electrode / electrolyte interface of the EDLC device.

  The main EDLC technology is based on double layer type charging with high surface area carbon electrodes, where the capacitor is formed at the carbon / electrolyte interface and balances its charge by charging electrons on the carbon surface. Therefore, the counter ion moves to the carbon surface in the solution phase. Another technique is based on pseudocapacitance-type charging at electrodes that conduct polymers and certain metal oxides. Conductive polymers have been investigated for use in EDLC. A higher energy density can be achieved because charging occurs not only on the outer surface, but also over the entire volume of active polymer material. Metal oxides have also been investigated for use in EDLC. Charging within such actives has been reported to occur over the entire volume of the material, so that the observed charging and energy density is equivalent to or even better than that obtained for conducting polymers. It is expensive.

  In one embodiment of the invention, the EDLC device includes a single cell. Referring to FIG. 1, a schematic cross-sectional view of a single cell EDLC 10 is shown. The single cell EDLC 10 includes a pair of electrodes 12, 12 ′ coupled to current collector plates 14, 14 ′, and two electrodes. It includes a sandwiched separation film or membrane 16 and an electrolyte solution 18 (not shown) that penetrates and fills the pores of the separator and one or more electrodes.

  In another embodiment of the present invention, referring to FIGS. 2A and 2B, the battery electrodes can be fabricated in a bipolar arrangement 20, where the two electrodes 22, 24 are connected to a “bipolar” current collector 26. It is attached on both sides. A multi-cell EDLC can be fabricated by placing several single cells in a bipolar stack to obtain the higher voltage (and power) needed. An exemplary multi-cell EDLC 30 is shown in FIG. 2B, in which the bipolar stack consists of four unit cells 32-38. Each cell has the same structure as the single cell 10 of FIG. In a bipolar stack, each cell is separated from its adjacent cells having a single current collector that also functions as an ion barrier between the cells. Such a design optimizes the current path through the cells, reduces ohmic losses between cells, and minimizes the packaging mass due to current collection. The result is an efficient capacitor with higher energy and power density.

  In some embodiments, the EDLC is formed using a planar or flat structure electrode / separator / electrode assembly. In other embodiments, the EDLC is formed using wound spiral structures, such as cylindrical and prismatic electrode / separator / electrode assemblies.

  In some embodiments, the electrodes are made from high surface area microparticles or nanoparticles of an active material that are grouped together by a binder material to form a porous structure. In addition to the powder that is compressed with the binder, the active material can be made in other forms such as fibers, woven fibers, felts, foams, fabrics, aerogels, and meso beads. Examples of active materials include, but are not limited to: carbon such as carbon black, graphite, graphene; carbon-metal composites; conductive polymers such as polyaniline, polypyrrole, polythiophene; lithium, ruthenium, tantalum, Rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides, and combinations thereof.

  In some embodiments, the electrode binder material is selected from, but not limited to, one or more of the following: polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polyacrylate, acrylate type copolymer (ACM), carboxymethylcellulose (CMC), polyacrylic acid (PAA), polyamide, polyimide, polyurethane, polyvinyl ether (PVE), or combinations thereof.

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

In one embodiment, the electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent such as, but not limited to, an alkyl group as described below. Of the phosphonium-based cation and one or more anions, or an ionic liquid composition or one or more ionic liquids or salts dissolved in a solvent. In some embodiments, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. It is. Any one or more of the salts may be liquid or solid at a temperature of 100 ° C. or lower. In some embodiments, the salt is composed of one cation and one anion pair. In other embodiments, the salt is composed of one cation and multiple anions. In other embodiments, the salt is composed of one anion and multiple cations. In a further embodiment, the salt is composed of multiple cations and multiple anions.

  In one embodiment, the electrolyte is comprised of an ionic liquid having one or more phosphonium-based cations and one or more anions, the ionic liquid composition having a thermodynamic stability of 375 ° C. or less. Exhibit an ionic conductivity of at least 1 mS / cm, or at least 5 mS / cm, or at least 10 mS / cm, at a liquidus range greater than 400 ° C. In another embodiment, the electrolyte is comprised of one or more salts dissolved in a solvent having one or more phosphonium-based cations and one or more anions, the electrolyte composition comprising: At room temperature, 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 The ionic conductivity of is shown.

In another embodiment, the electrolyte composition further comprises one or more conventional, non-phosphonium salts. In some embodiments, the electrolyte composition may be composed of conventional salts, in which case the phosphonium-based ionic liquids or salts disclosed herein are additives. In some embodiments, the electrolyte composition is comprised of a phosphonium-based ionic liquid or salt and one or more conventional salts, which are phosphonium-based ionic liquids or salts: moles of conventional salts (or (Molar concentration) ratio exists in the range of 1: 100 to 1: 1. Examples of conventional salts include, but are not limited to, tetraalkylammonium, such as (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 ⁺ etc., selected from the group consisting of imidazolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, pyridazinium, pyrrolidinium And one or more cations formed, ClO ₄ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ^— and a salt composed of one or more anions selected from the group consisting of. In some embodiments, one or more conventional salts include, but are not limited to, tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), tetrafluoroboric acid 1-ethyl-3-methylimidazolium (EMIBF ₄ ), 1-ethyl-1-methylpyrrolidinium tetrafluoroborate (EMPBF ₄ ), 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ( EMIIm) and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF ₆ ). In some embodiments, one or more conventional salts include, but are not limited to, 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-based salts including bis (pentafluoromethanesulfonyl) imidolithium (Li (CF ₃ CF ₂ SO ₂ ) ₂ N or LiBETI).

  In some embodiments, the electrolyte composition is further comprised of, but 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) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), Vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenyl ethylene carbonate (PhEC), propyl methyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL) ), And γ-valerolactone (GVL).

  In one embodiment, the phosphonium electrolyte composition disclosed herein is applied to the porous electrode and separator prior to cell assembly by any suitable means such as dipping, spraying, screen printing, etc. May be. In another embodiment, the phosphonium electrolyte composition disclosed herein is applied to the porous electrode and separator after cell assembly by any suitable means, such as by using a vacuum injection device. May be. In another embodiment, the phosphonium electrolyte composition disclosed herein may be formed into a polymer gel electrolyte film or membrane. Alternatively, the polymer gel electrolyte may be applied directly to the electrode. Both such free standing gel electrolyte films or gel electrolyte coated electrodes are particularly suitable for high volume and high productivity manufacturing processes such as 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. By using such an electrolyte film as an electrolyte delivery vehicle, the amount and distribution of the electrolyte solution can be precisely controlled, thus improving cell assembly consistency and increasing product yield. In some embodiments, the electrolyte film is described in co-pending patent application 12 / 027,924, filed on Feb. 7, 2008, the entire disclosure of which is incorporated herein by reference. It is composed of a film like

  In some embodiments, the current collector is selected from, but not limited to, one or more of the following: aluminum plate or foil or film, carbon coated aluminum, stainless steel, carbon coating Stainless steel, gold, platinum, silver, highly conductive metal or carbon doped plastic, or combinations thereof.

  In one embodiment, a symmetrical electrode configuration can be provided by fabricating both electrodes 12, 12 'of a single cell EDLC 10 with the same type of active material. Alternatively, the EDLC can have an asymmetric electrode configuration where each electrode is formed of a different type of active material. Symmetric EDLC is the preferred embodiment and is simpler than making an asymmetric EDLC. Symmetric EDLC can also reverse the polarity of the two electrodes, which is a powerful advantage for continuous high performance during long term charge cycling. However, an asymmetric EDLC may be selected if the choice of electrode material is determined by cost and performance.

  In an exemplary embodiment, an EDLC device comprises a pair of porous electrodes made of activated carbon coupled to an aluminum current collector, an NKK cellulose separator sandwiched between two electrodes, and the pores of the separator and electrodes. And the phosphonium electrolyte disclosed herein that penetrates and fills these.

  In another exemplary embodiment, the EDLC is made as a stack of cell components. The electrode active material and binder of activated carbon particles are illustrated in FIGS. 2A and 2B by forming a single-sided electrode by bonding to one side of the current collector, or by bonding to both sides of a “bipolar” current collector. Bipolar or double-sided electrodes as formed are formed. The multi-cell stack places the first NKK cellulose separator on the first single-sided electrode, the first bipolar electrode on the first separator, and the second separator on the first bipolar electrode. Place the second bipolar electrode on the second separator, place the third separator on the second bipolar electrode, place the third bipolar electrode on the third separator, and the third bipolar It is fabricated by placing a fourth separator on top of the electrode and placing a second single-sided electrode on top of the fourth separator to form a 4-cell stack. By first forming a multi-cell module as described above, an EDLC containing more cells can be made. The modules then stack one module on top of another module until the desired number of modules is reached. The electrode / separator / electrode assembly partially seals around the edges. A sufficient amount of the phosphonium electrolyte disclosed herein is added to the assembly such that the separator and electrode pores are filled before the edges are completely sealed.

  In another exemplary embodiment, a spirally wound EDLC is formed. A double-sided electrode similar to the structure illustrated in FIGS. 2A and 2B is formed by adhering an electrode active substance of activated carbon particles and a binder to both sides of the current collector. The electrode / separator stack or assembly is placed on the first Celgard® polypropylene / polyethylene separator, the second separator on the first electrode, and the second separator Made by placing a second electrode on top. The stack is wrapped around a rigid cell core that is either a circular helix to form a cylindrical structure or a flat helix to form a prismatic structure. The stack is then partially sealed at the edges or placed in a can. Sufficient amounts of any of the electrolytes described herein are added to the stack separator and electrode pores prior to final sealing.

  In another exemplary embodiment, the phosphonium electrolyte composition and conductive polymer disclosed herein are used as an electrode active material on one or both electrodes to increase the overall memory density of the device. An EDLC device can also be constructed. The conductive polymer can be selected from any of the classes of conductive organic materials including polyaniline, polypyrrole, and polythiophene. Of particular interest are polythiophenes, such as poly (3- (4-fluorophenyl) thiophene) (PFPT), which are known to have good stability against electrochemical cycling. Can be handled easily.

  In a further exemplary embodiment, an EDLC device is made of a phosphonium electrolyte composition disclosed herein, a cathode (anode) made of high surface area activated carbon, and graphite intercalated with lithium ions. Can be constructed using a modified anode (cathode). The formed EDLC is an asymmetric hybrid capacitor called a lithium ion capacitor (LIC).

  An important requirement for increased energy cycle efficiency and maximum power delivery is a low equivalent series resistance (ESR) of the cell. Therefore, it is useful that the EDLC electrolyte has a high conductivity for ion transport. Surprisingly, when the phosphonium electrolyte composition disclosed herein replaces a conventional electrolyte, as described above, or when a phosphonium salt is used as an additive with a conventional electrolyte, The ionic conductivity is significantly increased and the performance stability of the EDLC device is greatly improved, as can be seen in the examples below.

In one exemplary embodiment, undiluted (neat) phosphonium ionic liquid (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ without solvent is 15.2 mS The ionic conductivity is / cm.

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

In another exemplary embodiment, the phosphonium ionic liquid (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ is mixed in a propylene carbonate (PC) solvent, It exhibits an ionic conductivity of 22 mS / cm at a PC / ionic liquid volume ratio between 0.75 and 1.25.

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

In another exemplary embodiment, a conventional electrolyte solution of 1.0 M LiPF _{6 in} a 1: 1 mixed solvent of EC (ethylene carbonate) and DEC (diethyl carbonate) (denoted as EC: DEC = 1: 1). 10% by weight of phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ is added. With the addition of the phosphonium additive, the ionic conductivity of the electrolyte increases by 109% at -30 ° C and by about 25% at + 20 ° C and + 60 ° C. . In general, the ionic conductivity of conventional electrolyte solutions is increased by at least 25% as a result of the phosphonium additive. .

In a further exemplary embodiment, a 1: 1 mixed solvent ratio of EC (ethylene carbonate), DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) is described as EC: DEC: EMC 1: 1: 1. 10% by weight of phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ is added to 1.0 M LiPF ₆ conventional electrolyte solution. With the addition of the phosphonium additive, the ionic conductivity of the electrolyte increases by 36% at 20 ° C, 26% at 60 ° C, and 38% at 90 ° C. . In general, the ionic conductivity of conventional electrolyte solutions is increased by at least 25% as a result of the phosphonium additive. .

  The separator has been found to be the largest single source of cell ESR. Thus, a suitable separator must have a high ionic conductivity when it is immersed in an electrolyte and has 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 μm thick. In another embodiment, the separator is less than about 30 μm thick. In yet another embodiment, the separator is less than about 10 μm thick.

  Another important advantage of using the novel phosphonium electrolyte compositions disclosed herein as replacements for conventional electrolytes or using phosphonium salts as additives in conventional electrolytes is that they are conventional electrolytes. A broader electrochemical voltage stability window.

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

  In a further exemplary embodiment, the single cell EDLC is composed of two carbon electrodes, a cellulose separator sandwiched between the two electrodes, and various dissolved in propylene carbonate (PC) solvent at a concentration of 1.0M. A phosphonium salt electrolyte solution. In one arrangement, the EDLC can be charged and discharged from 0V to 3.9V. In another arrangement, the EDLC can be charged and discharged from 0V to 3.6V. In another arrangement, the EDLC can charge and discharge from 0V to 3.3V. In further EDLC configurations composed of symmetrical structures, the EDLC should operate between -3.9V and + 3.9V, or between 3.6V and + 3.6V, or between 3.3V and + 3.3V. Can do.

Another important advantage of using the phosphonium electrolyte compositions disclosed herein as replacements for conventional electrolytes, or using phosphonium salts as additives in EDLC conventional electrolytes is that they are conventional electrolytes. It exhibits a lower vapor pressure and thus lower flammability compared to, thus improving the safety of EDLC operation. In one aspect of the invention, when a phosphonium salt is used as an additive with a conventional electrolyte (contains a conventional non-phosphonium salt), the phosphonium salt and the conventional salt are in a phosphonium salt / conventional salt mole in the electrolyte. It exists in the range of 1/100 to 1/1. Examples of 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-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIIm), 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF ₆ ).

In one 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 at a concentration of 1.0 M in a solvent of acetonitrile (ACN). Formed by dissolving. The vapor pressure of ACN decreased by about 39% at 25 ° C and 38% at 105 ° C. Significant suppression of vapor pressure by the phosphonium salt is an advantage in reducing the flammability of the electrolyte solution and thus improving the safety of device operation.

In another exemplary embodiment, a 1.0 M LiPF ₆ conventional electrolyte solution in a 1: 1 mixed solvent of EC (ethylene carbonate) and DEC (diethyl carbonate) (denoted as EC: DEC = 1: 1) is used. Provided by Novolyte Technologies (part of 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 solution in a proportion of 20% by weight. Addition of phosphonium additive to conventional electrolytes reduced self-extinguishing time by 53%. This indicates that the safety and reliability of the energy storage device could be substantially improved by using phosphonium salts as additives in conventional electrolytes.

  A further important advantage of EDLCs formed according to the present invention compared to the prior art is their wide temperature range. As can be seen in the examples below, EDLCs made using the novel phosphonium electrolytes disclosed herein are between about -50 ° C and + 120 ° C, or about -40 ° C. It can operate in a temperature range between ˜ + 105 ° C., or between −20 ° C. and + 85 ° C., or between −10 ° C. and + 65 ° C. Thus, the materials and structures disclosed herein allow EDLCs that can function in an extended temperature range to be made here. This allows these devices to be implemented for a wide range of applications that experience a wide temperature range during fabrication and / or operation.

  In some preferred embodiments, the EDLC is designed to operate at different voltage and temperature combinations. In one arrangement, the EDLC can operate at 2.5V and 120 ° C. In another arrangement, the EDLC can operate at 2.7V and 105 ° C. In another arrangement, the EDLC can operate at 2.8V and 85 ° C. In another arrangement, the EDLC can operate at 3.0V and 70 ° C. In a further arrangement, the EDLC can operate at 3.5V, 60 ° C,

  In a further embodiment, the above approach for energy storage can be combined with a battery to form a capacitor battery hybrid energy storage system including a series of batteries and an EDLC.

Electrolytic Capacitors Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited for electrolytes of electrolytic capacitors. In one embodiment, an electrolytic capacitor is provided that includes an anode, a cathode, a separator between the positive and negative electrodes, and an electrolyte. The electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
An ion comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent Consists of one or more ionic liquids or salts dissolved in a liquid composition or solvent. In one embodiment, the electrolyte is comprised of an ionic liquid having one or more phosphonium-based cations and one or more anions, the ionic liquid composition having a thermodynamic stability of 375 ° C. or less. A liquidus range wider 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 one or more salts dissolved in a solvent having one or more phosphonium-based cations and one or more anions, the electrolyte composition comprising: At room temperature, 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 The ionic conductivity of is shown. In some embodiments, the electrolyte composition is composed of, but 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) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene Carbonate (VC), vinyl ethylene carbonate (VEC), phenyl ethylene carbonate (PhEC), propyl methyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL) , And γ-valerolactone (GVL). In one embodiment, the anode, or anode, is typically an aluminum foil with a thin oxide film formed by electrolytic oxidation or anodization. Aluminum is the preferred metal for the anode, but other metals such as tantalum, magnesium, titanium, niobium, zirconium and zinc may be used. The cathode, or cathode, is usually an etched aluminum foil. In a further aspect, the phosphonium electrolyte exhibits lower flammability compared to conventional electrolytes, thus improving the safety 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 dye-sensitized solar cell (DSSC) electrolytes. In one embodiment, a DSSC is provided that includes an anode to which dye molecules are attached, an electrolyte containing a redox system, and a cathode. The electrolyte has the general formula:
R ¹ R ² R ³ R ⁴ P
An ion comprising one or more phosphonium-based cations and one or more anions, wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituent Consists of one or more ionic liquids or salts dissolved in a liquid composition or solvent. In another embodiment, the electrolyte is characterized as having one or more phosphonium-based cations and one or more anions, and the electrolyte composition comprises at least two or more of the following: Show: thermodynamic stability, low volatility, wide liquid phase range, ionic conductivity, chemical stability, and electrochemical stability. In another embodiment, the electrolyte is characterized as having one or more phosphonium-based cations and one or more anions, and the electrolyte composition has a temperature of about 375 ° C. or higher. Thermodynamic stability up to and ionic conductivity of at least 5 mS / cm, or at least 10 mS / cm, or at least 15 mS / cm.

Electrolytic Films Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited for electrolytic films or electrolyte films. In one embodiment, an electrolytic film is provided that includes a phosphonium ionic liquid composition applied to a substrate. In another embodiment, an electrolytic film is provided that includes a salt dissolved in one or more phosphonium ionic liquids or solvents applied to a substrate. In one example, a coating solution is formed by dissolving one or more phosphonium ionic liquids or salts in a solvent. The solution is applied to the substrate by any suitable means, such as spraying, spin coating, and the like. The substrate is then heated to partially or completely remove the solvent and form an electrolyte or ion conductive film. In other embodiments, a solution of ionic liquid, salt and polymer dissolved in a suitable solvent is coated onto the substrate, such as by spraying or spin coating, and then the solvent is partially or fully evaporated. This results in the formation of an ion conducting polymer gel / film. Such films are particularly suitable for electrolytes for batteries, EDLC and DSSC and fuel cell membranes.

Heat Transfer Medium The desirable properties of the phosphonium ionic liquid of the present invention, high thermodynamic stability, low volatility and wide liquid phase range, are well suited for heat transfer media. Some embodiments of the present invention comprise an ionic liquid composition or one or more salts dissolved in a solvent comprising one or more phosphonium-based cations and one or more anions. A heat transfer medium is provided, the heat transfer medium exhibiting thermodynamic stability at temperatures below about 375 ° C., a liquidus range greater than 400 ° 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, an embedded capacitor has been demonstrated. In one embodiment, the embedded capacitor is comprised of a dielectric disposed between two electrodes, the dielectric comprising an electrolytic film of a phosphonium ion composition as described above. The embedded capacitor of the present invention can be embedded in an integrated circuit package. Further embodiments include the placement of “on-board” capacitors.

  The above description is intended to be illustrative and is not intended to limit the use of these phosphonium ionic liquid electrolyte compositions to the listed uses or processes.

  Embodiments of the present invention will now be described in more detail with reference to specific examples. The examples provided below are intended for illustrative purposes only and are in no way intended to limit the scope and / or teachings of the present invention.

  In general, phosphonium ionic liquids are metathesis reactions of appropriately substituted phosphonium salts with appropriately substituted metal salts, or reactions of appropriately substituted phosphine precursors with appropriately substituted anion precursors. It is prepared by either. FIGS. 3-6 illustrate reaction schemes for making four exemplary embodiments of the phosphonium ionic liquids of the present invention.

(Example 1)
A phosphonium ionic liquid was prepared. AgSO ₃ CF ₃ was charged into a 50 ml round bottom (Rb) flask and attached to a 3 cm swivel frit. The flask was evacuated and brought into the glove box. In the glove box, di-n-propylethylmethylphosphonium iodide was added, the flask was reattached, brought to the vacuum line, degassed, and anhydrous THF was vacuum transferred. The flask was allowed to warm to room temperature and then heated to 40 ° C. for 2 hours. This resulted in the formation of a light green bead-like solid. This solid was removed by filtration. This resulted in a pearly, milky white solution. Volatiles were removed under high vacuum while heating using a 30 ° C. water bath. This produced a white crystalline material with a yield of 0.470 g. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG.

(Example 2)
Additional phosphonium ionic liquids were prepared. Di-n-propylethylmethylphosphonium iodide was charged into a 100 ml Rb flask in the glove box, then removed and dissolved in 50 ml DI H ₂ O. When AgO ₂ CCF ₃ was added to this solution, a yellow bead-like precipitate immediately formed. After stirring for 2 hours, AgI was removed by filtration and the cake was washed 3 times with 5 ml of DI H ₂ O each time. Most of the water was removed on a rotary evaporator. This resulted in a clear, low viscosity liquid which was then dried under high vacuum with heating and stirring. This caused solidification of the material. Mild warming to the white solid in a warm water bath yields a liquid that appears to melt immediately above room temperature. This experiment yielded 0.410 g of material. The reaction scheme is depicted in FIG. 8A. The material was subjected to thermogravimetric analysis (TGA) and evolved gas analysis (EGA) tests, the results of which are shown in FIGS. 8B and 8C, respectively.

(Example 3)
In this example, di-n-propylethylmethylphosphonium iodide was added to a 100 ml Rb flask in the glove box and then removed from the draft chamber and dissolved in 70 ml MeOH. Next, when AgO ₂ CCF ₂ CF ₂ CF ₃ was added, a yellow colored slurry was immediately obtained. After stirring for 3 hours, the solid was removed by filtration, most of the MeOH was removed by evaporation on a total evaporator, and the remaining residue was dried under high vacuum. This gave a yellow, mushy gel-like substance. “Liquid” type crystals were observed to form on the sides of the Rb flask and then “melted” out by rubbing the flask. This experiment yielded 0.618 g of material. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG. 9A. Evolved gas analysis (EGA) was also performed and the results are shown in FIG. 9B.

(Example 4)
The pressure flask was brought into the glove box and charged with 0.100 g of P (CH ₂ OH) ₃ followed by 5 mL of THF-d8. When the solid dissolved, Me ₂ SO ₄ was added. The flask was then sealed and removed from the glove box. This was heated in a 110 ° C. oil bath for 10 minutes, then cooled, returned to the glove box, and a ¹ mL aliquot was removed for ¹ H NMR. The reaction scheme is illustrated in FIG. 10A. ^{The 1} H NMR spectrum is shown in FIG. 10B.

(Example 5)
In this experiment, 1-ethyl-1-methylphosphoranium nitrate was added to a 100 ml 14/20 Rb flask in a glove box. To this was added KC (CN) ₃ and then this Rb was attached to a 3 cm swivel frit. This frit was brought into the line and CHCl ₃ was vacuum transferred. The flask was allowed to stir for 12 hours. A sticky brown material was observed at the bottom of the flask. Filtration of the solution gave a pearly, milky filtrate from which the brown oil was separated. The brown material was washed twice with recycled CHCl ₃ to become whiter and more granular. All volatile components were removed under high vacuum to give a low viscosity brown oil. This experiment yielded 1.52 g of material. The reaction scheme is shown in FIG. 11A. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG. 11B.

(Example 6)
In this experiment, 1-ethyl-1-methylphosphorinanium iodide was added to a 100 ml Rb flask in a glove box and then brought into a draft chamber where it was dissolved in 70 ml MeOH. Then, when AgO ₂ CCF ₂ CF ₂ CF ₃ was added, 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 evaporation on a rotary evaporator and the residue was dried under high vacuum. This procedure gave an off-white, pale yellow colored solid. This experiment yielded 0.620 g of material. A thermogravimetric analysis (TGA) was performed on this 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 the draft chamber, then dissolved in water and stirred. When AgO ₃ SCF ₃ was added, a yellow precipitate immediately formed. The flask was stirred for 2 hours and then vacuum filtered. A solution formed during filtration and milky material was observed after filtration. This material was evaporated by rotary evaporator and the residue was dried under vacuum on an oil bath to melt the solid. This experiment yielded 0.490 g of material. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG.

(Example 8)
In further experiments, 1-butyl-1-ethyl phosphorinanium iodide was added to the flask in the draft chamber. MeOH was added and the flask was then stirred for 15 minutes. Silver p-toluenesulfonate was added. The flask was stirred for 4 hours. A yellow precipitate was formed. This material was gravity filtered and then evaporated on a rotary evaporator. This material was dried under vacuum to yield a liquid. This experiment yielded 0.253 g of material. The reaction scheme is shown in FIG. 14A. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG. 14B.

(Example 9)
In another experiment, 250 mg (0.96 mmol) of triethylmethylphosphonium iodide is added to 15 mL of deionized water followed by 163 mg (0.96 mmol) of silver nitrate previously dissolved in 5.0 mL of deionized water. The reaction is stirred for 10 minutes, at which point the white to yellow precipitate is filtered off. The solid is then washed with 5.0 mL deionized water and the aqueous fractions are combined. Removal of the water on a rotary evaporator under vacuum leaves a white solid residue which is recrystallized from a 3: 1 mixture of ethyl acetate and acetonitrile to give triethylmethylphosphonium nitrate. Yield: 176 mg, 94%. Phosphonium nitrate (176 mg, 0.90 mmol) is dissolved in 5 mL anhydrous acetonitrile. 113 mg (0.90 mmol) potassium tetrafluoroborate dissolved in 5 mL anhydrous acetonitrile is added to the phosphonium salt and after stirring for 5 minutes, the solid is removed by filtration. The solvent is removed on a rotary evaporator and the resulting off-white solid is recrystallized from hot 2-propanol to give pure trifluoromethylphosphonium tetrafluoroborate in the analysis. Yield: 161 mg, 81%. The composition is confirmed by the ¹ H NMR spectrum as shown in FIG. 15A and by the ³¹ P NMR spectrum shown in FIG. 15B. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG.

(Example 10)
In another experiment, 250 mg (1.04 mmol) triethylpropylphosphonium bromide and 135 mg (1.06 mmol) potassium tetrafluoroborate were combined in 10 mL acetonitrile. A fine white precipitate of KBr began to form immediately. The mixture was stirred for 1 hour, filtered, and the solvent was removed on a rotary evaporator to produce a white solid. Yield: 218 mg, 85%. By recrystallizing this crude product from 2-propanol, pure material can be produced in the analysis. The composition is confirmed by the ¹ H NMR spectrum as shown in FIG. 17A and by the ³¹ P NMR spectrum shown in FIG. 17B. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG.

(Example 11)
In further experiments, the reaction was carried out in a glove box under a nitrogen atmosphere. 1.00 g of triethylpropylphosphonium iodide, 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 constant stirring. A silver iodide white precipitate formed immediately and the reaction was stirred for 5 min. The precipitate was filtered and washed several times with anhydrous CH ₃ CN. The filtrate was removed 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 μm PTFE membrane. Cooling the filtrate gave white crystals that were collected by filtration. Yield: 744 mg, 70%. The composition is confirmed by the ¹ H NMR spectrum as shown in FIG. 19A and by the ³¹ P NMR spectrum shown in FIG. 19B. A thermogravimetric analysis (TGA) was performed on this material and the results are shown in FIG.

(Example 12)
In this example, (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 in} a molar ratio of 1: 3: 1 PCF ₃ BF ₃ / (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) A ternary phosphonium ionic liquid composition containing PCF ₃ BF ₃ is converted into (CH ₃ CH ₂ CH ₂ ) (CH ₃ Compared to a one-component composition comprising CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ . Differential scanning calorimetry (DSC) was performed on this material and the results are shown in FIG. 21A for a one-component composition and FIG. 21B for a ternary composition. As illustrated in FIGS. 21A and 21B, the ternary composition exhibits the advantage of a lower freezing temperature and thus a larger liquid phase range compared to the one-component composition.

(Example 13)
In another experiment, the phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was prepared. This salt has a low viscosity of 19.5 cP at 25 ° C, a melting point of -10.0 ° C, an onset decomposition temperature of 396.1 ° C, a liquid range of 407 ° C, an ionic conductivity of 15.2 mS / cm, and a Pt working electrode and a Pt counter electrode and When measured in an electrochemical cell with an Ag / Ag ⁺ reference electrode, an electrochemical voltage window of -1.5V to + 1.5V is shown. The results are summarized in Table 14 below.

(Example 14)
In another experiment, the 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) having an ACN / salt volume ratio ranging from 0-4. The ionic conductivity of the produced electrolyte solution was measured at room temperature, and the result is shown in FIG. As FIG. 22 shows, the ACN / salt ratio increases from 13.9 mS / cm at zero ratio (undiluted ionic liquid) to a peak value of 75 mS / cm at a ratio between 1.5 and 2.0, Ionic conductivity is increasing.

(Example 15)
In another experiment, the phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was prepared. Salt was dissolved in propylene carbonate (PC) solvent with PC / salt volume ratio in the range of 0-2.3. The ionic conductivity of the produced electrolyte solution was measured at room temperature, and the result is shown in FIG. As FIG. 23 shows, the PC / salt ratio increased from 13.9 mS / cm at zero ratio (undiluted ionic liquid) to a peak value of 22 mS / cm at a ratio between 0.75 and 1.25 and ion conduction The rate is increasing.

(Example 16) to (Example 35)
In further experiments, various phosphonium salts were prepared. An electrolyte solution was formed at a concentration of 1.0M by dissolving the salt in a solvent of acetonitrile (ACN). The ionic conductivity of the produced electrolyte solution was measured at room temperature. The electrochemical voltage stability window (Echem Window) was determined in an electrochemical cell with a Pt working electrode and a Pt counter electrode and an Ag / Ag + reference electrode. The results are summarized in Table 15. The electrolyte exhibited an ionic conductivity at room temperature 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. In one arrangement, the electrochemical window was between about -3.2V and + 2.4V. In another arrangement, the electrochemical window was between about -3.0V to + 2.4V. In yet another arrangement, the electrochemical window was between about -2.0V and + 2.4V.

(Example 36) to (Example 41)
In further experiments, various phosphonium salts were prepared and compared to the ammonium salt as a control. An electrolyte solution was formed at a concentration of 1.0 M by dissolving the salt in a solvent of propylene carbonate (PC). The ionic conductivity of the produced electrolyte solution was measured at room temperature. The electrochemical window was determined with an electrochemical cell having a Pt working electrode and a Pt counter electrode and an Ag / Ag + reference electrode. The results are summarized in Table 16. Here we demonstrate that phosphonium salts exhibit higher conductivity and a broader electrochemical voltage stability window compared to the control ammonium analog. In one arrangement, the Echem Window was between about -2.4V to + 2.5V. In another arrangement, the Echem Window was between about -1.9V and + 3.0V.

(Example 42) to (Example 45)
In further experiments, various phosphonium salts were prepared and compared to the ammonium salt as a control. Electrolyte solutions were formed at concentrations ranging from 0.6 M to 5.4 M by dissolving the salt in a solvent of propylene carbonate (PC). The ionic conductivity of the resulting electrolyte solution was measured at room temperature and the results are presented in FIG. The conductivity values at a concentration of 2.0M are shown in Table 17, which explains that the phosphonium salt exhibits a higher conductivity compared to the control ammonium analog. Yes.

Example 46
In another experiment, the phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was prepared and the ammonium salt (CH ₃ CH ₂ ) ₃ (CH ₃ ) as a control. Compared to NBF ₄ . An electrolyte solution was formed at a concentration of 1.0 M by dissolving these salts in a solvent of acetonitrile (ACN). The vapor pressure of the solution was measured by pressurized differential scanning calorimetry (DSC) at a temperature of 25-105 ° C. The ionic conductivity of the produced electrolyte solution was measured at room temperature. As illustrated in FIG. 25, the vapor pressure of ACN is reduced by 39% for phosphonium salts compared to 27% for ammonium salts at 25 ° C and compared to 13% for ammonium salts at 105 ° C. The phosphonium salt is 38% lower. Significant suppression of vapor pressure by phosphonium salts is an advantage in reducing the flammability of the electrolyte solution and thus improving the safety of EDLC operation.

(Example 47) to (Example 50)
In another experiment, phosphonium salts were used as additives in conventional electrolyte solutions for lithium batteries. In one embodiment of the present invention, a conventional electrolyte solution of 1.0 M LiPF _{6 in} a 1: 1 mixed solvent of EC (ethylene carbonate) and DEC (diethyl carbonate) (described as EC: DEC 1: 1) Provided by Novolyte Technologies (part of BASF group). 20% by weight of phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was added to the conventional electrolyte solution. In another embodiment of the present invention, a 1: 1 mixed solvent ratio of EC (ethylene carbonate), DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) (EC: DEC: EMC 1: 1: 1) Description) A conventional electrolyte solution of 1.0M LiPF ₆ was provided by Novolyte Technologies (part of BASF group). 10% by weight of phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ was added to the conventional electrolyte solution. A self-extinguishing test was performed by placing a 1 g sample of the electrolyte solution in a glass petri dish, igniting the sample, and recording the time required to extinguish the flame. The self-extinguishing time (SET) is normalized with respect to the sample mass. The results are summarized in Table 18 below. Phosphonium additives at concentrations between 10-20% by weight reduced the self-extinguishing time by 33-53%. This indicates that the safety and reliability of a lithium ion battery can be substantially improved by using a phosphonium salt as an additive in a conventional lithium ion electrolyte.

(Example 51)
In another experiment, phosphonium salts were used as additives in standard electrolyte solutions for lithium batteries. In one embodiment of the present invention, a standard electrolyte solution of 1.0 M LiPF _{6 in} a 1: 1 mixed solvent of EC (ethylene carbonate) and DEC (diethyl carbonate) (denoted as EC: DEC 1: 1) is , Provided by Novolyte Technologies (part of BASF Group). 10% by weight of phosphonium salt (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PC (CN) ₃ was added to the standard electrolyte solution. The ionic conductivity of both the standard electrolyte solution and the solution with phosphonium additive was measured at different temperatures from -30 to + 60 ° C. As illustrated in FIG. 26, the phosphonium additive improves the ionic conductivity of the electrolyte solution over a wide temperature range. At −30 ° C., the ionic conductivity is increased by 109% as a result of the phosphonium additive. . At + 20 ° C., the ionic conductivity is increased by 23% as a result of the phosphonium additive. . At + 60 ° C., the ionic conductivity is increased by about 25% as a result of the phosphonium additive. . In general, the ionic conductivity of standard electrolyte solutions is increased by at least 25% as a result of the phosphonium additive. .

(Example 52)
In another experiment, phosphonium salts were used as additives in standard electrolyte solutions for lithium batteries. In one embodiment of the present invention, a 1: 1 mixed solvent ratio of EC (ethylene carbonate), DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) is described as EC: DEC: EMC 1: 1: 1. A standard electrolyte solution of 1.0M LiPF ₆ was provided by Novolyte Technologies (part of BASF group). 10% by weight of 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 solution. The ionic conductivity of both the standard electrolyte solution and the solution with phosphonium additive was measured at different temperatures of 20-90 ° C. As illustrated in FIG. 27, the phosphonium additive improves the ionic conductivity of the electrolyte solution over a wide temperature range. At 20 ° C., the ionic conductivity is increased by about 36% as a result of the phosphonium additive. . At 60 ° C., the ionic conductivity is increased by about 26% as a result of the phosphonium additive. . At 90 ° C., the ionic conductivity is increased by about 38% as a result of the phosphonium additive. . In general, the ionic conductivity of standard electrolyte solutions is increased by at least 25% as a result of the phosphonium additive. .

(Example 53)
In further experiments, as illustrated in FIG. 28, a coin cell is composed of two 14 mm diameter disk-like carbon electrodes, a 19 mm diameter separator sandwiched between the two electrodes, and an impregnating electrolyte solution. Composed. In one embodiment of the present invention, two carbon electrodes with a thickness of 100 μm are prepared from activated carbon (Kuraray, YP-50F, 1500-1800 m ² / g), mixed with a binder, each 30 μm thick aluminum Combined with current collector. The separator was prepared from a 35 μm NKK cellulose separator (TF40-35). An electrolyte solution containing 1.0 M phosphonium salt in either acetonitrile or propylene carbonate was impregnated on both the carbon electrode and the separator. This assembly was placed in a 2032 coin cell case and sealed by applying an appropriate pressure using a crimper. The completed cell had a diameter of 20 mm and a thickness of 3.2 mm. The entire assembly process was performed in a glove box filled with nitrogen. The completed cell was characterized with a CHI constant potential electrolyzer by charging and discharging with constant current. FIG. 29 shows a charge / discharge curve for such a coin cell having 1.0 M (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in a propylene carbonate electrolyte. The cell was initially charged from 0V to 2.5V and then discharged to 1.0V at 10mA. The cell capacitance was determined to be 0.55F.

(Example 54) to (Example 57)
In further experiments, as illustrated in FIGS. 30A and 30B, the pouch cell is composed of two 15 mm × 15 mm carbon electrodes, a 20 mm × 20 mm separator sandwiched between the two electrodes, and an impregnating electrolyte solution. The In some cases, the pouch cell includes a reference electrode such as a third electrode-silver electrode so that a potential can be determined at each carbon electrode. In one embodiment of the present invention, two carbon electrodes with a thickness of 100 μm are prepared from activated carbon (Kuraray, YP-50F, 1500-1800 m ² / g), mixed with a binder, each 30 μm thick aluminum Combined with current collector. A separator was prepared from a 35 μm NKK cellulose separator (TF40-35). An electrolyte solution containing 1.0 M phosphonium salt in either acetonitrile or propylene carbonate was impregnated on both the carbon electrode and the separator. When this assembly was aligned, leakage around the tabs was prevented by using hot melt adhesive tape to bring the two current collector tabs together. The assembly was then vacuum sealed in an aluminum laminate pouch bag. The completed cell had dimensions of 70 mm x 30 mm and a thickness of 0.3 mm. The entire assembly process was performed in a glove box filled with nitrogen. The completed cell was characterized with a CHI constant potential electrolyzer by charging and discharging at a constant current density. FIG. 31A shows a charge / discharge curve for 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 between 0 and 2.7 V at 10 mA. FIG. 31B shows the resolved electrode potentials at the anode and cathode carbon electrodes measured with the silver reference electrode. In some cases, pouch cells could be fully charged to voltages as high as 3.9V. The results are summarized in Table 19 below. In one arrangement, the EDLC can be charged and discharged from 0V to 3.9V. In another arrangement, the EDLC can be charged and discharged from 0V to 3.6V. In another arrangement, the EDLC can be charged and discharged from 0V to 3.3V.

(Example 58)
In a further experiment, as illustrated in FIG. 32, a cylindrical cell consists of a 6 cm × 50 cm first separator strip and a 5.8 cm × 50 cm first carbon placed on top of the first separator. Consists of an electrode strip, a 6 cm x 50 cm second separator strip placed over the first carbon electrode, and a 5.8 cm x 50 cm second carbon electrode strip placed over the second separator Is done. The electrode / separator assembly was wound in a jelly roll form around a rigid cell core. In one embodiment of the present invention, a 100 μm thick carbon electrode was prepared from activated carbon (Kuraray, YP-50F, 1500-1800 m ² / g), mixed with a binder, and a 30 μm thick aluminum current collector. As a result, a double-sided electrode structure was formed. A separator was prepared from a 35 μm NKK cellulose separator (TF40-35). The jelly roll core was placed in an 18650 cylindrical cell case. By adding an electrolyte solution containing 1.0M phosphonium salt in either acetonitrile or propylene carbonate using a vacuum injector, the electrolyte penetrates into and completely fills the pores of the separator and the carbon electrode. I made sure. After filling the electrolyte, the cell was closed with a cap. The dimensions of the completed cylindrical cell were 18 mm in diameter and 65 mm in length. The entire assembly process was performed in a dry room or a nitrogen filled glove box. The completed cell was characterized by a PAR, VersaSTAT4-200 constant potential electrolyzer by charging and discharging with constant current. FIG. 33 shows the charge-discharge curve for such a cylindrical cell with an electrolyte solution of 1M (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ CF ₃ F ₃ in such propylene carbonate. Is shown. The cell was first charged from 1.0 V to 2.5 V, held at 2.5 V for 300 seconds, and then discharged to 2.5 V at 600 mA. The cell capacitance was determined to be 132F.

(Example 59) to (Example 61)
In a further experiment, an accelerated stress test was performed on pouch cells containing 1.0 M phosphonium salt in propylene carbonate at 2.7 V and 70 ° C. compared to the ammonium salt as a control. Cell performance stability was measured as the initial capacitance retention. The results are shown in FIG. Capacitance retention values at 80 hours are shown in Table 20 and illustrate that cells with phosphonium salts show higher retention rates compared to cells with ammonium salts.

(Example 62)
In further experiments, containing electrolyte solutions of 1.0M phosphonium salt- (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ PCF ₃ BF ₃ at different temperatures from -40 ° C to + 80 ° C The pouch cell was tested for cell performance as compared to a pouch cell with an ammonium salt- (CH ₃ CH ₂ ) ₃ (CH ₃ ) NBF ₄ electrolyte solution as a control. Cell performance stability was measured as capacitance retention at 25 ° C. As illustrated in FIG. 35, the cell with the phosphonium salt shows a higher retention at a temperature below 0 ° C. compared to the cell with the ammonium salt. As can be appreciated, EDLCs made using the novel phosphonium electrolytes disclosed herein can operate in a temperature range between -40 ° C and + 80 ° C. It is expected that EDLCs made with the phosphonium electrolytes disclosed herein can operate in a temperature range between about −50 ° C. and + 120 ° C. Thus, it is now possible to make EDLCs that can function over an extended temperature range using the materials and structures disclosed herein. This allows these devices to be introduced into a wide range of applications that are subject to a wide temperature range during fabrication and / or operation.

  The present invention should not be limited in scope by the specific embodiments disclosed in the examples, which are intended as illustrations of several aspects of the invention, and Any equivalent embodiment is within the scope of the present invention. Indeed, various modifications of the invention in addition to those shown and described herein will be apparent to those skilled in the art and are intended to be within the scope of the claims appended hereto.

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

10 Single cell battery
12 Anode
12 'cathode
14 Current collector
14 'current collector
16 Separation film or membrane
18 Electrolyte solution
20 Bipolar arrangement
22 Anode
24 cathode
26 “Bipolar” current collector
30 Multi-cell battery
32 unit cells
34 unit cells
36 unit cells
38 unit cells

Claims (45)

The anode,
A cathode,
A separator between the first electrode and the second electrode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises one or more phosphonium ionic liquids, or one or more phosphonium salts dissolved in a solvent;
The one or more phosphonium ionic liquids or phosphonium salts have the formula:
R ¹ R ² R ³ R ⁴ P
(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group)
An electrochemical double layer capacitor (EDLC) comprising one or more phosphonium-based cations and one or more anions. The electrochemical double layer capacitor (EDLC) according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 4 carbon atoms. R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group composed of 1 to 4 carbon atoms, and at least 2 of R ¹ , R ² , R ³ and R ⁴ The electrochemical double layer capacitor (EDLC) according to claim 1, wherein one of them is the same and none of R ¹ , R ² , R ³ and R ⁴ has oxygen. The electrochemical double layer capacitor of claim 1, wherein one or more of the hydrogen atoms in one or more of the R ¹ , R ² , R ³ and R ⁴ groups are substituted with fluorine. (EDLC).   2. The electrochemical double layer capacitor (EDLC) according to claim 1, wherein any one or more of the phosphonium salts may be liquid or solid at a temperature of 100 ° C. or lower.   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein at least one of the phosphonium ionic liquid or the phosphonium salt is composed of a pair of one cation and one anion.   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein at least one of the phosphonium ionic liquid or the phosphonium salt is composed of one anion and a plurality of cations.   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein at least one of the phosphonium ionic liquid or the phosphonium salt is composed of one cation and a plurality of anions.   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein at least one of the phosphonium ionic liquid or the phosphonium salt is composed of a plurality of cations and a plurality of anions. Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2 CH 2} ) 2 (CH 3 CH 2) (CH 3) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2 CH 2} ) (CH 3 CH 2) (CH 3) 2 composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2) 3} (CH 3) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2 CH 2} ) (CH 3 CH 2) 3 composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the formula: (CH ₃ CH _{2) 4} composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2 CH 2} ) 3 (CH 3) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CH 3 CH 2 CH 2} ) 3 (CH 3 CH 2) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CF 3 CH 2 CH 2} ) (CH 3 CH 2) 3 composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CF 3 CH 2 CH 2} ) 3 (CH 3 CH 2) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CF 3 CH 2 CH 2} ) 3 (CH 3) composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). Phosphonium based cation is comprised of the _{formula: (CF 3 CH 2 CH 2} ) 4 composed of P ^+, the electrochemical double layer capacitor of claim 1 (EDLC). The electrolyte composition comprises phosphonium cation, 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 And / or an anion selected from the group consisting of H or F). One or more _{^{anions, - 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 -, _2. The electrochemical double layer capacitor (EDLC) according to claim 1, comprising any one or more of (CF ₃ ) ₃ BF ⁻ , CF ₃ CF ₂ BF ₃ ⁻ , ^and —N (CN) _2. ).   The electrolyte composition comprises phosphonium salt, acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl. Carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenyl ethylene carbonate (PhEC), propyl methyl carbonate (PMC) ), Diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL), γ-valerolactone (GVL), or a mixture thereof. The electrochemical double layer capacitor (EDLC) according to claim 1, comprising: The electrolyte composition includes a 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 a 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 -, _{2. The} electrochemical double layer capacitor (EDLC) according to claim 1, which is composed of (CF ₃ SO ₂ ) ₂ N ⁻ or any one or more anions of these combinations. The electrolyte composition includes a phosphonium salt, the phosphonium salt being a cation of the formula: (CH ₃ ) (CH ₃ CH ₂ ) ₃ P and the 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 an electrochemical double layer capacitor (EDLC) according to claim 1, wherein the electrochemical double layer capacitor is composed of one or more anions of these or combinations thereof. The electrolyte composition includes a phosphonium salt, the phosphonium salt being a cation of the formula: (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₃ P ⁺ and the 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. The} electrochemical double layer capacitor (EDLC) according to claim 1, which is composed of any one or more anions of ₂ N ⁻ or a combination thereof. The electrolyte composition includes a phosphonium salt, the phosphonium salt being a cation of the formula: (CH ₃ CH ₂ ) ₄ P ⁺ and the 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 their The electrochemical double layer capacitor (EDLC) according to claim 1, which is composed of any one or more anions of the combination.   The anode active material and the cathode active material are carbon black, graphite, graphene, carbon-metal composite material, polyaniline, polypyrrole, polythiophene, lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium, respectively. The electrochemistry of claim 1, selected from the group consisting of oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides, and combinations thereof. Double layer capacitor (EDLC).   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein the anode active material and the cathode active material are the same.   The electrochemical double layer capacitor (EDLC) according to claim 1, wherein the anode active material and the cathode active material are different.   The electrochemical double layer capacitor (EDLC) of claim 1, wherein the electrolyte composition further comprises one or more conventional, non-phosphonium salts.   The phosphonium-based ionic liquid or salt and the conventional salt are present in the electrolyte composition in a phosphonium-based ionic liquid or salt: conventional salt molar ratio ranging from 1: 100 to 1: 1. Electrochemical double layer capacitor (EDLC). One or more conventional salts are tetraethylammonium tetrafluoroborate (TEABF ₄ ), triethylmethylammonium tetrafluoroborate (TEMABF ₄ ), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ) 32, selected from the group consisting of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIIm), and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF ₆ ). Electrochemical double layer capacitor (EDLC) described in 1. The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises one or more phosphonium ionic liquids, or one or more phosphonium salts dissolved in a solvent;
The one or more phosphonium ionic liquids or phosphonium salts have 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 and x + y ≦ 4)
One or more cations of
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 and x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (where n = 0 to 2 and 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 = 1-3, y = 0-4, 2x + y ≦ 6)
An electrochemical double layer capacitor (EDLC) comprising one or more anions of: The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises one or more phosphonium ionic liquids, or one or more phosphonium salts dissolved in a solvent;
The one or more phosphonium ionic liquids or phosphonium salts have 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 Yes, x + y ≦ 2)
One or more cations of
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 and x = 0 to 4)
(-OCO (CH ₂ ) _n COO-) (CF ₃ ) _x BF _2-x (where n = 0 to 2 and 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 = 1-3, y = 0-4, 2x + y ≦ 6)
An electrochemical double layer capacitor (EDLC) comprising one or more anions of:   35. The electrochemical double layer capacitor (EDLC) of claim 34, wherein one or more of the hydrogen atoms in the one or more cations or anions are substituted with fluorine.   36. The electrochemical double layer capacitor (EDLC) of claim 35, wherein one or more of the hydrogen atoms in the one or more cations or anions are substituted with fluorine. The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises a phosphonium salt dissolved in a solvent;
The phosphonium salt is
(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 ) Cations composed of (CH ₃ CH ₂ ) ₂ (CH ₃ ) P and formulas: 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 one or more anions of these combinations An electrochemical double layer capacitor (EDLC) consisting of ^{_{Anion, [BF 4 -]: [}} CF 3 BF 3 -] concentration of the molar ratio and 100 / 1-1 / 1 in the range of, BF ₄ ^- and CF ₃ BF ₃ ^- consists of a mixture of, claims Item 39. An electrochemical double layer capacitor (EDLC) according to Item 38. ^{_{Anion, [PF 6 -]: [}} CF 3 BF 3 -] concentration of the molar ratio and 100 / 1-1 / 1 in the range of, PF ₆ ^- and CF ₃ BF ₃ ^- consists of a mixture of, claims Item 39. An electrochemical double layer capacitor (EDLC) according to Item 38. 39. The anion is comprised of a mixture of PF ₆ ⁻ and BF ₄ ⁻ with a molar ratio of [PF ₆ ⁻ ]: [BF ₄ ⁻ ] and a concentration in the range of 100/1 to 1/1. Electrochemical double layer capacitor (EDLC). The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises a phosphonium salt dissolved in a solvent;
The phosphonium salt is
(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 ) a cation composed of (CH ₃ CH ₂ ) ₂ (CH ₃ ) P and
CF ₃ BF ₃ ^- including in configured anion, electrochemical double layer capacitors (EDLC). The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition includes a phosphonium salt dissolved in a phosphonium solvent, the salt comprising:
(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 ) a cation composed of (CH ₃ CH ₂ ) ₂ (CH ₃ ) P and
BF ₄ ^- containing constituted anions, electrochemical double layer capacitors (EDLC). The anode,
A cathode,
A separator between the anode and the cathode;
An electrochemical double layer capacitor (EDLC) comprising an anode, a cathode, and an electrolyte composition in contact with the separator,
The electrolyte composition comprises a phosphonium salt dissolved in a solvent;
The phosphonium salt has a molar ratio of 1: 3: 1 (CH ₃ CH ₂ CH ₂ ) (CH ₃ ) ₃ P / (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) (CH ₃ ) ₂ P / ( A cation composed of (CH ₃ CH ₂ CH ₂ ) (CH ₃ CH ₂ ) ₂ (CH ₃ ) P and
PF ₆ ^- containing constituted anions, electrochemical double layer capacitors (EDLC).   A hybrid energy storage system comprising an array of electrochemical double layer capacitors (EDLCs) according to claim 1 and an array of batteries.

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