Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
  • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the invention generally encompasses electrolyte compositions based on phosphonium ionic liquids, salts, compositions and their use in many applications, including but not limited to: as electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory, as electrolytes in energy storage devices such as batteries, electrochemical double layer capacitors (EDLCs) or supercapacitors or ultracapacitors, electrolytic capacitors, as electrolytes in dye-sensitized solar cells (DSSCs), as electrolytes in fuel cells, as a heat transfer medium, high temperature reaction and/or extraction media, among other applications.
• electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory
• energy storage devices such as batteries, electrochemical double layer capacitors (EDLCs) or supercapacitors or ultracapacitors
• electrolytic capacitors as electrolytes in dye-sensitized solar cells (DSSCs), as electrolytes in fuel cells, as a heat transfer medium, high temperature reaction and/or extraction media, among other applications.
• the invention relates to phosphonium ionic liquids, salts, compositions and molecules possessing structural features, wherein the compositions exhibit desired combination of at least two or more of: thermodynamic stability, low volatility, wide liquidus range, and ionic conductivity.
• the invention further encompasses methods of making such phosphonium ionic liquids, salts, compositions and molecules, and operational devices and systems comprising the same.
• Ionic liquids have received significant attention due in part to their wide potential use and application.
• the term "ionic liquid” is commonly used for salts whose melting point is relatively low (at and below 100 °C). Salts that are liquid at room temperature are commonly called room-temperature ionic liquids.
• Early investigators employed ionic liquids based on dialkylimidazolium salts. For example, Wilkes et. al developed ionic liquids based on dialkylimidazolium salts for use with an aluminum metal anode and chlorine cathode in an attempt to create a battery. J Wilkes, J. Levisky, R. Wilson, C. Hussey, Inorg. Chem, 21, 1263 (1982).
• ionic liquids are based on pyridinium salts, with N- alkylpyridinium and ⁇ , ⁇ '-dialkylimidazolium finding significant use.
• Pyridinium based ionic liquids including N-alkyl- pyridinium and N,N-dialkylimidazolium, and nitrogen-based ionic liquids generally possess thermodynamic stabilities limited to 300 °C , or less, are readily distillable, and tend to have measurable vapor pressures at temperatures significantly less than 200 °C. Such properties limit their usefulness, as well as their applications.
• such ionic liquids are susceptible to decomposition during back end of line (BEOL) thermal processing. Additionally, such ionic liquids are also decomposed during other heat-transfer processing steps which often subject the ionic liquids to continuous thermal cycling to temperatures exceeding 300 °C.
• BEOL back end of line
• the invention broadly encompasses phosphonium ionic liquids, salts, compositions and their use in many applications, including but not limited to: as electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory, as electrolytes in energy storage devices such as batteries, electrochemical double layer capacitors (EDLCs) or supercapacitors or ultracapacitors, electrolytic capacitors, as electrolytes in dye-sensitized solar cells (DSSCs), as electrolytes in fuel cells, as a heat transfer medium, high temperature reactions and/or extraction media, among other applications.
• electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory
• energy storage devices such as batteries, electrochemical double layer capacitors (EDLCs) or supercapacitors or ultracapacitors
• electrolytic capacitors as electrolytes in dye-sensitized solar cells (DSSCs), as electrolytes in fuel cells, as a heat transfer medium, high temperature reactions and/or extraction media, among other applications.
• the invention relates to phosphonium ionic liquids, salts, compositions and molecules possessing structural features, wherein the compositions exhibit desired combinations of at least two or more of: thermodynamic stability, low volatility, wide liquidus range and ionic conductivity.
• an ionic liquid composition comprising: one or more phosphonium based cations of the general formula:
• R ! R 2 R 3 R 4 P wherein: R ! , R 2 , R 3 and R 4 are optional and each independently a substituent group; and one or more anions. In some embodiments R ! , R 2 , R 3 and R 4 are each independently a different alkyl
• R 1 2 3 group comprised of 2 to 14 carbon atoms.
• at least one of R', R , R J and R 4 is an aliphatic, heterocyclic moiety.
• at least one of R', R 2 , R 3 and R 4 is an aromatic, heterocyclic moiety.
• R 1 and R 2 are the same and are comprised of: tetramethylene phospholane, pentamethylele phosphorinane, tetramethinyl phosphole, phospholane or phosphorinane.
• R 2 , R 3 and R 4 are the same and are comprised of: phospholane, phosphorinane or phosphole.
• an ionic liquid composition comprising one or more phosphonium based cations, and one or more anions, wherein the ionic liquid
• composition exhibits thermodynamic stability greater than 375 °C, a liquidus range greater than 400 °C, and ionic conductivity up to 10 mS/cmat room temperature.
• the invention encompasses electrolyte compositions comprised of phosphonium based cations with suitable anions.
• electrolyte or “electrolyte solution” or “electrolyte composition” or “ionic electrolyte” or “ion conducting electrolyte” or “ion conducting composition” or “ionic composition” is used and is herein defined 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 salts dissolved in at least one solvent together with at least one polymer to form a gel electrolyte.
• the one or more salts are defined to include: (a) one or more salts that are a solid at a temperature of 100 °C and below, and (b) one or more salts that are a liquid at a temperature of 100 °C and below.
• electrolyte compositions are provided and are comprised of : one or more salts dissolved in a solvent, the one or more salts comprising one or more phosphonium based cations of the general formula: R ! R 2 R 3 R 4 P (1) and one or more anions, and wherein: R 1 , R 2 , R 3 and R 4 are each independently a substituent group, such as but not limited to an alkyl group as described below.
• R ! , R", R J and R are each independently an alkyl group comprised of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. Any one or more of the salts may be liquid or solid at a temperature of 100 °C and below.
• a salt is comprised of one cation and one anion pair. In other embodiments, a salt is comprised of one cation and multiple anions. In other embodiments, a salt is comprised of one anion and multiple cations. In further embodiments, a salt is comprised of multiple cations and multiple anions.
• the electrolyte composition further comprises one or more conventional, non-phosphonium salts.
• the electrolyte composition may be comprised of conventional salts, and wherein the phosphonium based ionic liquids or salts disclosed herein are additives.
• electrolyte composition is comprised of phosphonium based ionic liquids or salts and one or more conventional salts, present at a mole (or molar) ratio in the range of 1 : 100 to 1 : 1, phosphonium based ionic liquid or salt:
• conventional salt examples include but are not limited to salts which are comprised of one or more cations selected from the group consisting of:
• the one or more conventional salts include but not limited to: tetraethyl ammonium tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride tetrafluoride
• EMIIm bis(trifluoromethanesulfonyl)imide
• the one or more conventional salts are lithium based salts including but not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate or lithium triflate (LiCF 3 S0 3 ), lithium bis(trifluoromethanesulfonyl)imide (Li(CF 3 S0 2 ) 2 N or Lilm), and lithium lithium based salts including but not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate or lithium triflate (LiCF 3 S0 3 ), lithium bis
• Li(CF3CF 2 S0 2 ) 2 N or LiBETI bis(pentafluoromethanesulfonyl)imide
• a battery comprising: a positive electrode, a negative electrode, a separator between said positive and negative electrode; and an electrolyte.
• the electrolyte is comprised of an ionic liquid composition or one or more salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• the electrolyte is comprised of an ionic liquid having one or more phosphonium based cations, and one or more anions, wherein the ionic liquid composition exhibits thermodynamic stability up to 375 °C, a liquidus range greater than 400 °C, and ionic conductivity of at least 1 mS/cm, or at least 5 mS/cm, or at least 10 mS/cm at room
• the electrolyte is comprised of one or more salts having one or more phosphonium based cations, and one or more anions dissolved in a solvent, wherein the electrolyte composition exhibits ionic conductivity of at least 5 mS/cm, or at least 10 mS/cm, or at least 15 mS/cm, or at least 20 mS/cm, or at least 30 mS/cm, or at least 40 mS/cm, or at least 50 mS/cm, or at least 60 mS/cm at room temperature.
• the phosphonium electrolyte exhibits reduced flammability as compared to conventional electrolytes, and thus improves the safety of battery operation.
• 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 protective layer.
• SEI solid electrolyte interphase
• the SEI layer may widen the electrochemical stability window, suppress battery degradation or decomposition reactions and hence improve battery cycle life.
• an electrochemical double layer capacitor comprising: a positive electrode, a negative electrode, a separator between said positive and negative electrode; and an electrolyte.
• the electrolyte is comprised of an ionic liquid composition or one or more salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• the electrolyte is comprised of an ionic liquid having one or more phosphonium based cations, and one or more anions, wherein the ionic liquid composition exhibits thermodynamic stability up to 375 °C, a liquidus range greater than 400 °C, and ionic conductivity of at least 1 mS/cm, or at least 5 mS/cm, or at least 10 mS/cm at room
• the electrolyte is comprised of one or more salts having one or more phosphonium based cations, and one or more anions dissolved in a solvent, wherein the electrolyte composition exhibits ionic conductivity of at least 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 at room temperature.
• the phosphonium electrolyte exhibits reduced fiammability as compared to conventional electrolytes, and thus improves the safety of EDLC operation.
• 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 protective layer.
• SEI solid electrolyte interphase
• the protective layer acts to widen the electrochemical stability window, suppress EDLC degradation or decomposition reactions and hence improve EDLC cycle life.
• Embodiments of the present invention further provide a heat transfer medium, comprising an ionic liquid composition or one or more salts dissolved in a solvent, comprising: one or more phosphonium based cations, and one or more anions, wherein the heat transfer medium exhibits thermodynamic stability at temperatures greater than 375 °C, a liquidus range of greater than 400 °C.
• phosphonium ionic liquid compositions and salts are useful in forming a variety of hybrid electrical devices.
• a device comprising a first electrode, a second electrode; and an electrolyte comprised of an ionic liquid composition or one or more salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• the first electrode is comprised of redox active molecules (ReAMs).
• ReAMs redox active molecules
• a molecular storage device comprising a working electrode and a counter electrode configured to afford electrical capacitance; and an ion conducting composition comprising: one or more phosphonium based cations of the general formula above and wherein the ion conducting composition is electrically coupled to at least the working and counter electrodes.
• the invention encompasses a molecular memory element that includes a switching device, a bit line and a word line coupled to the switching device and a molecular storage device accessible through the switching device.
• the molecular storage device is capable of being placed in two or more discrete states, wherein the molecular storage device is placed in one of the discrete states by signals applied to the bit and word line.
• the molecular storage device comprises a first electrode, a second electrode and an electrolyte of phosphonium based cations and suitable anions between the first and second electrode.
• Another embodiment encompasses molecular memory arrays comprising a plurality of molecular storage elements where each molecular storage element is capable of being placed in two or more discrete states.
• a 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.
• FIG. 1 is cross-sectional view of a battery cell according to one embodiment of the present invention.
• FIGS. 2A and 2B are cross-sectional views of bipolar electrode and multi-cell stack structures of a battery according to one embodiment of the present invention.
• FIG. 3 depicts one reaction scheme to form a phosphonium ionic liquid according to some embodiments of the present invention.
• FIG. 4 depicts another reaction scheme to form other embodiments of a phosphonium ionic liquid of the present invention
• FIG. 5 depicts another reaction scheme to form a phosphonium ionic liquid according to other embodiments of the present invention.
• FIG. 6 depicts another reaction scheme to form a phosphonium ionic liquid according to further embodiments of the present invention.
• FIG. 7 is a thermogravimetnc analysis (TGA) graph performed on exemplary embodiments of phosphonium ionic liquids prepared according to Example 1 ;
• FIG. 8A depicts a reaction scheme
• FIGS. 8B and 8C illustrate thermogravimetnc analysis (TGA) and evolved gas analysis (EGA) graphs, respectively, for exemplary embodiments of phosphonium ionic liquids prepared according to Example 2;
• FIG. 9A and 9B are graphs illustrating thermogravimetnc analysis (TGA) and evolved gas analysis (EGA), respectively, for exemplary embodiments of phosphonium ionic liquids prepared according to Example 3;
• FIG. 10A depicts a reaction scheme
• FIG. 10B shows the ⁇ NMR spectrum for exemplary embodiments of phosphonium ionic liquids prepared as described in FIG. 4 and Example 4;
• FIG. 11A is a reaction scheme
• FIG. 1 IB is a graph showing thermogravimetnc analysis (TGA) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 5;
• FIG. 12 is a graph showing thermogravimetnc analysis (TGA) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 6;
• FIG. 13 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 7;
• FIG. 14A depicts a reaction scheme, and
• FIG. 14B is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 8;
• FIG. 15A and FIG. 15B show the ⁇ and 3 I P NMR spectra respectively for exemplary embodiments of phosphonium salt prepared as described in Example 9;
• FIG. 16 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of phosphonium salt prepared according to Example 9;
• FIG. 17A and FIG. 17B show the ⁇ and 31 P NMR spectra respectively for exemplary embodiments of phosphonium salt prepared as described in Example 10;
• FIG. 18 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of phosphonium salt prepared according to Example 10;
• FIG. 19A and FIG. 19B show the ⁇ and 3 I P NMR spectra respectively for exemplary embodiments of phosphonium salt prepared as described in Example 1 1 ;
• FIG. 20 is a graph showing thermogravimetric analysis (TGA) results for exemplary embodiments of phosphonium salt prepared according to Example 1 1 ;
• FIG. 21 A and FIG. 21B are graphs showing differential scanning calorimetry (DSC) results for exemplary embodiments of phosphonium ionic liquids prepared according to Example 12.
• FIG. 22 depicts ionic conductivity as a function of ACN/salt volume ratio for phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH2)(CH 3 )2PC(CN) 3 in acetonitrile (ACN) as described in Example 14;
• FIG. 23 depicts ionic conductivity as a function of PC/salt volume ratio for 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;
• FIG. 24 depicts ionic conductivity as a function of molar concentration of phosphonium salts compared to an ammonium salt in propylene carbonate as described in Examples 42-45;
• FIG. 25 depicts 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. 26 shows the impact of phosphonium salt
• FIG. 27 shows the impact of phosphonium salt
• FIG. 28 is cross sectional view of a battery coin cell according to one embodiment of the present invention as described in Example 53;
• FIG. 29 shows the charge - discharge curve for a coin cell of Li/NMC with 1.0 M LiPF 6 in EC:DEC 1 : 1 and 10 w% phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 as described in Example 53 ;
• FIG. 30 is cross sectional view of a battery pouch cell according to one embodiment of the present invention as described in Example 54;
• FIG. 31 shows the linear sweep voltammetry of LNMO cathode in 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC with a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at concentrations of 0, 5, and 20 w% as described in Example 55-60;
• FIG. 32 shows onset oxidation potential as a function of the phosphonium additive concentration as described in Example 55-60;
• FIG. 33 shows the linear sweep voltammetry of LNMO cathode in 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC with a phosphonium additive [1 :3 : 1 ratio
• FIG. 34 shows the linear sweep voltammetry of NMC cathode in 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at 10 w% as described in Example 62;
• FIG. 35 shows the linear sweep voltammetry of NMC cathode in 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive [1 :3 : 1 ratio
• FIG. 36 shows AC impedance of lithium electrode inl .O M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 PCF 3 BF 3 at 10 w% as described in Example 64;
• FIG. 37 shows the charge - discharge performance of graphite electrode in 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC with and without a phosphonium additive
• FIG. 38 shows the charge - discharge performance of graphite electrode in 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC with and without a phosphonium additive
• FIG. 39 shows the charge - discharge performance of a Li/LNMO cell in 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at 10 w% as described in Example 67;
• FIG. 40 shows the charge - discharge performance of a Li/NMC cell in 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at 10 w% as described in Example 68; and.
• FIG. 41 shows the impact of phosphonium additives on the capacitance retention of a Graphite/LCO cell in 1.0 M LiPF 6 in EC:DEC:EMC 1 : 1 : 1 and 20 w% FEC as described in Example 69.
• the present invention is generally directed to phosphonium ionic liquids, salts, and compositions and their use in battery applications.
• the invention encompasses novel phosphonium ionic liquids, salts, compositions and their use in many applications, including but not limited to: as electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory, as electrolytes in batteries, electrochemical double layer capacitors, electrolytic capacitors, fuel cells, dye-sensitized solar cells, and electrochromic devices. Additional applications include use as a heat transfer medium, high temperature reaction and/or extraction media, among other applications.
• the invention relates to phosphonium ionic liquids, salts, compositions and molecules possessing structural features, wherein the composition exhibits desirable combination of at least two or more of: thermodynamic stability, low volatility, wide liquidus range, ionic conductivity, and electrochemical stability.
• the invention further encompasses methods of making such phosphonium ionic liquids, compositions and molecules, and operational devices and systems comprising the same.
• embodiments of the present invention provide devices having an electrolyte comprised of phosphonium ionic liquid compositions or one or more salts dissolved in a solvent.
• embodiments of the present invention provide a battery comprising an electrolyte comprised of phosphonium ionic liquid compositions or one or more salts dissolved in a solvent.
• embodiments of the present invention provide an electrochemical double layer capacitor (EDLC) comprising an electrolyte comprised of phosphonium ionic liquid compositions or one or more salts dissolved in a solvent.
• EDLC electrochemical double layer capacitor
• the advantageous properties of the phosphonium ionic liquid compositions make them particularly suited for applications as an electrolyte in electronic devices, batteries, EDLC's, fuel cells, dye-sensitized solar cells (DSSCs), and electrochromic devices.
• a heat transfer medium comprised of phosphonium ionic liquid compositions or one or more salts dissolved in a solvent.
• the advantageous properties of the compositions of the present invention are well suited as a heat transfer medium, and useful in processes and systems where a heat transfer medium is employed such as in heat extraction process and high temperature reactions. Definitions
• electrolyte or “electrolyte solution” or “electrolyte composition” or “ionic electrolyte” or “ion conducting electrolyte” or “ion conducting composition” or “ionic composition” is used and is herein defined 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 salts dissolved in at least one solvent together with at least one polymer to form a gel electrolyte.
• the one or more salts are defined to include: (a) one or more salts that are a solid at a temperature of 100 °C and below, and (b) one or more salts that are a liquid at a temperature of 100 °C and below.
• acyl refers to an organic acid group in which the OH of the carboxyl group is replaced by some other substituent (RCO-), such as described herein as “R” substituent groups. Examples include, but are not limited to, halo, acetyl, and benzoyl.
• alkoxy group means an -O- alkyl group, wherein alkyl is as defined herein.
• An alkoxy group can be unsubstituted or substituted with one, two or three suitable substituents.
• the alkyl chain of an alkoxy group is from 1 to 6 carbon atoms in length, referred to herein, for example, as "(CI - C6) alkoxy.”
• alkyl by itself or as part of another substituent, refers to a saturated or unsaturated, branched, straight-chain or cyclic monovalent hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane, alkene or alkyne. Also included within the definition of an alkyl group are cycloalkyl groups such as C5, C6 or other rings, and heterocyclic rings with nitrogen, oxygen, sulfur or phosphorus (heterocycloalkyl). Alkyl also includes heteroalkyl, with heteroatoms of sulfur, oxygen, nitrogen, phosphorous, and silicon finding particular use in certain
• Alkyl groups can be optionally substituted with R groups, independently selected at each position as described below.
• alkyl groups include, but are not limited to, (C1-C6) alkyl groups, such as methyl, ethyl, propyl, isopropyl, 2-methyl-l -propyl, 2-methyl-2-propyl, 2-methyl-l -butyl, 3- methyl- 1 -butyl, 2-methyl-3-butyl, 2,2-dimethyl-l -propyl, 2-methyl-l-pentyl, 3-methyl-l - pentyl, 4-methyl-l -pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2- dimethyl-l -butyl, 3, 3 -dimethyl- 1 -butyl, 2-ethyl-l -butyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, and hexyl, and longer al
• alkyl is specifically intended to include groups having any degree or level of saturation, i.e., groups having exclusively carbon-carbon single bonds, groups having one or more carbon-carbon double bonds, groups having one or more carbon-carbon triple bonds and groups having mixtures 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, refers to a saturated branched, straight-chain or cyclic alkyl radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane.
• Heteroalkanyl is included as described above.
• alkenyl by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon double bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkene.
• the group may be in either the cis or trans conformation about the double bond(s).
• Suitable alkenyl groups include, but are not limited to (C2-C6) alkenyl groups, such as vinyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, 2-ethylhexenyl, 2-propyl-2-butenyl, 4-(2-methyl- 3-butene)-pentenyl.
• An alkenyl group can be unsubstituted or substituted with one or more independently selected R groups.
• Alkynyl by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon triple bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkyne.
• alkyl also included within the definition of “alkyl” is “substituted alkyl”. “Substituted” is usually designated herein as “R”, and refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s).
• R substituents can be independently selected from, 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, amido, nitro, ethers, esters, aldehydes, sulfonyl, sulfoxyl, carbamoyl, acyl, cyano, thiocyanato, silicon moieties, halogens, sulfur containing moieties, phosphorus containing moieties, etc.
• R substituents include redox active moieties (ReAMs).
• ReAMs redox active moieties
• R and R' together with the atoms to which they are bonded form a cycloalkyl (including cycloheteroalkyl) and/or cycloaryl (including cycloheteroaryl), which can also be further substituted as desired.
• R is hydrogen when the position is unsubstituted. It should be noted that some positions may allow two or three substitution groups, R, R', and R", in which case the R, R', and R" groups may be either the same or different.
• the R groups are used to adjust the redox potential(s) of the subject compound.
• an R group such as a redox active subunit can be added to a macrocycle, particularly a porphyrinic macrocycle to alter its redox potential.
• Certain preferred substituents include, but are not limited to, 4-chlorophenyl, 3-acetamidophenyl, 2,4-dichloro-4-trifluoromethyl, and ferrocene (including ferrocene derivatives).
• 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.
• the R groups are as defined and depicted in the figures and the text from U.S. Provisional Ser. No. 60/687,464 which is incorporated herein by reference.
• a number of suitable proligands and complexes, as well as suitable substituents, are outlined in U.S. Pat. Nos. 6,212,093; 6,728, 129; 6,451 ,942; 6,777,516; 6,381 ,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; and U.S. Ser. Nos.
• aryl or grammatical equivalents herein is meant an aromatic monocyclic or polycyclic hydrocarbon moiety generally containing 5 to 14 carbon atoms (although larger polycyclic rings structures may be made) and any carbocyclic ketone, imine, or thioketone derivative thereof, wherein the carbon atom with the free valence is a member of an aromatic ring.
• Aromatic groups include arylene groups and aromatic groups with more than two atoms removed. For the purposes of this application aryl includes heteroaryl.
• Heteroaryl means an aromatic group wherein 1 to 5 of the indicated carbon atoms are replaced by a heteroatom chosen from nitrogen, oxygen, sulfur, phosphorus, boron and silicon wherein the atom with the free valence is a member of an aromatic ring, and any heterocyclic ketone and thioketone derivative thereof.
• heterocycle includes both single ring and multiple ring systems, e.g. thienyl, furyl, pyrrolyl, pyrimidinyl, indolyl, purinyl, quinolyl, isoquinolyl, thiazolyl, imidazolyl, naphthalene, phenanthroline, etc.
• aryl is substituted aryl, with one or more substitution groups "R" as defined herein and outlined above and herein.
• substitution groups "R” as defined herein and outlined above and herein.
• perfluoroaryl refers to an aryl group where every hydrogen atom is replaced with a fluorine atom.
• oxalyl is also included within the definition of aryl.
• halogen refers to one of the electronegative elements of group VIIA of the periodic table (fluorine, chlorine, bromine, iodine, and astatine).
• nitro refers to the -N0 2 group.
• amino groups or grammatical equivalents herein is meant -NH2, -NHR and -NRR' groups, with R and R' independently being as defined herein.
• pyridyl refers to an aryl group where one CH unit is replaced with a nitrogen atom.
• cyano refers to the -CN group.
• thiocyanato refers to the -SCN group.
• sulfoxyl refers to a group of composition RS(O)- where R is a substitution group as defined herein, including alkyl, (cycloalkyl, perfluoroalkyl, etc.), or aryl (e.g., perfluoroaryl group). Examples include, but are not limited to methylsulfoxyl, phenylsulfoxyl, etc.
• sulfonyl refers to a group of composition RS02- where R is a substituent group, as defined herein, with alkyl, aryl, (including cycloalkyl, perfluoroalkyl, or perfluoroaryl groups). Examples include, but are not limited to methylsulfonyl, phenylsulfonyl, p- toluenesulfonyl, etc.
• carbamoyl refers to the group of composition R(R')NC(0)- where R and R' are as defined herein, examples include, but are not limited to N-ethylcarbamoyl, N,N- dimethylcarbamoyl, etc.
• amido refers to the group of composition R]CONR 2 - where Ri and R 2 are substituents as defined herein. Examples include, but are not limited to acetamido, N- ethylbenzamido, etc.
• a metal when a metal is designated, e.g., by "M” or “M n ", where n is an integer, it is recognized that the metal can be associated with a counterion.
• the term “amperometric device” is a device capable of measuring the current produced in an electrochemical cell as a result of the application of a specific field potential ("voltage").
• aryloxy group means an -O- aryl group, wherein aryl is as defined herein.
• An aryloxy group can be unsubstituted or substituted with one or two suitable substituents.
• the aryl ring of an aryloxy group is a monocyclic ring, wherein the ring comprises 6 carbon atoms, referred to herein as "(C6) aryloxy.”
• benzyl means -CH2-phenyl.
• carbonyl is a divalent group of the formula -C(O)-.
• the term “coulometric device” is a device capable of measuring the net charge produced during the application of a potential field ("voltage”) to an electrochemical cell.
• the term “cyano” refers to the -CN group.
• the term “different and distinguishable” when referring to two or more oxidation states means that the net charge on the entity (atom, molecule, aggregate, subunit, etc.) can exist in two different states. The states are said to be “distinguishable” when the difference between the states is greater than thermal energy at room temperature.
• the term “electrically coupled” when used with reference to a storage molecule and/or storage medium and electrode refers to an association between that storage medium or molecule and the electrode such that electrons move from the storage medium/molecule to the electrode or from the electrode to the storage medium/molecule and thereby alter the oxidation state of the storage medium/molecule.
• Electrical coupling can include direct covalent linkage between the storage medium/molecule and the electrode, indirect covalent coupling (e.g. via a linker), direct or indirect ionic bonding between the storage medium/molecule and the electrode, or other bonding (e.g. hydrophobic bonding).
• no actual bonding may be required and the storage medium/molecule may simply be contacted with the electrode surface.
• electrochemical cell consists minimally of a reference electrode, a working electrode, a redox-active medium (e.g. a storage medium), and, if necessary, some means (e.g., a dielectric) for providing electrical conductivity between the electrodes and/or between the electrodes and the medium.
• a redox-active medium e.g. a storage medium
• some means e.g., a dielectric
• the dielectric is a component of the storage medium.
• 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 manufactured to virtually any 2-dimensional or 3-dimensional shape (e.g. , discrete lines, pads, planes, spheres, cylinders, etc.).
• the term "fixed electrode” is intended to reflect the fact that the electrode is essentially stable and unmovable with respect to the storage medium. That is, the electrode and storage medium are arranged in an essentially fixed geometric relationship with each other. It is of course recognized that the relationship alters somewhat due to expansion and contraction of the medium with thermal changes or due to changes in conformation of the molecules comprising the electrode and/or the storage medium. Nevertheless, the overall spatial arrangement remains essentially invariant.
• linker is a molecule used to couple two different molecules, two subunits of a molecule, or a molecule to a substrate.
• R groups include, but are not limited to, hydrogen, alkyl, alcohol, aryl, amino, amido, nitro, ethers, esters, aldehydes, sulfonyl, silicon moieties, halogens, cyano, acyl, sulfur containing moieties, phosphorus containing moieties, Sb, imido, carbamoyl, linkers, attachment moieties, ReAMs and other subunits .
• R and R' may allow two substitution groups, R and R', in which case the R and R 1 groups may be either the same or different, and it is generally preferred that one of the substitution groups be hydrogen.
• the R groups are as defined and depicted in the figures and the text from U.S A number of suitable proligands and complexes, as well as suitable substituents, are outlined in U.S. Pat. Nos. 6,212,093; 6,728,129; 6,451 ,942; 6,777,516; 6,381 , 169; 6,208,553 ; 6,657,884; 6,272,038; 6,484,394; and U.S. Ser. Nos.
• subunit refers to a redox- active component of a molecule.
• embodiments of novel phosphonium ionic liquids, salts, and compositions of the present invention exhibit desirable properties and in particular a combination of at least two or more of: high thermodynamic stability, low volatility, wide liquidus range, high ionic conductivity, and wide electrochemical stability window. .
• the combination of up to, and in some embodiments, all of these properties at desirable levels in one composition was unexpected and not foreseen, and provides a significant advantage over known ionic compositions.
• Embodiments of phosphonium compositions of the present invention exhibiting such properties enable applications and devices not previously available.
• phosphonium ionic liquids of the present invention comprise phosphonium cations of selected molecular weights and substitution patterns, coupled with selected anion(s), to form ionic liquids with tunable combinations of thermodynamic stability, ionic conductivity, liquidus range, and low volatility properties.
• ionic liquid herein is meant a salt that is in the liquid state at and below 100 °C.
• Room temperature ionic liquid is further defined herein in that it is in the liquid state at and below room temperature.
• the term “electrolyte” “or “electrolyte solution” or “electrolyte composition” or “ionic electrolyte” or “ion conducting electrolyte” or “ion conducting composition” or “ionic composition” is used and is herein defined 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 salts dissolved in at least one solvent together with at least one polymer to form a gel electrolyte.
• the one or more salts are defined to include: (a) one or more salts that are a solid at a temperature of 100 °C and below, and (b) one or more salts that are a liquid at a temperature of 100 °C and below.
• the present invention comprises phosphonium ionic liquids and phosphonium electrolytes that exhibit thermodynamic stability up to temperatures of approximately 400 °C, and more usually up to temperatures of approximately 375 °C.
• Embodiments of phosphonium ionic liquids and phosphonium electrolytes of the present invention further exhibit ionic conductivity of 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/cm, or at least 40 mS/cm, or at least 50 mS/cm, or at least 60 mS/cm at room temperature.
• Embodiments of phosphonium ionic liquids and phosphonium electrolytes of the present invention exhibit volatilities that are about 20 % lower compared to their nitrogen-based analogs. This combination of high thermal stability, high ionic conductivity, wide liquidus range, and low volatility, is highly desirable and was unexpected. Generally, in the prior art it is found that thermal stability and ionic conductivity of ionic liquids exhibit an inverse relationship.
• phosphonium ionic liquids and phosphonium electrolytes are comprised of cations having molecular weight of up to 500 Dal tons. In other embodiments, phosphonium ionic liquids and phosphonium electrolytes are comprised of cations having molecular weight in the range of 200 to 500 Daltons for ionic liquids at the lower thermal stability ranges.
• Phosphonium ionic compositions of the present invention are comprised of phosphonium based cations of the general formula:
• R'R R 4 ? (1) wherein: R 1 , R 2 , R 3 and R 4 are each independently a substituent group. In some embodiments, wherein the cations are comprises of open chains.
• 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, an alkyl group is comprised 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 comprised of 2 to 14 carbon atoms. In some
• the alkyl groups contain no branching.
• R R in an aliphatic, heterocyclic moiety.
• R 1 R 2 in an aromatic, heterocyclic moiety.
• R 1 or R 2 are comprised of phenyl or substituted alkylphenyl. In some embodiments, R 1 and R 2 are the same and are comprised of tetramethylene
• R and R are the same and are comprised of tetramethinyl (phosphole).
• R 1 and R 2 are the same and are comprised of phospholane or phosphorinane.
• R 2 R 3 and R 4 are the same and are comprised of phospholane, phosphorinane or phosphole.
• At least one, more, of or all of R 1 , R 2 , R 3 and R 4 are selected such that each does not contain functional groups that would react with the redox active molecules (ReMAs) described below. In some embodiments, at least one, more, of or all of R 1 ,
• R , R and R do not contain halides, metals or O, N, P, or Sb.
• the alkyl group comprises from 1 to 7 carbon atoms. In other embodiments the total carbon atoms from all alkyl groups is 12 or less. In yet other
• the alkyl groups are each independently comprised of 1 to 6 carbon atoms, more typically, from 1 to 5 carbon atoms.
• phosphonium ionic compositions are provided and are comprised of: one or more salts dissolved in a solvent, the one or more salts comprising one or more phosphonium based cations of the general formula:
• R ! R R 3 R 4 P (1) and one or more anions and wherein: R 1 , R 2 , R 3 and R 4 are each independently a substituent group, such as but not limited to an alkyl group as described below. In some embodiments R 1 , R 2 , R 3 and R 4 are each independently an alkyl group comprised of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. In some embodiments one or more of the hydrogen atoms in one or more of the R groups are substituted by fluorine. Any one or more of the salts may be liquid or solid at a temperature of 100 °C and below. In some embodiments, a salt is comprised of one cation and one anion.
• a salt is comprised of one cation and multiple anions. In other embodiments, a salt is comprised of one anion and multiple cations. In further embodiments, a salt is comprised of multiple cations and multiple anions.
• 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), ethylmethyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), , fluoroethylene carbonate (FEC),
• FB fluorobenzene
• VC vinylene carbonate
• VEC vinyl ethylene carbonate
• PhEC phenylethylene carbonate
• PMC propylmethyl carbonate
• DEE diethoxyethane
• DME dimethoxyethane
• THF tetrahydrofuran
• GBL ⁇ -butyrolactone
• VL ⁇ -valerolactone
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• phosphonium cations are comprised of the following formula:
• examples of suitable phosphonium cations include but are not limited to: di-n-propyl ethyl phosphonium; n-butyl n-propyl ethyl phosphonium; n-hexyl n- butyl ethyl phosphonium; and the like.
• examples of suitable phosphonium cations include but are not limited to: ethyl phospholane; n-propyl phospholane; n-butyl phospholane; n-hexyl
• examples of suitable phosphonium cations include but are not limited to: ethyl phosphole; n-propyl phosphole; n-butyl phosphole; n-hexyl phophole; and phenyl phosphole.
• examples of suitable - phosphonium cations include but are not limited to: 1 -ethyl phosphacyclohexane; n-propyl phosphacyclohexane; n-butyl phosphacyclohexane; n-hexyl phophacyclohexane; and phenyl phosphacyclohexane.
• Phosphonium ionic liquids or salts of the present invention are comprised of cations and anions. As will be appreciated by those of skill in the art, there are a large variety of possible cation and anion combinations. Phosphonium ionic liquids or salts of the present invention comprise cations as described above with anions that are generally selected from compounds that are easily ion exchanged with reagents or solvents of the general formula:
• C + is a cation and A + is an anion.
• C + is preferably Li + , K + , Na + , NH 4 + or Ag + .
• C+ is preferably Ag + .
• anions may be selected.
• the anion is bis- perfluoromethyl sulfonyl imide.
• suitable anions include, but are not limited to, any one or more of: N0 3 " , 0 3 SCF 3 " , N(S0 2 CF 3 ) 2 " , PF 6 " , 0 3 SC 6 H 4 CH 3 ⁇ ,
• phosphonium ionic liquids or salts of the present invention are comprised of a single cation-anion pair.
• two or more phosphonium ionic liquids or salts may be used to form common binaries, mixed binaries, common ternaries, mixed ternaries, and the like.
• Composition ranges for binaries, ternaries, etc. include from 1 ppm, up to 999,999 ppm for each component cation and each component anion.
• phosphonium electrolytes are comprised of one or more salts dissolved in a solvent, and the salts may be liquid or solid at a temperature of 100 °C.
• a salt is comprised of a single cation-anion pair.
• a salt is comprised of a one cation and multiple anions.
• a salt is comprised of one anion and multiple cations.
• a salt is comprised of multiple cations and multiple anions.
• Electrolyte compositions according to some embodiments of the present invention are further described in co-pending United States Patent application serial number
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Tables 1 A and IB, below.
• phosphonium electrolytes compositions are comprised of phosphonium salts having cation and anion combinations shown in Tables 1C, ID , IE, and IF below. For clarity, signs of charge have been omitted in the formulas.
• Table 1A illustrates examples of anion binaries with a common cation:
• Table IB illustrates examples of cation and anion combinations:
• phosphonium electrolytes compositions are comprised of salts having cations as shown in Tables lC-1 to l C-3 below: Table lC-1:
• phosphonium electrolytes compositions are comprised of salts having anions as shown in Tables lD-1 to 1D-4 below:
• phosphonium electrolyte compositions are comprised of salts having cation and anion combinations as shown in Tables ⁇ -lto 1E-4 below:
• the phosphonium electrolyte is comprised of a salt dissolved a solvent, where the salt is comprised of: one or more cations of the formula:
• the phosphonium electrolyte is comprised of a salt dissolved a solvent, wherein the salt is comprised of: one or more cations of the formula:
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, wherein the salt is comprised of: one or more cations of the formula:
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of one or more anions selected from the group consisting of: PF 6 , (CF 3 ) 3 PF 3 , (CF 3 ) 4 PF 2 , (CF 3 CF 2 ) 4 PF 2 , (CF 3 CF 2 CF 2 ) 4 PF 2 , (-OCOCOO-)PF 4 ,
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of: a cation of the formula:
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula (CH 3 )(CH 3 CH 2 ) 3 P + and an anion of any one or more of the formula BF 4 ⁇ , PF 6 " , CF 3 BF 3 " , (-OCOCOO-)BF 2 " ,
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula (CH 3 CH 2 CH 2 ) 3 (CH 3 )P + and an anion of any one or more of the formula BF 4 " , PF 6 " , CF 3 BF 3 " , (-OCOCOO-)BF 2 " , (-OCOCOO-)(CF 3 ) 2 B ⁇ (-OCOCOO-) 2 B ⁇ CF 3 S0 3 " , C(CN) 3 " , (CF 3 S0 2 ) 2 N " or combinations thereof.
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula (CH 3 CH 2 CH 2 ) 2 (CH 3 CH 2 ) (CH 3 )P + and an anion of any one or more of the formula BF 4 " , PF 6 " , CF3BF3 " ,
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of : a cation of the formula (CH 3 CH 2 ) 4 P + and an anion of any one or more of the formula BF 4 " , PF 6 “ , CF 3 BF 3 “ , (-OCOCOO-)BF 2 " ,
• the phosphonium electrolyte is comprised of a salt dissolved in a solvent, where the salt is comprised of: a cation of the formula 1 :3: 1 mole ratio of (CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P /(CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 2 (CH 3 )P and an anion of any one or more of the formula BF 4 " , PF 6 " , CF 3 BF 3 " , (-OCOCOO-)BF 2 " ,
• the anions are comprised of a mixture of BF 4 " and CF 3 BF 3 " at a concentration of [BF 4 " ] :[CF 3 BF 3 " ] mole ratio in the range of 100/1 to 1/1.
• the anions are comprised of a mixture of PF 6 " and CF 3 BF3 _ at a concentration of [PF 6 " ]:[CF 3 BF 3 " ] mole ratio in the range of 100/1 to 1/1.
• the anions are comprised of a mixture of PF 6 " and BF 4 " at a concentration of [PF 6 " ]:[BF 4 " ] mole ratio in the range of 100/1 to 1/1.
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 2 below: Table 2
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 3 below:
• phosphonium ionic liquid compositions are comprised of the cation and anion combinations as shown in Table 4 below:
• phosphonium ionic liquid compositions are comprised of the cation and anion combinations as shown in Table 5 below:
• phosphonium ionic liquid compositions are comprised of the cation and anion combinations as shown in Table 6 below: Table 6
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 7 below:
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 8 below:
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 9 below: Table 9
• phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 10 below:
• Additional preferred embodiments include phosphonium ionic liquid compositions are comprised of cation and anion combinations as shown in Table 1 1 below:
• Another preferred exemplary embodiment includes phosphonium ionic liquid compositions comprised of cation and anion combinations as shown in Table 13 below: Table 13
• suitable phosphonium ionic liquid compositions include but are not limited to: di-n-propyl ethyl methyl phosphonium bis- (trifluoromethyl sulfonyl) imide; n-butyl n-propyl ethyl methyl phosphonium bis- (trifluoromethyl sulfonyl) imide; n-hexly n-butyl ethyl methyl phosphonium bis- (trifluoromethyl sulfonyl) imide; and the like.
• Illustrative examples of suitable phosphonium ionic liquid compositions further include but are not limited to: 1 -ethyl- 1 -methyl phospholanium bis-(trifluoromethyl sulfonyl) imide; n-propyl methyl phospholanium bis-(trifluoromethyl sulfonyl) imide; n-butyl methyl phospholanium bis-(trifluoromethyl sulfonyl) imide; n-hexyl methyl phopholanium bis- (trifluoromethyl sulfonyl) imide; and phenyl methyl phospholanium bis-(trifluoromethyl sulfonyl) imide.
• examples of suitable phosphonium ionic liquid compositions include but are not limited to: 1 -ethyl- 1 -methyl phospholanium bis-(trifluoromethyl sulfonyl) imide; n-propyl methyl phospholanium bis-(trifluoromethyl sulfonyl) imide; n-butyl methyl phospholanium bis-(trifluoromethyl sulfonyl imide; n-hexyl methyl phopholanium bis- (trifluoromethyl sulfonyl) imide; and phenyl methyl phospholanium bis-(trifluoromethyl sulfonyl) imide.
• suitable phosphonium ionic liquid compositions include but are not limited to: 1 -ethyl- 1 -methyl phosphacyclohexane bis-(trifluoromethyl sulfonyl) imide; n-propyl methyl phosphacyclohexane bis-(trifluoromethyl sulfonyl) imide; n- butyl methyl phosphacyclohexane bis-(trifluoromethyl sulfonyl) imide; n-hexyl methyl phosphacyclohexane bis-(trifluoromethyl sulfonyl) imide; and phenyl methyl
• Phosphonium ionic liquids of the present invention may also form a eutectic from one or more solids, or from a solid and a liquid, according to some embodiments.
• the term "ionic liquid” is further defined to include ionic liquid that are eutectics from ionic solids, or from an ionic liquid and an ionic solid, such as binaries, ternaries, and the like.
• Phosphonium ionic liquids of the present invention described herein can be employed to synthesize a wide range of hybrid components and/or devices, such as for example memory devices and elements.
• phosphonium ionic liquids herein are used to form molecular memory devices where information is stored in a redox-active information storage molecule.
• Redox-active molecule herein is meant to refer to a molecule or component of a molecule that is capable of being oxidized or reduced, e.g., by the application of a suitable voltage.
• ReAMs can include, but are not limited to macrocycles including porphyrin and porphyrin derivatives, as well as non-macrocyclic compounds, and includes sandwich compounds, e.g. as described herein.
• ReAMs can comprise multiple subunits, for example, in the case of dyads or triads.
• ReAMs can include ferrocenes, Bipys, PAHs, viologens, and the like.
• suitable proligands and complexes, as well as suitable substituents are outlined in U.S. Patent Nos.
• Suitable proligands fall into two categories: ligands which use nitrogen, oxygen, sulfur, carbon or phosphorus atoms (depending on the metal ion) as the coordination atoms (generally referred to in the literature as sigma ( ⁇ ) donors) and organometallic ligands such as metallocene ligands (generally referred to in the literature as pi ( ⁇ ) donors, and depicted herein as Lm).
• a single ReAM may have two or more redox active.
• Figure 13A of U. S. Publication No. 2007/0108438 shows two redox active subunits, a porphyrin (shown in the absence of a metal), and ferrocene.
• sandwich coordination compounds are considered a single ReAM. This is to be distinguished from the case where these ReAMs are polymerized as monomers.
• the metal ions/complexes of the invention may be associated with a counterion, not generally depicted herein.
• the ReAM is a macrocyclic ligand, which includes both macrocyclic proligands and macrocyclic complexes.
• macrocyclic proligand herein is meant a cyclic compound which contain donor atoms (sometimes referred to herein as
• coordination atoms oriented so that they can bind to a metal ion and which are large enough to encircle the metal atom.
• the donor atoms are heteroatoms including, but not limited to, nitrogen, oxygen and sulfur, with the former being especially preferred.
• different metal ions bind preferentially to different heteroatoms, and thus the heteroatoms used can depend on the desired metal ion.
• a single macrocycle can contain heteroatoms of different types.
• a "macrocyclic complex” is a macrocyclic proligand with at least one metal ion; in some embodiments the macrocyclic complex comprises a single metal ion, although as described below, polynucleate complexes, including polynucleate macrocyclic complexes, are also contemplated.
• macrocyclic ligands find use in the present invention, including those that are electronically conjugated and those that may not be; however, the macrocyclic ligands of the invention preferably have at least one, and preferably two or more oxidation states, with 4, 6 and 8 oxidation states being of particular significance.
• FIG. 1 1 and 14 A broad schematic of suitable macrocyclic ligands are shown and described in Figures 1 1 and 14 of U.S. Publication No. 2007/0108438, all of which is incorporated by reference herein in addition to Figures 1 1 and 14.
• a 16 member ring when the -X— moiety contains a single atom, either carbon or a heteroatom
• 17 membered rings where one of the -X— moieties contains two skeletal atoms
• 18 membered rings where two of the -X— moieties contains two skeletal atoms
• 19 membered rings where three of the -X— moieties contains two skeletal atoms
• 20 membered rings where all four of the -X— moieties contains two skeletal atoms
• Each -X— group is independently selected.
• the rings, bonds and substituents are chosen to result in the compound being electronically conjugated, and at a minimum to have at least two oxidation states.
• the macrocyclic ligands of the invention are selected from the group consisting of porphyrins (particularly porphyrin derivatives as defined below), and eye 1 en derivatives.
• porphyrins including porphyrin derivatives.
• Such derivatives include porphyrins with extra rings ortho- fused, or ortho-perifused, to the porphyrin nucleus, porphyrins having a replacement of one or more carbon atoms of the porphyrin ring by an atom of another element (skeletal replacement), derivatives having a replacement of a nitrogen atom of the porphyrin ring by an atom of another element (skeletal replacement of nitrogen), derivatives having substituents other than hydrogen located at the peripheral (meso-, (3- or core atoms of the porphyrin, derivatives with saturation of one or more bonds of the porphyrin (hydroporphyrins, e.g., chlorins,
• bacteriochlorins bacteriochlorins, isobacteriochlorins, decahydropo ⁇ hyrins, corphins, pyrrocorphins, etc.
• derivatives having one or more atoms including pyrrolic and pyrromethenyl units, inserted in the porphyrin ring (expanded porphyrins), derivatives having one or more groups removed from the porphyrin ring (contracted porphyrins, e.g., corrin, corrole) and combinations of the foregoing derivatives (e.g. phthalocyanines, sub-phthalocyanines, and porphyrin isomers).
• porphyrin derivatives include, but are not limited to the chlorophyll group, including etiophyllin, pyrroporphyrin, rhodoporphyrin, phylloporphyrin, phylloerythrin, chlorophyll a and b, as well as the hemoglobin group, including deuteroporphyrin,
• each unsaturated position can include one or more substitution groups as defined herein, depending on the desired valency of the system.
• the redox-active molecule may be a metallocene, which can be substituted at any appropriate position, using R groups independently selected herein.
• a metallocene which finds particular use in the invention includes ferrocene and its derivatives.
• preferred substituents include, but are not limited to, 4chlorophenyl, 3- acetamidophenyl, 2,4-dichloro-4-trifluoromethyl. Preferred substituents provide a redox potential range of less than about 2 volts.
• F is a redox-active subunit (such as ferrocene, a substituted ferrocene, a metal loporphyrin, or a metallochlorin, and the like)
• Jl is a linker
• M is a metal (such as Zn, Mg, Cd, Hg, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Mn, B, Al,
• S I and S2 are independently selected from the group of aryl, phenyl, cyclalkyl, alkyl, halogen, alkoxy, alkythio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl wherein said substituents provide a redox potential range of less than about 2 volts, Kl , 2, K3 and K4 are independently selected from the group of N, O, S, Se, Te and CH; L is a linker, X is selected from the group of a substrate, a couple to a substrate, and a reactive site that can ionically couple to a substrate. In preferred embodiments, X or L-X may be an alcohol or a thiol. In some embodiments, L-X
• the hole-storage properties depend on the oxidation potential of the redox-active units or subunits that are themselves or are that are used to assemble the storage media used in the devices of this invention.
• the hole-storage properties and redox potential can be tuned with precision by choice of base molecule(s), associated metals and peripheral substituents (Yang et al. (1999) J. Porphyrins Phthalocyanines, 3: 1 17-147), the disclosure of which is herein incorporated by this reference.
• Mg porphyrins are more easily oxidized than Zn porphyrins, and electron withdrawing or electron releasing aryl groups can modulate the oxidation properties in predictable ways.
• Hole-hopping occurs among isoenergetic porphyrins in a nanostructure and is mediated via the covalent linker joining the porphyrins (Seth et al. (1994) J. Am. Chem. Soc, 1 16: 10578-10592, Seth et al (1996) J. Am. Chem. Soc, 1 18:
• Electrochemistry of the Elements Moreover, in general, the effects of various substituents on the redox potentials of a molecule are generally additive. Thus, a theoretical oxidation potential can be readily predicted for any potential data storage molecule. The actual oxidation potential, particularly the oxidation potential of the information storage molecule(s) or the information storage medium can be measured according to standard methods. Typically the oxidation potential is predicted by comparison of the experimentally determined oxidation potential of a base molecule and that of a base molecule bearing one substituent in order to determine the shift in potential due to that particular substituent. The sum of such substituent- dependent potential shifts for the respective substituents then gives the predicted oxidation potential.
• redox-active molecules for use in the methods of this invention can readily be determined.
• the molecule(s) of interest are simply polymerized and coupled to a surface (e.g., a hydrogen passivated surface) according to the methods of this invention.
• sinusoidal voltammetry can be performed (e.g., as described herein or in U.S. Patents, 6,272,038; 6,212,093; and 6,208,553, PCT Publication WO 01/03126, or by (Roth et al. (2000) Vac. Sci. Technol. B 18:2359-2364; Roth et al. (2003) J.Am. Chem. Soc.
• 125:505- 517) to evaluate 1 ) whether or not the molecule(s) coupled to the surface, 2) the degree of coverage (coupling); 3) whether or not the molecule(s) are degraded during the coupling procedure, and 4) the stability of the molecule(s) to multiple read/write operations.
• porphyrin included within the definition of “porphyrin” are porphyrin complexes, which comprise the porphyrin proligand and at least one metal ion. Suitable metals for the porphyrin compounds will depend on the heteroatoms used as coordination atoms, but in general are selected from transition metal ions.
• transition metals typically refers to the 38 elements in groups 3 through 12 of the periodic table. Typically transition metals are characterized by the fact that their valence electrons, or the electrons they use to combine with other elements, are present in more than one shell and consequently often exhibit several common oxidation states.
• the transition metals of this invention include, but are not limited to one or more of 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, rutherfordium, and/or oxides, and/or nitrides, and/or alloys, and/or mixtures thereof.
• Other Macrocycles include, but are not limited to one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palla
• FIG. 17 and 13C of U.S. Publication No. 2007/0108438 shows a number of macrocyclic proligands loosely based on cyclen/cyclam derivatives, which can include skeletal expansion by the inclusion of independently selected carbons or heteroatoms.
• at least one R group is a redox active subunit, preferably electronically conjugated to the metal.
• two or more neighboring R2 groups form cycle or an aryl group.
• macrocyclic complexes relying organometallic ligands are used.
• organometallic ligands include organic compounds for use as redox moieties, and various transition metal coordination complexes with ⁇ -bonded organic ligand with donor atoms as heterocyclic or exocyclic substituents.
• transition metal organometallic compounds with ⁇ -bonded organic ligands see Advanced Inorganic Chemistry, 5th Ed., Cotton & Wilkinson, John Wiley & Sons, 1988, chapter 26;
• organometallic ligands include cyclic aromatic compounds such as the cyclopentadienide ion [C5H5(-1)] and various ring substituted and ring fused derivatives, such as the indenylide (-1) ion, that yield a class of bis(cyclopentadieyl)metal compounds, (i.e.
• Metallocene derivatives of a variety of the first, second and third row transition metals are useful as redox moieties (and redox subunits).
• organometallic ligands include cyclic arenes such as benzene, to yield bis(arene)metal compounds and their ring substituted and ring fused derivatives, of which bis(benzene)chromium is a prototypical example,
• Other acyclic ⁇ -bonded ligands such as the allyl(-l) ion, or butadiene yield potentially suitable organometallic compounds, and all such ligands, in conjunction with other ⁇ -bonded and ⁇ -bonded ligands constitute the general class of organometallic compounds in which there is a metal to carbon bond. Electrochemical studies of various dimers and oligomers of such compounds with bridging organic ligands, and additional non-bridging ligands, as well as with and without metal -metal bonds are all useful.
• the ligand is generally attached via one of the carbon atoms of the organometallic ligand, although attachment may be via other atoms for heterocyclic ligands.
• Preferred organometallic ligands include metallocene ligands, including substituted derivatives and the metalloceneophanes (see page 1 174 of Cotton and Wilkenson, supra).
• derivatives of metallocene ligands such as methylcyclopentadienyl, with multiple methyl groups being preferred, such as pentamethylcyclopentadienyl, can be used to increase the stability of the metallocene.
• the metallocene is derivatized with one or more substituents as outlined herein, particularly to alter the redox potential of the subunit or moiety.
• any combination of ligands may be used.
• Preferred combinations include: a) all ligands are nitrogen donating ligands; b) all ligands are organometallic ligands.
• the ReAMs are sandwich coordination complexes.
• “sandwich coordination compound” or “sandwich coordination complex” refer to a compound of the formula L-Mn-L, where each L is a heterocyclic ligand (as described below), each M is a metal, n is 2 or more, most preferably 2 or 3, and each metal is positioned between a pair of ligands and bonded to one or more hetero atom (and typically a plurality of hetero atoms, e.g.,
• sandwich coordination compounds are not organometallic compounds such as ferrocene, in which the metal is bonded to carbon atoms.
• the ligands in the sandwich coordination compound are generally arranged in a stacked orientation (i.e., are generally cofacially oriented and axially aligned with one another, although they may or may not be rotated about that axis with respect to one another) (see, e.g., 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 compound" and "triple-decker sandwich coordination compounds”.
• double-decker sandwich coordination compound refers to a sandwich coordination compound as described above where n is 2, thus having the formula L'-M'-LZ, wherein each of LI and LZ may be the same or different (see, e.g., Jiang et al. (1999) J.
• triple-decker sandwich coordination compound refers to a sandwich coordination compound as described above where n is 3, thus having the formula L'-M' LZ- MZ-L3, wherein each of LI, LZ and L3 may be the same or different, and Ml and MZ may be the same or different (see, e.g., Arnold et al. (1999) Chemistry Letters 483-484), and U.S. Patent Nos. 6,212,093; 6,451 ,942; 6,777,516; and polymerization of these molecules is described in U.S. Publication No. 2007/0123618, hereby incorporated by reference in their entirety.
• polymers of these sandwich compounds are also of use; this includes “dyads” and “triads” as described in U.S. S.N 6,212,093; 6,451 ,942; 6,777,516; and
• ReAMs comprising non-macrocyclic chelators are bound to metal ions to form non-macrocyclic chelate compounds, since the presence of the metal allows for multiple proligands to bind together to give multiple oxidation states.
• nitrogen donating proligands are used.
• Suitable nitrogen donating proligands include, but are not limited to, NH2; NHR; NRR'; pyridine; pyrazine; isonicotinamide; imidazole; bipyridine and substituted derivatives of bipyridine; terpyridine and substituted derivatives; phenanthrolines, particularly 1 ,10- phenanthroline (abbreviated phen) and substituted derivatives of phenanthrolines such as 4,7- dimethylphenanthroline and dipyridol[3,2-a:2',3'-c]phenazine (abbreviated dppz);
• dipyridophenazine 1,4,5,8,9,12-hexaazatriphenylene (abbreviated hat); 9,10- phenanthrenequinone diimine (abbreviated phi); 1 ,4,5,8-tetraazaphenanthrene (abbreviated tap); 1 ,4,8,1 1 -tetra-azacyclotetradecane (abbreviated cyclam) and isocyanide.
• Substituted derivatives, including fused derivatives may also be used.
• macrocylic ligands that do not coordinatively saturate the metal ion, and which require the addition of another proligand, are considered non-macrocyclic for this purpose.
• Suitable sigma donating ligands using carbon, oxygen, sulfur and phosphorus are known in the art.
• suitable sigma carbon donors are found in Cotton and
• oxygen, sulfur, phosphorus and nitrogen-donating ligands are attached in such a manner as to allow the heteroatoms to serve as coordination atoms.
• polydentate ligands that are polynucleating ligands, e.g. they are capable of binding more than one metal ion. These may be macrocyclic or non-macrocyclic.
• the term "memory element,” “memory cell,” or “storage cell” refer to an electrochemical cell that can be used for the storage of information.
• Preferred “storage cells” are discrete regions of storage medium addressed by at least one and preferably by two electrodes (e.g., a working electrode and a reference electrode).
• the storage cells can be individually addressed (e.g., a unique electrode is associated with each memory element) or, particularly where the oxidation states of different memory elements are distinguishable, multiple memory elements can be addressed by a single electrode.
• the memory element can optionally include a dielectric (e.g., a dielectric impregnated with counter ions).
• Electrode refers to any medium capable of transporting charge (e.g., electrons) to and/or from a storage molecule.
• Preferred electrodes are metals and conductive organic molecules, including, but 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 (including doped and oxidized Group V elements) and transition metals (including transition metal oxides and transition metal nitrides).
• the electrodes can be manufactured to virtually and 2-dimensional or 3 -dimensional shape (e.g., discrete lines, pads, planes, spheres, cylinders).
• the term “multiple oxidation states” means more than one oxidation state.
• the oxidation states may reflect the gain of electrons (reduction) or the loss of electrons (oxidation).
• multiporphyrin array refers to a discrete number of two or more covalently-linked porphyrinic macrocycles.
• the multiporphyrin arrays can be linear, cyclic, or branched.
• output of an integrated circuit refers to a voltage or signal produced by one or more integrated circuit(s) and/or one or more components of an integrated circuit.
• the term "present on a single plane,” when used in reference to a memory device of this invention refers to the fact that the component(s) (e.g. storage medium, electrode(s), etc.) in question are present on the same physical plane in the device (e.g. are present on a single lamina). Components that are on the same plane can typically be fabricated at the same time, e.g., in a single operation. Thus, for example, all of the electrodes on a single plane can typically be applied in a single (e.g., sputtering) step (assuming they are all of the same material).
• a potentiometric device is a device capable of measuring potential across an interface that results from a difference in the equilibrium concentrations of redox molecules in an electrochemical cell.
• oxidation refers to the loss of one or more electrons in an element, compound, or chemical substituent/subunit.
• electrons are lost by atoms of the element(s) involved in the reaction. The charge on these atoms must then become more positive. The electrons are lost from the species undergoing oxidation and so electrons appear as products in an oxidation reaction.
• An oxidation taking place in the reaction Fe 2+ (aq) -> Fe 3+ (aq) + e because electrons are lost from the species being oxidized, Fe 2+ (aq), despite the apparent production of electrons as "free” entities in oxidation reactions.
• reduction refers to the gain of one or more electrons by an element, compound, or chemical substituent/subunit.
• the term “oxidation state” refers to the electrically neutral state or to the state produced by the gain or loss of electrons to an element, compound, or chemical substituent/subunit. In a preferred embodiment, the term “oxidation state” refers to states including the neutral state and any state other than a neutral state caused by the gain or loss of electrons (reduction or oxidation).
• the term “read” or “interrogate” refer to the determination of the oxidation state(s) of one or more molecules (e.g. molecules comprising a storage medium).
• redox-active unit or “redox- active subunit” refers to a molecule or component of a molecule that is capable of being oxidized or reduced by the application of a suitable voltage.
• the term “refresh” when used in reference to a storage molecule or to a storage medium refers to the application of a voltage to the storage molecule or storage medium to re-set the oxidation state of that storage molecule or storage medium to a predetermined state (e.g., the oxidation state the storage molecule or storage medium was in immediately prior to a read).
• reference electrode is used to refer to one or more electrodes that provide a reference (e.g., a particular reference voltage) for measurements recorded from the working electrode.
• a reference e.g., a particular reference voltage
• the reference electrodes in a memory device of this invention are at the same potential although in some embodiments this need not be the case.
• a "sinusoidal voltammeter” is a voltammetric device capable of determining the frequency domain properties of an
• the term “storage density” refers to the number of bits per volume and/or bits per molecule that can be stored. When the storage medium is said to have a storage density greater than one bit per molecule, this refers to the fact that a storage medium preferably comprises molecules wherein a single molecule is capable of storing at least one bit of information.
• the term “storage location” refers to a discrete domain or area in which a storage medium is disposed. When addressed with one or more electrodes, the storage location may form a storage cell. However if two storage locations contain the same storage media so that they have essentially the same oxidation states, and both storage locations are commonly addressed, they may form one functional storage cell.
• the term “storage medium” refers to a composition comprising a storage molecule of the invention, preferably bonded to a substrate.
• a substrate is a, preferably solid, material suitable for the attachment of one or more molecules.
• Substrates can be formed of materials including, but not limited to glass, plastic, silicon, minerals (e.g., quartz), semiconducting materials, ceramics, metals, etc.
• the term “voltammetric device” is a device capable of measuring the current produced in an electrochemical cell as a result of the application of a voltage or change in voltage.
• a voltage source is any source (e.g. molecule, device, circuit, etc.) capable of applying a voltage to a target (e.g., an electrode).
• working electrode is used to refer to one or more electrodes that are used to set or read the state of a storage medium and/or storage molecule.
• a device comprising a first electrode, a second electrode; and an electrolyte comprised of an ionic liquid composition, the ionic liquid composition comprising: one or more phosphonium based cations of the general formula:
• R'R 2 R 3 R 4 P where R 1 , R 2 , R 3 and R 4 are each independently a substituent group; and one or more anions, and wherein said electrolyte is electrically coupled to at least one of said first and second electrodes.
• the first electrode is comprised redox active molecules (ReAMs) as described in detail above.
• a molecular storage device comprising a working electrode and a counter electrode configured to afford electrical capacitance; and an ion conducting composition comprising: one or more phosphonium based cations of the general formula above and wherein the ion conducting composition is electrically coupled to at least the working and counter electrodes.
• the invention encompasses a molecular memory element that includes a switching device, a bit line and a word line coupled to the switching device and a molecular storage device accessible through the switching device.
• the molecular storage device is capable of being placed in two or more discrete states, wherein the molecular storage device is placed in one of the discrete states by signals applied to the bit and word line.
• the molecular storage device comprises a first electrode, a second electrode and an electrolyte of phosphonium based cations and suitable anions between the first and second electrode.
• Another embodiment encompasses molecular memory arrays comprising a plurality of molecular storage elements where each molecular storage element is capable of being placed in two or more discrete states.
• a 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.
• the molecular memory device may include an addressable array of molecular storage elements.
• An address decoder receives a coded address and generates word line signals corresponding to the coded address.
• a word line driver is coupled to the address decoder and produces amplified word line signals.
• the amplified word line signals control switches that selectively couple members of the array of molecular storage elements to bit lines.
• Read/write logic coupled to the bit lines determines whether the molecular memory device is in a read mode or a write mode. In a read mode, sense amplifiers coupled to each bit line detect an electronic state of the selectively coupled molecular storage elements and produce a data signal on the bit line indicative of the electronic state of the selectively coupled molecular storage elements. In a write mode, the read/write logic drives a data signal onto the bit lines and the selectively coupled molecular storage elements.
• Another embodiment encompasses devices including logic integrated with embedded molecular memory devices such as application specific integrated circuit (ASIC) and system on chip (SOC) devices and the like.
• ASIC application specific integrated circuit
• SOC system on chip
• Such implementations comprise one or more functional components formed monolithically with and interconnected to molecular memory devices.
• the functional components may comprise solid state electronic devices and/or molecular electronic devices.
• the molecular storage device is implemented as a stacked structure formed subsequent to and above a semiconductor substrate having active devices formed therein.
• the molecular storage device is implemented as a micron or nanometer sized hole in a semiconductor substrate having active devices formed therein.
• the molecular storage device is fabricated using processing techniques that are compatible with the semiconductor substrate and previously formed active devices in the semiconductor substrate.
• the molecular storage device comprises, for example, an
• electrochemical cell having two or more electrode surfaces separated by an electrolyte (e.g., a ceramic or solid electrolyte).
• electrolyte e.g., a ceramic or solid electrolyte.
• Storage molecules e.g., molecules having one or more oxidation states that can be used for storing information
• Other embodiments of the invention include the use of components independently selected from transistor switching devices including field effect transistor; a row decoder coupled to the word line; a column decoder coupled to the bit line; a current preamplifier connected to the bit line; a sense amplifier connected to the bit line, an address decoder that receives a coded address and generates word line signals corresponding to the coded address, a line driver coupled to the address decoder wherein the line driver produces amplified word line signals (optionally wherein the amplified word line signals control switches that selectively couple members of the array of molecular storage elements to bit lines), read/write logic coupled to the bit lines, wherein the read/write logic determines whether the molecular memory devices is in a read mode or a write mode, sense amplifiers coupled to each bit line, wherein when the device is in a read mode, sense amplifiers coupled to each bit line detect an electronic state of the selectively coupled molecular storage elements and produce a data signal on the bit line indicative of the electronic state of the selectively
• Additional embodiments have the memory arrays of the invention comprising volatile memory such as DRAM or SRAM, or non-volatile memory such as Flash or ferroelectric memory.
• a further embodiment provides arrays wherein the molecular storage device comprises an attachment layer formed on the first electrode, wherein the attachment layer comprises an opening and wherein the molecular material is in the opening and electronically coupled to the second electrode layer and an electrolyte layer formed on the attachment layer.
• Another embodiment encompasses a monolithically integrated device comprising logic devices configured to perform a particular function and embedded molecular memory devices of the invention coupled to the logic devices.
• the device may optionally comprise an application specific integrated circuit (ASIC), a system on chip (SOC), a solid state electronic devices or molecular electronic devices.
• ASIC application specific integrated circuit
• SOC system on chip
• the memory devices of this invention can be fabricated using standard methods well known to those of skill in the art.
• the electrode layer(s) are applied to a suitable substrate (e.g., silica, glass, plastic, ceramic, etc.) according to standard well known methods (see, e.g., Rai-Choudhury (1997) The Handbook of Microlithography, Micromachining, and Micro fabrication, SPIE Optical Engineering Press; Bard & Faulkner (1997) Fundamentals of Micro fabrication).
• a suitable substrate e.g., silica, glass, plastic, ceramic, etc.
• 200701236108 all of which are expressly incorporated by reference, in particular for the fabrication techniques outlined therein.
• Memory devices are operated by receiving an N-bit row address into row address decoder and an M-bit column address into column address decoder.
• the row address decoder generates a signal on one word line.
• Word lines may include word line driver circuitry that drives a high current signal onto word lines. Because word lines tend to be long, thin conductors that stretch across much of the chip surface, it requires significant current and large power switches to drive a word lines signal. As a result, line driver circuits are often provided with power supply in addition to power supply circuits (not shown) that provide operating power for the other logic. Word line drivers, therefore, tend to involve large components and the high speed switching of large currents tends to create noise, stress the limits of power supplies and power regulators, and stress isolation structures.
• a conventional memory array there are more columns (bit lines) than rows (word lines) because during refresh operations, each word line is activated to refresh all of storage elements coupled to that word line. Accordingly, the fewer the number of rows, the less time it takes to refresh all of the rows.
• the molecular memory elements can be configured to exhibit significantly longer data retention than typical capacitors, in the order of tens, hundreds, thousands or effectively, unlimited seconds. Hence, the refresh cycle can be performed orders of magnitude less frequently or omitted altogether. Accordingly, refresh considerations that actually affect the physical layout of a memory array can be relaxed and arrays of various geometry can be implemented. For example, memory array can readily be manufactured with a larger number of word lines, which will make each word line shorter.
• word line driver circuits can be made smaller or eliminated because less current is required to drive each word line at a high speed.
• shorter word lines can be driven faster to improve read/write access times.
• each row of memory locations can be provided with multiple word lines to provide a mechanism for storing multiple states of information in each memory location.
• Sense amplifiers are coupled to each bit line and operate to detect signals on bit lines 109 that indicate the state of a memory element coupled to that bit line, and amplify that state to an appropriate logic level signal.
• sense amplifiers may be implemented with substantially conventional designs as such conventional designs will operate to detect and amplify signals from a molecular memory element.
• some molecular storage elements provide very distinct signals indicating their state. These distinct signals may reduce the need for conventional sense amplifier logic as the state signal from a molecular storage device can be more readily and reliably latched into buffers of read/write logic than can signals stored in conventional capacitors. That is, the present invention can provide devices which are sufficiently large as to obviate the need for a sense amplifier.
• Read/write logic includes circuitry for placing the memory device in a read or write state.
• a read state data from molecular array is placed on bit lines (with or without the operation of sense amplifiers), and captured by buffers/latches in read/write logic.
• Column address decoder will select which bit lines are active in a particular read operation.
• read/write logic drives data signals onto the selected bit lines such that when a word line is activated, that data overwrites any data already stored in the addressed memory element(s).
• a refresh operation is substantially similar to a read operation; however, the word lines are driven by refresh circuitry (not shown) rather than by externally applied addresses.
• sense amplifiers if used, drive the bit lines to signal levels indicating the current state of the memory elements and that value is automatically written back to the memory elements.
• the state of bit lines is not coupled to read/write logic during a refresh. This operation is only required if the charge retention time of the molecules used is less than the operational life of the device used, for example, on the order of 10 years for Flash memory.
• a memory bus couples a CPU and molecular memory device to exchange address, data, and control signals.
• embedded system may also contain conventional memory coupled to memory bus.
• Conventional memory may include random access memory (e.g., DRAM, SRAM, SDRAM and the like), or read only memory ⁇ e.g., ROM, EPROM, EEPROM and the like). These other types of memory may be useful for caching data molecular memory device, storing operating system or BIOS files, and the like.
• Embedded system may include one or more input/output (I/O) interfaces that enable CPU to communicate with external devices and systems.
• I/O interface may be implemented by serial ports, parallel ports, radio frequency ports, optical ports, infrared ports and the like. Further, interface may be configured to communicate using any available protocol including packet-based protocols.
• Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes in a variety of batteries such as lithium primary batteries and lithium secondary batteries including lithium-ion batteries and rechargeable lithium metal batteries (sometimes collectively referred to herein as "lithium batteries").
• batteries such as lithium primary batteries and lithium secondary batteries including lithium-ion batteries and rechargeable lithium metal batteries (sometimes collectively referred to herein as "lithium batteries").
• lithium primary batteries include, but are not limited to: lithium/manganese dioxide (Li/Mn0 2 ), lithium/carbon monofluoride (Li/CFx), lithium/silver vanadium oxide (Li/Ag 2 V40n), Li-(CF) Xi lithium iron disulfide (Li/FeS 2 ), and lithium/copper oxide (Li/CuO).
• lithium-ion batteries include, but are not limited to: an anode of carbon, graphite, graphene, silicon(Si), tin (Sn), Si/Co doped carbon, metal oxide such as lithium titanate oxide (LTO), and a cathode of lithium cobalt oxide (LCO) (LiCo0 2 ), lithium manganese oxide (LMO) (LiMn 2 0 4 ), lithium iron phosphate (LFP) (LiFeP0 4 ), lithium nickel manganese cobalt oxide (NMC) (Li(NiMnCo)0 2 ), lithium nickel cobalt aluminum oxide (NCA) (Li(NiCoAl)0 2 ), lithium nickel manganese oxide (LNMO) (Li 2 NiMn 3 0 8 ), and lithium vanadium oxide (LVO).
• LCO lithium cobalt oxide
• LMO lithium manganese oxide
• LFP lithium iron phosphate
• NMC nickel manganese cobalt oxide
• NMC lithium nickel
• Examples of rechargeable lithium metal batteries include, but are not limited to: a lithium metal anode with a cathode of lithium cobalt oxide (LCO) (LiCo0 2 ), lithium manganese oxide (LMO) (Li/Mn 2 0 4 ), lithium iron phosphate (LFP) (LiFeP0 4 ), lithium nickel manganese cobalt oxide (NMC) (Li(NiMnCo)0 2 ), lithium nickel cobalt aluminum oxide (NCA) (Li(NiCoAl)0 2 ), lithium nickel manganese oxide (LNMO) (Li 2 NiMn 3 0 8 ), a lithium/sulfur battery, and a lithium/air battery.
• LCO lithium cobalt oxide
• LMO lithium manganese oxide
• LFP lithium iron phosphate
• NMC lithium nickel manganese cobalt oxide
• NCA lithium nickel cobalt aluminum oxide
• NCA lithium nickel manganese oxide
• Li 2 NiMn 3 0 8 lithium/
• a battery device comprises a single cell.
• FIG. 1 there is shown a schematic cross-sectional view of a single-cell battery 10, which includes a pair of electrodes: an anode 12 and a cathode 12' bonded to current collector plates 14,14', a separator film or membrane 16 sandwiched between the two electrodes, and an electrolyte solution 18 (not shown) which permeates and fills the pores of the separator and one or more of the electrodes.
• the battery electrode can be fabricated into a bipolar arrangement 20 where an anode 22 and a cathode 24 are attached on both sides of a "bipolar" current collector 26.
• Multi-cell batteries can be fabricated by arranging a number of single cells into a bipolar stack in order to provide needed higher voltage (and power).
• An exemplary multi-cell battery 30 is shown in FIG. 2B where the bipolar stack consists of four unit cells from 32 to 38. Each cell has a structure the same as that of the single cell 10 in FIG. 1. In the bipolar stack, each cell is separated from its neighboring cell with a single current collector plate that also acts as an ionic barrier between cells.
• Such a design optimizes the current path through the cell, reduces ohmic losses between cells, and minimizes the weight of packaging due to current collection. The result is an efficient battery with higher energy and power densities.
• the batteries are formed with an electrode/separator/electrode assembly in planar or flat structures. In other embodiments, the batteries are formed with electrode/separator/electrode assembly in wound spiral structures such as cylindrical and prismatic structures.
• the anode (negative) electrode active material can be any of a variety of materials depending on the type of chemistry for which the cell is designed.
• the cell is a lithium metal battery wherein the anode is made of a lithium or lithium alloy foil.
• an anode current collector may not be needed as lithium has enough electronic conductivity to serve this purpose as well.
• the cell is a lithium-ion battery wherein the anode active material is typically a graphite carbon which has layered structure allowing lithium ion intercalation/de-intercalation (insertion/desertion).
• the graphite anode is made from graphite powders which are held together by a binder material to form a porous structure.
• the anode material can be any of other materials that can serve as a host material (i.e. , can absorb and release) for lithium ions. Examples of such materials include, but are not limited to graphene, lithium alloys such as Li-Al, Li-Si, Li-Sn, and Li-Mg. Silicon and silicon alloys are known to be useful as anode electrode materials in lithium ion batteries.
• Examples include silicon alloys of tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) and mixtures thereof.
• metal oxides, silicon oxides or silicon carbides and their combinations with graphite can also be used as anode electrode materials.
• the cathode (positive) electrode active material can be any of a variety of materials depending on the type of chemistry for which the cell is designed.
• the cell is a lithium or lithium ion battery wherein the cathode active material is typically a metal oxide which has layered or tunneled structure allowing lithium ion
• the cathode electrode is made from metal oxide powders which are held together by a binder material to form a porous structure.
• the cathode active material can be any material that can serve as a host material for lithium ions. Examples of such materials include, but are not limited to materials described by the general formula Li x A].
• A comprises at least one transition metal selected from the group consisting of Mn, Co, and Ni
• M comprises at least one element selected from the group consisting of B, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, In, Nb, Mo, W, Y, and Rh
• x is described by 0.05 ⁇ x ⁇ 1 .1
• y is described by 0 ⁇ y ⁇ 0.5.
• the positive electrode material is LiNio.5Mno.5O2.
• the cathode active material is described by the general formula: Li x Mn 2- yMy02, where M is selected from Mn, Ni, Co, and/or Cr; x is described by 0.05 ⁇ x ⁇ 1.1 ; and y is described by 0 ⁇ y ⁇ 2.
• the cathode active material is described by the general formula: Li x M y Mri4- y 08, where M is selected from Fe and/or Co; x is described by 0 . 05 ⁇ x ⁇ 2; and y is described by 0 ⁇ y ⁇ 4.
• the cathode active material is given by the general formula Li x (Fe y Mi -y )P0 4 , where M is selected from transition metals such as Mn, Co and/or Ni; x is described by 0.9 ⁇ x ⁇ 1.1 ; and y is described by 0 ⁇ y ⁇ 1.
• the cathode active material is given by the general formula: Li(Nio.5- x Coo .5 -xM2 X )0 2 , where M is selected from Al, Mg, Mn, and/or Ti; and x is described by 0 ⁇ x ⁇ 0.2.
• the cathode material includes LiNiV0 2 .
• the electrode binder materials are 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), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyamide, polyimide, polyurethane, polyvinyl ether (PVE), or combinations thereof.
• PVdF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• SBR styrene-butadiene rubber
• PAN polyacrylonitrile
• ACM acrylate-type copolymer
• CMC carboxymethyl cellulose
• PAA polyacrylic acid
• PVE polyamide
• PVDF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• SBR st
• the separator materials are selected from but not limited to one or more of the following: films or membranes of micro porous polyolefin such as polyethylene (PE) and polypropylene (PP), polyvinylidene fluoride (PVdF), PVdF coated polyolefin, polytetrafluoroethylene (PTFE), polyvinyl chloride, resorcinol formaldehyde polymer, cellulose paper, non-woven polystyrene cloth, acrylic resin fibers, non-woven polyester film, polycarbonate membrane, and fiberglass paper, or combinations thereof.
• micro porous polyolefin such as polyethylene (PE) and polypropylene (PP), polyvinylidene fluoride (PVdF), PVdF coated polyolefin, polytetrafluoroethylene (PTFE), polyvinyl chloride, resorcinol formaldehyde polymer, cellulose paper, non-woven polystyrene cloth, acrylic resin fibers, non-woven polyester film, polycarbon
• the electrolyte is comprised of an ionic liquid composition or one or more ionic liquids or salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• R ! R 2 R 3 R 4 P and one or more anions and wherein: R 1 , R 2 , R 3 and R 4 are each independently a substituent group, such as but not limited to an alkyl group as described below. In some embodiments R 1 , R 2 , R 3 and R 4 are each independently an alkyl group comprised of 1 to 6 carbon atoms, more usually 1 to 4 carbon atoms. Any one or more of the salts may be liquid or solid at a temperature of 100 °C and below. In some embodiments, a salt is comprised of one cation and one anion pair. In other embodiments, a salt is comprised of one cation and multiple anions. In other embodiments, a salt is comprised of one anion and multiple cations. In further embodiments, a salt is comprised of multiple cations and multiple anions.
• the electrolyte is comprised of an ionic liquid having one or more phosphonium based cations, and one or more anions, wherein the ionic liquid composition exhibits thermodynamic stability up to 375 °C, a liquidus range greater than 400 °C, and ionic conductivity of at least 1 mS/cm, or at least 5 mS/cm, or at least 10 mS/cm at room
• the electrolyte is comprised of one or more salts having one or more phosphonium based cations, and one or more anions dissolved in a solvent, wherein the electrolyte composition exhibits ionic conductivity of at least 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 at room temperature.
• the electrolyte composition is comprised of one or more lithium salts having one or more anions selected from the group consisting of: PF 6 , (CF 3 ) 3 PF 3 ,
• the one or more conventional salts are lithium based salts including but not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium
• lithium triflate LiCF 3 S0 3
• Li(CF3CF 2 S0 2 ) 2 N or LiBETI bis(pentafluoromethanesulfonyl)imide
• the electrolyte composition further comprises one or more conventional, non-phosphonium salts.
• the electrolyte composition may be comprised of conventional salts, and wherein the phosphonium based ionic liquids or salts disclosed herein are additives.
• electrolyte composition is comprised of phosphonium based ionic liquids or salts and one or more conventional salts, present at a mole (or molar) ratio in the range of 1 : 100 to 1 : 1 , phosphonium based ionic liquid or salt:
• conventional salt examples include but are not limited to salts which are comprised of one or more cations selected from the group consisting of:
• the one or more conventional salts include but not limited to: tetraethylammonium te
• EMIIm bis(trifluoromethanesulfonyl)imide
• 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), ethylmethyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), ⁇ -butyrolactone (GBL), and ⁇ -valerolactone (GVL).
• solvents acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate
• the phosphonium electrolyte composition disclosed herein is in contact with the separator and the porous electrodes and may be applied onto the porous electrodes and separator prior to the cell assembly by any suitable means, such as by soaking, spray, screen printing, and the like.
• the phosphonium electrolyte composition disclosed herein may be applied onto the porous electrodes and separator after the cell assembly by any suitable means, such as by using a vacuum injection apparatus.
• 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 onto the electrodes directly.
• both of such free-standing gel electrolyte films or gel electrolyte coated electrodes are particularly suitable for high volume and high throughput manufacturing process, such as roll-to-roll winding process.
• Another advantage of such electrolyte film can function not only as the electrolyte but also as a separator.
• Such electrolyte films may also be used as an electrolyte delivery vehicle to precisely control the amount and distribution of the electrolyte solution thus improving cell assembly consistency and increasing product yield.
• the electrolyte film is comprised of a membrane as described in co-pending Patent Application Serial No. 12/027,924 filed on February 7, 2008, the entire disclosure of which is hereby incorporated by reference.
• the current collectors are selected from but not limited to one or more of the following: plates or foils or films of aluminum, carbon coated aluminum, stainless steel, carbon coated stainless steel, gold, platinum, silver, highly conductive metal or carbon doped plastics, or combinations thereof.
• a lithium metal battery comprises an anode made of lithium foil and cathode made of lithium nickel manganese oxide (LNMO) bonded to an aluminum current collector, a Celgard® polypropylene/polyethylene separator sandwiched between the two electrodes, and a phosphonium electrolyte as disclosed herein which are in contact with the separator and the electrodes.
• LNMO lithium nickel manganese oxide
• a lithium metal battery comprises an anode made of lithium foil and cathode made of lithium nickel manganese cobalt oxide (NMC) bonded to an aluminum current collector, a Celgard® polypropylene/polyethylene/polypropylene separator sandwiched between the two electrodes, and a phosphonium electrolyte as disclosed herein which are in contact with the separator and the electrodes.
• NMC nickel manganese cobalt oxide
• a lithium ion battery comprises an anode made of graphite particles bonded to a copper current collector and a cathode made of lithium cobalt oxide (LCO) bonded to an aluminum current collector, a Celgard®
• a battery is made as a stack of cell components.
• Anode active material particles and binder are adhered to one side of a current collector to form a single-side anode electrode.
• Cathode active material particles and binder are adhered to one side of a current collector to form a single-side cathode electrode.
• Anode and cathode active material particles and binder are adhered to both sides of a "bipolar" current collector to form a bipolar or double-sided electrode as illustrated in FIGS. 2A and 2B.
• a multi-cell stack is made by positioning a first Celgard® separator on top of the single-sided anode, a first bipolar electrode with cathode facing down on top of the first separator, a second separator on top of the first bipolar electrode, a second bipolar electrode with cathode side facing down on top of the second separator, a third separator on top of the second bipolar electrode, a third bipolar electrode with cathode side facing down on top of the third separator, a fourth separator on top of the third bipolar electrode, and a single-sided cathode on top of the fourth separator to form a 4-cell stack.
• a battery that includes many more cells can be made first forming multi-cell modules as described above.
• the modules are then stacked one on top of another until a desired number of modules has been reached.
• the anode/separator/cathode assembly is sealed partially around the edges.
• a sufficient amount of a phosphonium electrolyte disclosed herein is added to the assembly to fill the pores of the separator and the electrodes before the edges are sealed completely.
• a spiral-wound battery is formed.
• Anode active material particles and binder are adhered to both sides of current collector to form a double- sided anode electrode.
• Cathode active material particles and binder are adhered to both sides of a current collector to form a double-sided cathode electrode.
• An anode/separator/cathode stack or assembly is made by positioning the double-sided anode on top of a first Celgard® separator, a second separator on top of the anode electrode, and the double-sided cathode electrode on top of the second separator.
• the stack is wound into a tight cell core of either a round spiral to form a cylindrical structure or a flattened spiral to form a prismatic structure.
• the stack is then either partially sealed at the edges or placed into a can.
• a sufficient amount of any of the electrolytes described herein is added to the pores of the separator and the electrodes of the stack before final sealing.
• Such assembly can be automated in a roll-to-roll winding process.
• a key requirement for enhanced energy cycle efficiency and delivery of maximum power is a low cell equivalent series resistance (ESR).
• ESR electrospray resistance
• a phosphonium electrolyte composition disclosed herein, as described above replaces a conventional electrolyte 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 battery device is greatly improved, as can be seen in the Examples below.
• the phosphonium ionic liquid [0273] In another exemplary embodiment, the phosphonium ionic liquid
• the phosphonium ionic liquid [0274] In another exemplary embodiment, the phosphonium ionic liquid
• various phosphonium salts were dissolved in acetonitrile (ACN) solvent at 1.0 M concentration.
• ACN acetonitrile
• the resulting electrolytes exhibited ionic conductivity at room temperature 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.
• a phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 PC(CN)3 is added at 10 w%.
• the ionic conductivity of the electrolyte is increased by 109% at -30°C, and about 25% at +20°C and +60°C with the addition of the phosphonium additive.
• ionic conductivity of the conventional electrolyte solution increased by at least 25% as a result of the phosphonium additive.
• a conventional electrolyte solution of 1.0 M LiPF 6 in a mixed solvent of EC (ethylene carbonate), DEC (diethyl carbonate) and EMC (ethylmethyl carbonate) at 1 : 1 : 1 weight ratio noted as EC:DEC:EMC 1 : 1 : 1
• a phosphonium salt (CH 3 CH 2 CH 2 )(CH3CH2)(CH3) 2 PCF3BF 3 is added at 10 w%.
• the ionic conductivity of the electrolyte is increased by 36% at 20°C, 26% at 60°C, and 38% at 90°C with the addition of the phosphonium additive.
• ionic conductivity of the conventional electrolyte solution is increased by at least 25% as a result of the phosphonium additive.
• the separator is the largest single source of cell ESR. Therefore it is useful if a suitable separator has high ionic conductivity when soaked with electrolyte and minimum thickness.
• the separator is less than about 100 ⁇ thick. In another embodiment, the separator is less than about 50 ⁇ thick. In another embodiment, the separator is less than about 30 ⁇ thick. In yet another embodiment, the separator is less than about 10 ⁇ thick.
• novel phosphonium electrolyte compositions either as replacements or using phosphonium salts as additives in conventional electrolytes, disclosed herein is that they exhibit wider electrochemical voltage stability window compared to the conventional electrolytes.
• various phosphonium salts are dissolved in acetonitrile (ACN) solvent to form electrolyte solutions at 1.0 M concentration.
• ACN acetonitrile
• the electrochemical voltage window is determined in cells with a Pt working electrode and a Pt counter electrode and an Ag/Ag+ reference electrode.
• the stable voltage window is between about -3.0 V and +2.4 V.
• the voltage window is between about -3.2 V and +2.4 V.
• the voltage window is between about -2.4 V and +2.5 V.
• the voltage window is between about -1.9 V and +3.0 V.
• phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 is added at 10w%.
• the onset oxidation potential (positive stability window) is increased from 4.4 V for the electrolyte solution without phosphonium additive to a more positive potential up to 7.1 V by the use of phosphonium additive.
• the addition of phosphonium additive in concentrations between 10 and 25 w% increases the onset oxidation potential between about 2.1 and 2.7 V.
• single-cell batteries are comprised of a lithium metal or graphite anode, a NMC or LNMO or LCO cathode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 with various phosphonium salts as additives.
• the battery can be charged to 4.7 V.
• the battery can be charged to 4.6 V.
• the battery can be charged up to 4.4 V.
• the batteries are designed to operate at different cell voltages.
• the battery operates at cell voltages ranging from 4.7 V to 5.1 V.
• the battery operates at cell voltages ranging from 4.3 V to 4.6 V.
• the battery operates at cell voltages ranging from 4.2 V to 4.4 V.
• the battery operates at cell voltages ranging from 3.5 V to 4.1 V.
• phosphonium electrolyte compositions disclosed herein are used as additives with conventional electrolytes (which contain conventional, non- phosphonium salts), the phosphonium salt and the conventional salt are present in the electrolyte at a mole ratio in the range of 1/100 to 1/1, phosphonium salt/conventional salt.
• conventional electrolytes which contain conventional, non- phosphonium salts
• the phosphonium salt and the conventional salt are present in the electrolyte at a mole ratio in the range of 1/100 to 1/1, phosphonium salt/conventional salt.
• the conventional electrolyte salts that can be used in the conventional electrolytes.
• the one or more conventional salts are lithium based salts including but not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate or lithium triflate (L1CF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF 3 S0 2 )2N or Lilm), and lithium bis(pentafluoromethanesulfonyl)imide (Li(CF3CF 2 S0 2 ) 2 N or LiBETI).
• LiPF 6 lithium hexafluorophosphate
• LiBF 4 lithium tetrafluoroborate
• LiC10 4 lithium perchlorate
• LiAsF 6 lithium hexafluoroarsenate
• LiAsF 6 lithium tri
• an electrolyte is formed by dissolving phosphonium salt- (CH 3 CH 2 CH 2 )(CH3CH 2 )(CH3) 2 PCF 3 BF 3 in a solvent of acetonitrile (ACN) at 1.0 M
• the vapor pressure of ACN is lowered by about 39% at 25 °C, and by 38% at 105 °C.
• the significant suppression in vapor pressure by phosphonium salt is an advantage in reducing the flammability of the electrolyte solution, thus improving the safety of device operation.
• phosphonium additive (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH3) 2 PC(CN)3 is added at 20 w%.
• the fire self-extinguishing time is reduced by 53% with the addition of the phosphonium additive to the conventional electrolyte. This is an indication that the safety and reliability of lithium ion batteries can be substantially improved by using the phosphonium salt as an additive in the conventional lithium ion electrolytes.
• a further important advantage of the batteries formed according to the present invention compared to the prior art is their wide temperature range.
• the batteries made with the novel phosphonium electrolytes disclosed herein can be operated in a temperature range between about -30 °C and +90 °C, or between about -20 °C and +70 °C, or between -10 °C and +50 °C.
• the materials and structures disclosed herein it is now possible to make batteries that can function in extended temperature ranges. This makes it possible to implement these devices into broad applications that experience a wide temperature range during fabrication and/or operation.
• the above approaches to energy storage may be combined with electrochemical double layer capacitors (EDLCs) to form a hybrid energy storage system comprising an array of batteries and EDLCs.
• EDLCs electrochemical double layer capacitors
• Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes in electrochemical double layer capacitor (EDLCs).
• EDLCs electrochemical double layer capacitor
• an EDLC comprising: a positive electrode, a negative electrode, a separator between said positive and negative electrode; and an electrolyte.
• the electrolyte is comprised of an ionic liquid composition or one or more salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• the electrolyte is comprised of an ionic liquid having one or more phosphonium based cations, and one or more anions, wherein the ionic liquid composition exhibits thermodynamic stability up to 375 °C, a liquidus range greater than 400 °C, and ionic conductivity of at least 1 mS/cm, or at least 5 mS/cm, or at least 10 mS/cm at room
• the electrolyte is comprised of one or more salts having one or more phosphonium based cations, and one or more anions dissolved in a solvent, wherein the electrolyte composition exhibits ionic conductivity of at least 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 at room temperature.
• the electrolyte composition further comprises one or more conventional, non-phosphonium salts.
• the electrolyte composition may be comprised of conventional salts, and wherein the phosphonium based ionic liquids or salts disclosed herein are additives.
• electrolyte composition is comprised of phosphonium based ionic liquids or salts and one or more conventional salts, present at a mole (or molar) ratio in the range of 1 : 100 to 1 : 1 , phosphonium based ionic liquid or salt:
• conventional salt examples include but are not limited to salts which are comprised of one or more cations selected from the group consisting of:
• 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 + , imidazolium, pyrazolium, pyridinium, pyrazinium, pyrimidinium, pyridazinium, pyrrolidinium and one or more anions selected from the group consisting of: C1CV, BF 4 " , CF 3 S0 3 " , PF 6 " , AsF 6 " , SbF 6 _ , (CF 3 S0 2 ) 2 N ⁇ (CF3CF 2 S0 2 ) 2 N-, (CF 3 S0 2 ) 3 C " .
• the one or more conventional salts include but not limited to: tetraethylammonium tetrafluorborate (TEABF 4 ), triethylmethylammonium tetrafluoroborate (TEMABF 4 ), l-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ), 1-ethyl-l- methylpyrrolidinium tetrafluoroborate (EMPBF 4 ), l-ethyl-3-methylimidazolium
• EMIIm bis(trifluoromethanesulfonyl)imide
• the one or more conventional salts are lithium based salts including but not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate or lithium triflate (LiCF 3 S0 3 ), lithium
• Li(CF3CF 2 S0 2 ) 2 N or LiBETI bis(pentafluoromethanesulfonyl)imide
• the electrolyte composition is 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), ethylmethyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), ⁇ -butyrolactone (GBL), and ⁇ -valerolactone (GVL).
• solvents acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (
• the phosphonium electrolyte exhibits reduced flammability as compared to conventional electrolytes, and thus improves the safety of EDLC operation.
• 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 protective layer.
• SEI solid electrolyte interphase
• the protective layer acts to widen the electrochemical stability window, suppress EDLC
• Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes in a variety of EDLCs, wherein the electrode active materials are selected from any one or more in the group consisting of carbon blacks, graphite, grapheme; carbon-metal composites; polyaniline, polypyrrole, polythiophene; oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides of lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium, and combinations thereof.
• an EDLC device may be built using the phosphonium electrolyte composition disclosed herein, a cathode (positive electrode) made of high surface area activated carbon and an anode (negative electrode) made of lithium ion intercalated graphite.
• the EDLC formed is an asymmetric hybrid capacitor, called lithium ion capacitor (LIC).
• EDLCs may be combined with batteries to form a capacitor-battery hybrid energy storage system comprising an array of batteries and EDLCs.
• an electrolytic capacitor provided comprising: a positive electrode, a negative electrode, a separator between said positive and negative electrode; and an electrolyte.
• the electrolyte is comprised of an ionic liquid composition or one or more ionic liquids or salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• the electrolyte is comprised of an ionic liquid having one or more phosphonium based cations, and one or more anions, wherein the ionic liquid composition exhibits thermodynamic stability up to 375 °C, a liquidus range greater than 400 °C, and ionic conductivity of at least 1 mS/cm, or at least 5 mS/cm, or at least 10 mS/cm at room
• the electrolyte is comprised of one or more salts having one or more phosphonium based cations, and one or more anions dissolved in a solvent, wherein the electrolyte composition exhibits ionic conductivity of at least 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 at room temperature.
• the electrolyte composition is 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), ethylmethyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinyl ene carbonate (VC), vinyl ethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), ⁇ -butyrolactone (GBL), and ⁇ -valerolactone (GVL.
• solvents acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate
• the positive electrode - the anode is typically an aluminum foil with thin oxide film formed by electrolytic oxidation or anodization. While aluminum is the preferred metal for the anode, other metals such as tantalum, magnesium, titanium, niobium, zirconium and zinc may be used.
• the negative electrode - the cathode is usually an etched an etched aluminum foil.
• the phosphonium electrolyte exhibits reduced flammability as compared to conventional electrolytes, and thus improves the safety of the electrolytic capacitor operation.
• Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytes in dye sensitized solar cells (DSSCs).
• a DSSC comprising: a dye molecule attached anode, an electrolyte containing a redox system, and a cathode.
• the electrolyte is comprised of an ionic liquid composition or one or more ionic liquids or salts dissolved in a solvent, comprising: one or more phosphonium based cations of the general formula:
• R 1 , R 2 , R 3 and R 4 are each independently a substituent group; and one or more anions.
• the electrolyte is characterized as having one or more phosphonium based cations, and one or more anions, wherein the electrolyte composition exhibits least two or more of: thermodynamic stability, low volatility, wide liquidus range, ionic conductivity, chemical stability, and electrochemical stability.
• the electrolyte is characterized as having one or more phosphonium based cations, and one or more anions, wherein the electrolyte composition exhibits theiinodynamic stability up to a temperature of approximately 375 °C or greater, and ionic conductivity of at least 5 mS/cm, or at least 10 mS/cm, or at least 15 mS/cm at room temperature.
• Phosphonium ionic liquids, salts, and compositions according to embodiments of the present invention are well suited as electrolytic or electrolyte films.
• an electrolytic film comprising: a phosphonium ionic liquid composition applied to a substrate.
• an electrolytic film is provided comprising: one or more phosphonium ionic liquids or salts dissolved in a solvent applied to a substrate.
• one or more phosphonium ionic liquids or salts are dissolved in a solvent to form a coating solution. The solution is applied to a substrate by any suitable means, such as by spray, spin coating, and the like.
• the substrate is then heated to partially or completely remove the solvent, forming the electrolyte or ion-conducting film.
• solutions of ionic liquids, salts, and polymers, dissolved in suitable solvents are coated onto substrates, such as by spray or spin coating, and then the solvents -are partially or completely evaporated. This results in the formation of ion-conducting polymer gels/films.
• Such films are particularly suitable as electrolytes for batteries, EDLCs, and DSSCs, and as fuel cell membranes.
• thermodynamic stability low volatility and wide liquidus range of the phosphonium ionic liquids of the present invention are well suited as heat transfer medium.
• Some embodiments of the present invention provide a heat transfer medium, comprising 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, wherein the heat transfer medium exhibits thermodynamic stability up to a temperature of approximately 375 °C, a liquidus range of greater than 400 °C.
• the heat transfer medium of the invention is a high temperature reaction media.
• the heat transfer medium of the invention is a heat extraction media.
• the phosphonium ionic liquids of the present invention find use in additional applications.
• an embedded capacitor is proved.
• the embedded capacitor is comprised of a dielectric disposed between two electrodes, where the dielectric is comprised of an electrolytic film of a phosphonium ionic composition as described above.
• the embedded capacitor of the present invention may be embedded in an integrated circuit package. Further embodiments include "on-board" capacitor arrangements.
• phosphonium ionic liquids were prepared by either metathesis reactions of the appropriately substituted phosphonium salt with the appropriately substituted metal salt, or by reaction of appropriately substituted phosphine precursors with an appropriately substituted anion precursor.
• FIGS. 3 to 6 illustrate reaction schemes to make four exemplary
• Phosphonium ionic liquids were prepared. AgS0 3 CF 3 was charged into a 50 ml round bottom (Rb) flask and assembled to a 3 cm swivel frit. The flask was evacuated and brought into a glove box. In the glove box, di-n-proply ethyl methyl phosphonium iodide was added and the flask re-assembled, brought to the vacuum line, evacuated, and anydrous THF was vacuum transferred in. The flask was allowed to warm to room temperature and was 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.
• Thermogravimetric Analysis was performed on the material and the results are shown in FIG. 9A.
• Evolved Gas Analysis was also performed and the results are shown in FIG. 9B.
• TGA Thermogravimetric Analysis
• the water is removed under vacuum on a rotary evaporator to leave 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%.
• the phosphonium nitrate salt (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 5 minutes the solids are removed by filtration.
• the filtrate was cooled to obtain white crystals which were collected by filtration. Yield: 744 mg, 70%.
• the composition is confirmed by the ⁇ NMR spectrum as shown in FIG. 19A and the P NMR spectrum shown in FIG. 19B.
• Thermogravimetric Analysis (TGA) was performed on the material and the results are shown in FIG. 20.
• a ternary phosphonium ionic liquid composition comprising 1 :3: 1 mole ratio of (CH3CH2CH 2 )(CH3)3PCF3BF3/(CH3CH2CH2)(CH 3 CH2)(CH3) 2 P CF 3 BF 3
• phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH2)(CH3)2PC(CN)3 was prepared.
• This salt exhibits a low viscosity of 19.5 cP at 25 °C, melting point of- 10.0 °C, onset decomposition temperature of 396.1 °C, liquid range of 407 °C, ionic conductivity of 15.2 mS/cm, and electrochemical voltage window of -1.5 V to +1.5 V when measured in an electrochemical cell with a Pt working electrode and a Pt counter electrode and an Ag/Ag + reference electrode.
• Table 14 The results are summarized in Table 14 below.
• phosphonium salt (CH 3 CH 2 CH 2 )(CH3CH 2 )(CH 3 ) 2 PC(CN)3 was prepared.
• the salt was dissolved in a solvent of acetonitrile (ACN) with ACN/salt volume ratios ranging from 0 to 4.
• ACN acetonitrile
• the ionic conductivities of the resulting electrolyte solution were measured at room temperature and the results are shown in FIG. 22. As FIG. 22 shows, the ionic conductivity increases with the increase of ACN/salt ratio from 13.9 mS/cm at zero ratio (neat ionic liquid) to a peak value of 75 mS/cm at ratios between 1.5 and 2.0.
• phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 PC(CN)3 was prepared.
• the salt was dissolved in a solvent of propylene carbonate (PC) with PC/salt volume ratios ranging from 0 to 2.3.
• PC propylene carbonate
• the ionic conductivities of the resulting electrolyte solution were measured at room temperature and the results are shown in FIG. 23. As FIG. 23 shows, the ionic conductivity increases with the increase of PC/salt ratio from 13.9 mS/cm at zero ratio (neat ionic liquid) to a peak value of 22 mS/cm at ratios between 0.75 and 1.25.
• the electrochemical stable voltage 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 electrolytes exhibited ionic conductivity at room temperature 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 Echem window was between about -3.2 V and +2.4 V. In another arrangement, the Echem window was between about -3.0 V and +2.4 V. In yet another arrangement, the Echem window was between about -2.0 V and +2.4 V. Table 15
• phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH 2 XCH 3 ) 2 PCF 3 BF 3 was prepared and compared to an ammonium salt (CH 3 CH 2 )3(CH 3 )NBF 4 as control.
• the salts were dissolved in a solvent of acetonitrile (ACN) to form electrolyte solution at 1.0 M concentration.
• ACN acetonitrile
• the vapor pressure of the solutions was measured by pressure Differential Scanning Calorimetry (DSC) at temperatures from 25 to 105 °C. As illustrated in FIG.
• the vapor pressure of ACN is lowered by 39% with the phosphonium salt compared to 27% with the ammonium salt at 25 °C, 38% with the phosphonium salt compared to 13% for the ammonium salt at 105 °C.
• the significant suppression in vapor pressure by phosphonium salt is an advantage in reducing the flammability of the electrolyte solution thus improving the safety of battery operation.
• phosphonium salt was used as an additive in a lithium battery conventional electrolyte solution.
• the phosphonium salt was provided by Novolyte Technologies (part of BASF Group).
• phosphonium salt was used as an additive in a lithium battery standard electrolyte solution.
• the phosphonium salt (CH 3 CH 2 CH 2 )(CH3CH 2 )(CH 3 ) 2 PC(CN)3 was added to the standard electrolyte solution at 10 w%.
• the ionic conductivities of both the standard electrolyte solution and the solution with phosphonium additive were measured at different temperatures from -30 to +60 °C.
• the phosphonium additive improves the ionic conductivity of the electrolyte solution in a broad temperature range.
• the ionic conductivity is increased by 109% as a result of the phosphonium additive.
• the ionic conductivity is increased by 23% as a result of the phosphonium additive.
• the ionic conductivity is increased by about 25% as a result of the phosphonium additive.
• ionic conductivity of the standard electrolyte solution increased by at least 25% as a result of the phosphonium additive.
• phosphonium salt was used as an additive in a lithium battery standard electrolyte solution.
• a standard electrolyte solution of 1.0 M LiPF 6 in a mixed solvent of EC (ethylene carbonate), DEC (diethyl carbonate) and EMC (ethylmethyl carbonate) at 1 : 1 : 1 weight ratio noted as
• EC:DEC:EMC 1 : 1 : 1 was provided by Novolyte Technologies (part of BASF Group).
• the phosphonium salt (CH 3 CH 2 CH 2 )(CH 3 CH2)(CH 3 ) 2 PCF 3 BF 3 was added to the standard electrolyte solution at 10 w%.
• the ionic conductivities of both the standard electrolyte solution and the solution with phosphonium additive were measured at different temperatures from 20 to 90 °C. As illustrated in FIG. 27, the phosphonium additive improves the ionic conductivity of the electrolyte solution in a broad 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
• ionic conductivity of the standard electrolyte solution increased by at least 25% as a result of the phosphonium additive.
• a coin cell is comprised of a disk shipped anode and a cathode electrode of 14 mm diameter, a separate of 19 mm diameter sandwiched between the two electrodes, and an impregnating electrolyte solution.
• the anode was prepared from 200 ⁇ thick lithium foil or 100 ⁇ thick graphite electrode.
• the cathode was prepared from 100 ⁇ thick NMC (lithium nickel manganese cobalt oxide) or 60 ⁇ thick LNMO (lithium nickel manganese oxide).
• the separator was prepared from 25 ⁇ thick Celgard® polypropylene/polyethylene/polypropylene separator (PP/PE/PP 2325). Both the two electrodes and the separator were impregnated with an electrolyte solution containing 1.0 M LiPF 6 in a mixed solvent such as EC:DEC or
• FIG. 29 shows the charge - discharge curve for a coin cell of Li/NMC with 1.0 M LiPF 6 in EC:DEC 1 : 1 with 10 w% phosphonium additive (CH 3 CH 2 )3(CH 3 )PBF 4 .
• the cell was first charged to 4.6 V then discharged to 2.0 V at a current density of 1.6 mA/cm 2 resulting in a specific capacity of 190 mAh/g active material.
• a pouch cell is comprised of an anode and a cathode electrode of 10 mm x 20 mm, a separator of 12 mm x 22 mm sandwiched between the two electrodes, and an impregnating electrolyte solution.
• the pouch cell is optionally comprised of a third lithium reference electrode so that the potential at the anode and cathode can be measured.
• the anode was prepared from 200 ⁇ lithium foil or 200 ⁇ thick graphite electrode.
• the cathode was prepared from 100 ⁇ thick NMC (lithium nickel manganese cobalt oxide) or 60 ⁇ thick LNMO (lithium nickel manganese oxide).
• the separator was prepared from 25 ⁇ thick Celgard®
• pouch cells assembled according to Example 54, are comprised of a Li anode, a LNMO cathode, a Li reference electrode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC (fluoro ethylene carbonate) with a phosphonium additive (CH 3 CH 2 )3(CH 3 )PBF 4 at concentrations ranging from 0 to 25 w%.
• Linear sweep voltammetry was recorded at 10 mV/s to determine the electrochemical oxidation stability window. As illustrated in FIG. 31, the potential at which bulk electrolysis occurs was shifted dramatically in the positive direction with phosphonium additive.
• FIG. 31 the potential at which bulk electrolysis occurs was shifted dramatically in the positive direction with phosphonium additive.
• onset oxidation or decomposition potential where the current density reached 10 mA/cm as a function of the phosphonium additive concentration.
• the numerical values are shown in Table 19 below.
• the onset oxidation potential was increased from 4.4 V for the electrolyte solution without phosphonium additive to a more positive potential up to 7.1 V by the use of phosphonium additive.
• including the phosphonium additive in concentrations between 10 and 25 w% increased the onset oxidation potential between about 2.1 and 2.7 V.
• SEI solid electrolyte interphase
• pouch cells assembled according to Example 54, are comprised of a Li anode, a LNMO cathode, a Li reference electrode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC (fluoroethylene carbonate) with and without a phosphonium additive [1 :3 : 1 ratio
• pouch cells assembled according to Example 54, are comprised of a Li anode, a NMC cathode, a Li reference electrode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC (fluoroethylene carbonate) with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF at 10 w%.
• Linear sweep voltammetry was recorded at 10 mV/s to determine the electrochemical oxidation stability window. The results are shown in FIG. 34.
• the onset oxidation potential was increased from 4.4 V for the electrolyte solution without phosphonium additive to 4.8 V with phosphonium additive, an increase of 0.4 V.
• pouch cells assembled according to Example 54, are comprised of a Li anode, a NMC cathode, a Li reference electrode, and an electrolyte solution containing 1.0 M LiPF 6 in EC: DEC 1 : 1 with and without a phosphonium additive [1 :3: 1 ratio (CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P/
• pouch cells assembled according to Example 54, are comprised of two Li electrodes, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 PCF 3 BF 3 at 10 w%.
• the cells were aged at 45 °C for a month.
• AC impedance was performed with a PAR VersaSTAT 4-200 potentiostat/impedance analyzer at 0 V bias, 5 mV amplitude, frequencies from 100 KHz to 10 mHz. As shown in FIG.
• the impedance of the cell without the phosphonium additive increased by three times after the aging.
• impedance of the cell with the phosphonium additive did not increase but decreased slightly.
• SEI solid electrolyte interphase
• coin cells assembled according to Example 53, are comprised of a Li electrode and a graphite electrode, and an electrolyte solution containing 1.0 M LiPF 6 in
• EC:DEC 1 1 and 20 w% FEC (fluoroethylene carbonate) with and without a phosphonium additive (CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 PPF6 at 5 w%.
• a phosphonium additive CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 PPF6 at 5 w%.
• the lithium ion intercalation property of the graphite electrode can be studied.
• Charge-discharge capacities were measured at 1.4 mA/cm (0.5 C rate) with a MTI battery analyzer. The results are shown in FIG. 37. The charge and discharge capacities were increased by 28% and 26% respectively with the addition of phosphonium additive.
• coin cells assembled according to Example 53, are comprised of a Li electrode and a graphite electrode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 and 20 w% FEC (fluoroethylene carbonate) with and without a phosphonium additive (CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 PBF 4 at 5 w%.
• Charge-discharge capacities were measured at 1.4 mA/cm (0.5 C rate) with a MTI battery analyzer. The results are shown FIG. 38. The charge and discharge capacities were increased by 35% and 36% respectively with the addition of phosphonium additive.
• coin cells assembled according to Example 53, are comprised of a Li anode, a LNMO cathode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at 10 w%.
• Charge and discharge capacities were measured between 3.0 V and 4.7 Vat 0.2 mA/cm (0.3 C rate) 0.3 mA/cm 2 (0.5 C rate) respectively with a MTI battery analyzer. The results are shown in FIG. 39. The charge and discharge capacities were increased by 1 1 % with the addition of phosphonium additive.
• coin cells assembled according to Example 53, are comprised of a Li anode, a NMC cathode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC 1 : 1 with and without a phosphonium additive (CH 3 CH 2 ) 3 (CH 3 )PBF 4 at 10 w%.
• electrochemical stability window suppress battery degradation or decomposition reactions and hence improve battery cycle life.
• coin cells assembled according to example 53, are comprised of a graphite anode, a LCO cathode, and an electrolyte solution containing 1.0 M LiPF 6 in EC:DEC:EMC 1 : 1 : 1 and 20 w% FEC with and without a phosphonium additive at 2 w%: Additive 1 - [1 :3: 1 ratio

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