Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
• • 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
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
• • 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
• • 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
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present disclosure relates generally to methods for forming electrolyte compositions, and more particularly to the synthesis of an electrolyte solution for use in ultracapacitors.
• Energy storage devices such as ultracapacitors may be used in many applications where a discrete power pulse is required. Such applications range from cell phones to hybrid vehicles.
• An important characteristic of an ultracapacitor is the energy density that it can provide.
• the energy density of the device which can comprise two or more carbon-based electrodes separated by a porous separator and/or an organic electrolyte, is largely determined by the properties of the electrolyte.
• ultracapacitors comprises tetraethyl ammonium tetrafluoroborate (TEA-TFB) salt dissolved in a solvent such as acetonitrile.
• TEA-TFB tetraethyl ammonium tetrafluoroborate
• This electrolyte system has a number of beneficial properties, including salt solubility and ion conductivity.
• TEA-TFB One factor that is important in the development of electrolyte solutions is cost. Due to its relatively expensive synthesis and purification, commercially- available TEA-TFB is expensive. An example synthesis of TEA-TFB is disclosed in U.S. Patent No. 5,705,696. The example process involves reacting tetraalkyl ammonium halides with metal
• a method of forming an electrolyte solution comprises combining ammonium tetrafluoroborate and a quaternary ammonium halide salt in a liquid solvent to form a quaternary ammonium tetrafluoroborate and an ammonium halide, and removing the ammonium halide from the solvent to form an electrolyte solution.
• the reaction can be carried out entirely at about room temperature. For instance, in an example embodiment, the combining and the removing are performed at about 25°C. In further embodiments, a stoichiometric excess of ammonium tetrafluoroborate is used to minimize the concentration of halide ions in the product and decrease the reaction time.
• the resulting product is an electrolyte solution comprising a quaternary ammonium tetrafluoroborate salt dissolved in a solvent, wherein a concentration of chloride ions in the electrolyte solution is less than 1 ppm, a concentration of bromide ions in the electrolyte solution is less than 1000 ppm, a concentration of potassium ions in the electrolyte solution is less than 50 ppm, a concentration of sodium ions in the electrolyte solution is less than 50 ppm, a concentration of water in the electrolyte solution is less than 20 ppm, and/or a concentration of ammonium ions in the electrolyte solution is greater than 1 ppm.
• FIG. 1 is a schematic illustration of a button cell according to one embodiment
• Fig. 2 is CV curve for an electrolyte solution prepared using a stoichiometric ratio of reactants
• Fig. 3 is a CV curve for an electrolyte solution prepared using a stoichiometric excess of ammonium tetrafluoroborate.
• a method of making quaternary ammonium tetrafluoroborate involves reacting one or more quaternary ammonium halides with ammonium tetrafluoroborate in an organic solvent.
• the reaction products are quaternary ammonium tetraflurorborate and ammonium bromide.
• the quaternary ammonium tetraflurorborate is soluble in the organic solvent, while the ammonium bromide forms as a precipitate.
• the precipitated NFUBr can be filtered to form a solution of, for example, TEA-TFB in an organic solvent such as acetonitrile.
• the complete reaction is carried out at about room temperature under constant agitation.
• the present method uses ammonium tetrafluoroborate as a reactant. While impurities derived from the conventionally-used metal compounds can contaminate the electrolyte and degrade device performance through Faradaic reactions, residual ammonium ions from the ammonium tetrafluoroborate reactant are not harmful to capacitor performance.
• the ammonium tetrafluoroborate reactant can have a moisture content of less than 1000 ppm (e.g., less than 500 ppm or less than 100 ppm, including 0 ppm) and a total inorganic (e.g., metal) impurity content of less than 4000 ppm (e.g., less than 3000ppm or less than 2000 ppm, including 0 ppm).
• Example inorganic or metal impurities, the presence of which can be minimized in the ammonium tetrafluoroborate include sodium, potassium, calcium, iron, magnesium, phosphorus, cobalt, nickel, chromium, lead, arsenic, aluminum and zinc.
• a concentration of each metal ion in the electrolyte solution is less than 1 ppm.
• a range expressed as "less than” a certain value excludes that value but otherwise includes all non-negative rational numbers (including zero) within the range.
• a range expressed as "at most” (i.e., less than or equal to) a certain value includes that value and includes all non- negative rational numbers (including zero) within the range.
• TFB ammonium tetrafluoroborate
• Table 1 Properties of ammonium tetrafluoroborate (ATFB or TFB) reactant are summarized in Table 1.
• the analytical techniques used to measure the relevant parameters include thermogravimetric analysis and differential scanning calorimetry (TGA/DSC), Karl Fisher analysis (KF), and inductively coupled plasma mass spectrometry (ICP-MS).
• Suitable quaternary ammonium halides include spiro-bi-p rrolidinium bromide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, triethyl methyl ammonium bromide, trimethyl ethyl ammonium bromide, and dimethyl diethyl ammonium bromide.
• the ammonium halides may include ammonium chlorides.
• Corresponding quaternary ammonium tetrafluoroborates include spiro-bi- pyrrolidinium tetrafluoroborate, tetramethyl ammonium tetrafluoroborate, tetraethyl ammonium tetrafluoroborate, tetrapropyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, triethyl methyl ammonium tetrafluoroborate, trimethyl ethyl ammonium tetrafluoroborate, and dimethyl diethyl ammonium tetrafluoroborate.
• the quaternary ammonium halide reactant can have a moisture content of less than 10000 ppm (e.g., less than 2000 ppm or less than 1000 ppm, including 0 ppm) and a total inorganic impurity content of less than 50 ppm (e.g., less than 20 ppm or less than 10 ppm, including 0 ppm).
• TEA-Br tetraethyl ammonium bromide
• TEMA-Br triethylmethyl ammonium bromide
• TEMA-C1 triethylmethyl ammonium chloride
• example organic solvents include dipolar aprotic solvents such as propylene carbonate (PC), butylene carbonate (BC), ⁇ -butyrolactone, acetonitrile (ACN), propionitrile (PN), and methoxyacetonitrile.
• PC propylene carbonate
• BC butylene carbonate
• ACN acetonitrile
• PN propionitrile
• methoxyacetonitrile the initial moisture content can be less than 200 ppm (e.g., less than 100 ppm or less than 50 ppm, including 0 ppm).
• purity can be determined using gas chromatography-mass spectrometry (GC-MS) or nuclear magnetic resonance (NMR).
• a quaternary ammonium halide can be combined with a stoichiometric excess of ammonium tetrafluoroborate.
• the electrolyte solution can be formed using a stoichiometric amount of ammonium tetrafluoroborate, or by using up to 150% (by mole) excess ammonium tetrafluoroborate.
• a molar ratio of quaternary ammonium halide to ammonium tetrafluoroborate can range from 1 : 1 to 1 : 1.5 (e.g., 1 :1, 1 : 1.1 , 1 : 1.2, 1 : 1.3, 1 : 1.4 or 1 : 1.5).
• the resulting solution can include an excess of BF 4 and NH 4 ions.
• Excess ammonium ions from the ammonium tetrafluoroborate can beneficially scavenge halide ions during the synthesis.
• Halide ions can also contribute to unwanted Faradaic reactions in the resulting electrolyte.
• TEMA-TFB in ACN for example, can be synthesized via enhanced mixing of TEMA-Br and ATFB in ACN.
• TEMA-Br and ATFB have very low solubility in ACN, which means that only the amounts of these reactants that are dissolved and in solution as ions can react to form the product. The synthesis is thus mass transfer limited and can take considerably long reaction times for reaction completion.
• An electrolyte solution comprises a quaternary ammonium tetrafluoroborate salt dissolved in a solvent, wherein a concentration of chloride ions in the electrolyte solution is less than 1 ppm, a concentration of bromide ions in the electrolyte solution is less than 1000 ppm (e.g., less than 800, less than 700 ppm, or less than 600 ppm, including 0 ppm); a concentration of ammonium ions in the electrolyte solution is greater than 1 ppm (including 0 ppm), a concentration of potassium ions in the electrolyte solution is less than 50 ppm (e.g., less than 40 ppm, less than 30 ppm or less than 10 ppm, including 0 ppm), a concentration of sodium ions in the electrolyte solution is less than 50 ppm (e.g., less than 30 ppm or less than 10 ppm, including 0 ppm), and
• Example electrolyte solutions are TEA-TFB, triethyl methyl ammonium
• TEMA-TFB tetrafluoroborate in acetonitrile
• TEMA-TFB can be synthesized from TEMA- Br or from TEMA-Cl. The density is determined by mechanical oscillation.
• a conductivity of the electrolyte solution at 25°C can be at least 45 mS/cm (e.g., at least 45, 50, 55 or 60 mS/cm).
• a total concentration of the quaternary ammonium tetrafluoroborate salt in the electrolyte solution can range from 0.1M to 2M (e.g., 0.1, 0.2, 0.5, 1, 1.2, 1.5 or 2M).
• the electrolyte solution can appear clear "water white” and have a density of about 0.86-0.88 g/ml.
• the electrolyte solution can be stored, for example in a stainless steel drum, at room temperature under inert atmosphere (e.g., dry nitrogen) and under positive pressure.
• inert atmosphere e.g., dry nitrogen
• the electrolyte is filled into an argon-purged metal can, which is sealed using a polymer plug and, in turn, encapsulated within a nitrogen-purged and evacuated Shield Pack (West Monroe, LA) barrier liner.
• the electrolyte solution can be incorporated into an ultracapacitor.
• a pair of electrodes is separated by a porous separator and the electrode/separator/electrode stack is infiltrated with the electrolyte solution.
• the electrodes may comprise activated carbon that has optionally been mixed with other additives.
• the electrodes can be formed by compacting the electrode raw materials into a thin sheet that is laminated to a current collector via an optional conductive adhesion layer and an optional fused carbon layer.
• the disclosed electrolytes can also be incorporated into other electrochemical electrode/device structures such as batteries or fuel cells.
• activated carbon examples include coconut shell-based activated carbon, petroleum coke-based activated carbon, pitch-based activated carbon, polyvinylidene chloride-based activated carbon, polyacene-based activated carbon, phenolic resin-based activated carbon, polyacrylonitrile-based activated carbon, and activated carbon from natural sources such as coal, charcoal or other natural organic sources.
• suitable porous or activated carbon materials are disclosed in commonly-owned U.S. Patent Application Nos. 12/970,028 and 12/970,073, the entire contents of which are incorporated herein by reference.
• Activated carbon can be characterized by a high surface area.
• High surface area electrodes can enable high energy density devices.
• high surface area activated carbon is meant an activated carbon having a surface area of at least 100 m 2 /g (e.g., at least 100, 500, 1000 or 1500 m 2 /g).
• the electrodes used to form an ultraca acitor can be configured identically or differently from one another.
• at least one electrode comprises activated carbon.
• An electrode that includes a majority by weight of activated carbon is referred to herein as an activated carbon electrode.
• an activated carbon electrode includes greater that about 50 wt.% activated carbon (e.g., at least 50, 60, 70, 80, 90 or 95 wt.% activated carbon).
• the activated carbon comprises pores having a size of ⁇ 1 nm, which provide a combined pore volume of > 0.3 cm 3 /g; pores having a size of from > 1 nm to ⁇ 2 nm, which provide a combined pore volume of > 0.05 cm 3 /g; and ⁇ 0.15 cm 3 /g combined pore volume of any pores having a size of > 2 nm.
• Electrodes can include one or more binders. Binders can function to provide mechanical stability to an electrode by promoting cohesion in loosely assembled particulate materials. Binders can include polymers, co-polymers, or similar high molecular weight substances capable of binding the activated carbon (and other optional components) together to form porous structures.
• binders include polytetrafluoroethylene (PTFE), polyvinylidene fluoride, or other fluoropolymer particles; thermoplastic resins such as polypropylene, polyethylene, or others; rubber-based binders such as styrene-butadiene rubber (SBR); and combinations thereof.
• PTFE can be utilized as a binder.
• fibrillated PTFE can be utilized as a binder.
• an electrode can include up to about 20 wt% of binder (e.g., up to about 5, 10, 15, or 20 wt%).
• An electrode can also include one or more conductivity promoters.
• a conductivity promoter functions to increase the overall conductivity of the electrode.
• Exemplary conductivity promoters include carbon black, natural graphite, artificial graphite, graphitic carbon, carbon nanotubes or nanowires, metal fibers or nanowires, graphenes, and combinations thereof.
• carbon black can be used as a conductivity promoter.
• an electrode can include up to about 10 wt% of a conductivity promoter.
• an electrode can include from about 1 wt% to about 10 wt% of conductivity promoter (e.g., 1 , 2, 4, or 10 wt %).
• Example ultracapacitors can include one activated carbon electrode or two activated carbon electrodes.
• one electrode can include a majority of activated carbon and the other electrode can include a majority of graphite.
• the electrolyte solution can be characterized by measurements performed on the electrolyte solution itself, as well as by measurements performed on test cells that incorporate the electrolyte solution.
• FIG. 1 An embodiment of an EDLC, a button cell, is shown in Figure 1.
• the button cell 10 includes two current collectors 12, two sealing members 14, two electrodes 16, a separator 18, and an electrolyte solution 20.
• Two electrodes 16, each having a sealing member 14 disposed around the periphery of the electrode, are disposed such that the electrode 16 maintains contact with a current collector 12.
• a separator 18 is disposed between the two electrodes 16.
• An electrolyte solution 20 is contained between the two sealing members.
• An activated carbon-based electrode having a thickness in the range of about 50- 300 micrometers can be prepared by rolling and pressing a powder mixture comprising 80-90 wt.% microporous activated carbon, 0-10 wt.% carbon black and 5-20 wt.% binder (e.g., a fluorocarbon binder such as PTFE or PVDF).
• a liquid can be used to form the powder mixture into a paste that can be pressed into a sheet and dried.
• Activated carbon- containing sheets can be calendared, stamped or otherwise patterned and laminated to a conductive adhesion layer to form an electrode.
• the button cells were fabricated using activated carbon electrodes
• the activated carbon electrodes were fabricated by first mixing activated carbon with carbon black in an 85:5 ratio.
• PTFE was added to make a 85 :5: 10 ratio of carbon:carbon black:PTFE.
• the powder mixture was added to isopropyl alcohol, mixed, and then dried.
• the dried material was pressed into a 10 mil thick pre- form.
• the pre-forms were then laminated over a conductive adhesion layer (50 wt.% graphite, 50 wt.% carbon black), which was formed over a fused carbon-coated current collector.
• the current collectors were formed from platinum foil, and the separator was formed from cellulose paper. Prior to assembly, the activated carbon electrodes and the separator were soaked in an electrolyte. A thermoset polymer ring is formed around the periphery of the assembly to seal the cell, which is filled with an organic electrolyte such as tetraethylammonium-tetrafluoroborate (TEA-TFB) in acetonitrile. Prior to sealing the cell, an extra drop of the electrolyte was added to the cell.
• TEA-TFB tetraethylammonium-tetrafluoroborate
• Electrochemical experiments were used to test the cell, included cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge. Cyclic voltammetry experiments were performed at a scan rate of 20 mV/sec within various potential windows over the maximum range of 0 to 4.5 V. The EIS test included measuring impedance while applying an AC perturbation with an amplitude of 10 mV at a constant DC voltage of 0 V over the frequency range of 0.01 -10,000 Hz. Galvanostatic charge / discharge experiments were performed at a current magnitude of 10mA.
• CV cyclic voltammetry
• EIS electrochemical impedance spectroscopy
• galvanostatic charge/discharge were performed at a scan rate of 20 mV/sec within various potential windows over the maximum range of 0 to 4.5 V.
• the EIS test included measuring impedance while applying an AC perturbation with an amplitude of 10 mV at a constant DC voltage of 0 V over
• the energy density of the device was calculated using the Integrated Energy Method.
• the galvanostatic data (potential vs. time data) was numerically integrated and multiplied by the discharge current to obtain the energy delivered by the device (in Ws) between two potentials Vi and V 2 .
• the device capacitance (C dev i ce in Farads) can be calculated from the energy according to the following relationship:
• the stable voltage which is the maximum voltage the device can withstand without appreciable Faradaic reactions, was measured from a series of cyclic voltammetry (CV) experiments performed over several different voltage windows. From the CV data, a Faradaic Fraction was measured using the following equation:
• Faradaic Fraction [0051] The charge (Q) during anodic and cathodic scans was calculated by integrating the CV curve and dividing the result by the scan rate at which the CV was performed. The stable voltage was defined as the potential at which the Faradaic Fraction is approximately 0.1.
• the energy density at the stable voltage which is the maximum voltage the device can withstand without appreciable Faradaic reactions, was calculated using the following relation where device is the device capacitance (in Farads), Vi is the stable voltage, V2 is Vi / 2, and Volume is the device volume in liters:
• the suspension was filtered to remove the precipitate.
• the conductivity of the electrolyte solution was 64 mS/cm.
• the resulting electrolyte solution was incorporated into a button cell as described above using activated carbon having a surface area of 1800 m 2 /g.
• the energy density of the button cell was 15 Wh/1. Referring to Fig. 2, however, significant Faradaic reactions are seen with the electrolyte.
• the bromide ion content in the electrolyte solution determined by ion chromatography was 7123 ppm. The bromide ions cause Faradaic reactions and, together with other halide ions, undesirably increase the cell's ESR and reduce cycle life.
• the suspension was filtered to remove the precipitate.
• the conductivity of the electrolyte solution was 64 mS/cm.
• the resulting electrolyte solution was incorporated into a button cell as described above using activated carbon having a surface area of 1800 m 2 /g.
• the energy density of the button cell was 17 Wh/1.
• the CV curve showed no Faradaic reactions.
• the bromide ion content in the electrolyte solution determined by ion chromatography data was 751 ppm.
• the chloride ion content was less than 0.05 ppm, and concentration of ammonium ions was 245 ppm.
• a step-wise addition of reactants means that at least one (preferably both) of the reactants is introduced to the mixture both before and after the introduction of the other reactant.
• a step-wise addition of reactants A and B can include the introduction of the reactants in the following example sequences: ABA, BAB, ABAB, BABA, ABABA, BABAB, etc.
• Electrolyte solutions were prepared using ammonium tetrafluoroborate and spiro- bi-pyrrolidinium bromide in acetonitrile.
• the spiro-bi-pyrrolidinium bromide was synthesized from 1,4-dibromobutane, ammonium bicarbonate and the controlled addition of pyrollidine.
• the reactant synthesis involves the liberation of water and carbon dioxide, in addition to ammonium bromide, which can be separated as a precipitate.
• Synthesis parameters include the rate of pyrollidine addition, as well as the temperature (Tl) of the solution during addition of the pyrollidine, the reaction temperature (T2) at which the reaction proceeds to form the spiro-bi-pyrrolidinium bromide reactant, and the reaction temperature (T3) at which spiro-bi-pyrrolidinium bromide is combined with ammonium tetrafluoroborate to form spiro-bipyrrolidium tetrafluoroborate (SBP-TBF).
• a temperature of the mixture during pyrollidine addition can range from about 25-35°C
• a temperature of the mixture during reaction to form spiro-bi-pyrrolidinium bromide can range from about 30-40°C
• a final reaction temperature (T3) of the spiro-bi-pyrrolidinium bromide with the ammonium tetrafluorob orate can be about 20°C (e.g., about 20°C or about 25°C).
• the SBP-TBF electrolyte may be more electrochemically stable than the TEA-TFB electrolyte, particularly at negative potentials.
• Electrolyte solutions of SBP-TBF in acetonitrile and TEA-TFB in acetonitrile were evaluated in 2.7 V and 2.8V symmetric test cells and in 2.7V tuned test cells.
• the same activated carbon material was used in each of the positive and negative electrode, while in the tuned test cells, the activated carbon material incorporated into the positive electrode was different than the activated carbon material incorporated into the negative electrode.
• the pore size distribution of the carbon in the positive electrode tends toward larger pores than the pore size distribution of the carbon in the negative electrode (interacting with the typically smaller electrolyte anions).
• the capacitance of a 1.5M electrolyte solution of SBP-TBF in acetonitrile was evaluated in both symmetric and tuned cells.
• the initial capacitance at 2.7V was between about 425 and 450 Farads.
• the symmetric cell capacitance decreased to within the range of about 375-385 Farads after 100 hrs, and to within the range of about 350-375 Farads after 400 hrs.
• the tuned cells the initial capacitance at 2.7V was between about 575 and 600 Farads.
• the tuned cell capacitance decreased to within the range of about 500-525 Farads after 100 hrs.
• ISE ion selective electrode
• organic samples of the electrolyte can be diluted into quasi-aqueous solutions. For example, dilution of 0.25 g of TEMA-TFB in ACN in 25 mL of deionized water will produce a quasi-aqueous solution that can be measured for bromide ion concentration via the ion selective electrode method. Millivolt (mV) readings can then be correlated to a calibration curve prepared with aqueous solutions of known concentrations of bromide to determine the bromide content in the electrolyte sample.
• An ionic strength adjustor such as an aqueous solution of NaN0 3 may be added to the solution to reduce any interference from other ions. Results show good agreement with ion chromatography results.
• the ion selective electrode method is less capital intensive, specific and offers quick results for process and quality control of the electrolyte synthesis.
• Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, examples include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. [0081] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.
• references herein refer to a component of the present invention being “configured” or “adapted to” function in a particular way.
• a component is “configured” or “adapted to” embody a particular property, or function in a particular manner, where such recitations are structural recitations as opposed to recitations of intended use.
• the references herein to the manner in which a component is “configured” or “adapted to” denotes an existing physical condition of the component and, as such, is to be taken as a definite recitation of the structural characteristics of the component.

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