TW201423790A - Electrolyte synthesis for ultracapacitors - Google Patents

Abstract

A method of forming an electrolyte solution involves combining ammonium tetrafluoroborate and a quaternary ammonium halide in a liquid solvent to form a quaternary ammonium tetrafluoroborate and an ammonium halide. The ammonium halide precipitate is removed from the solvent to form an electrolyte solution. The reactants can be added step-wise to the solvent, and the method can include using a stoichiometric excess of the ammonium tetrafluoroborate to form a substantially halide ion-free electrolyte solution.

Description

Electrolyte synthesis of supercapacitors [Cross-reference to related applications]

This patent application claims priority under US Patent Application Serial No. 13/909,645, filed on Jun. 4, 2013, and filed on March 15, 2013, filed on March 15, 2013. U.S. Patent Application Serial No. 13/842,898, the entire disclosure of which is incorporated herein by reference. Application No. 682,211 is a partial continuation of US Patent Application Serial No. 13/011,066 filed on January 21, 2011. Application No. 13/011,066 has been waived. The contents of these applications are the case. The contents of this application are hereby incorporated by reference in its entirety.

The present disclosure relates generally to a method for forming an electrolyte composition, and more particularly to the synthesis of an electrolyte solution for a supercapacitor.

Energy storage devices, such as supercapacitors, can be used in many applications that require discrete power pulses. Such applications range from mobile phones to power mixes. Combined with the car. An important characteristic of supercapacitors is the energy density that supercapacitors can provide. The energy density of a device that may comprise two or more carbon-based electrodes separated by a porous separator and/or an organic electrolyte is primarily determined by the nature of the electrolyte. A typical electrolyte used in commercial supercapacitors comprises a tetraethylammonium tetrafluoroborate (TEA-TFB) salt dissolved in a solvent such as acetonitrile. This electrolyte system has many beneficial properties including the solubility of the salt and the ionic conductivity.

An important factor in the development of electrolyte solutions is cost. Commercially available TEA-TFB is expensive because of the relatively expensive synthesis and purification of TEA-TFB. An example of the synthesis of TEA-TFB is disclosed in U.S. Patent No. 5,705,696. This process example involves reacting a tetraalkylammonium halide with a metal tetrafluoroborate in an aqueous medium followed by membrane dialysis to remove the metal halide. Another method of synthesis is disclosed in U.S. Patent No. 7,641,807, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in its entirety in the the the the the the The product of this process typically includes a high concentration of halide ions, such as chloride ions (e.g., 0.71% by weight or 7100 ppm) and associated metal ions. It is known that this halide ion concentration is detrimental to the performance of the supercapacitor.

In view of the above, there is a need for a simple and economical synthetic process for producing high purity TEA-TFB salts and electrolyte solutions comprising TEA-TFB salts.

A method of forming an electrolyte solution, the method comprising the steps of: combining ammonium tetrafluoroborate and a quaternary ammonium halide 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 entire reaction can be carried out at about room temperature. For example, in an exemplary embodiment, the bonding and the removal are performed at about 25 °C. In a further embodiment, a stoichiometric excess of ammonium tetrafluoroborate is used to minimize halide ion concentration in the product and to shorten reaction time.

The obtained product is an electrolyte solution containing a quaternary ammonium tetrafluoroborate dissolved in a solvent, wherein the electrolyte solution has a chloride ion concentration of less than 1 ppm, and the electrolyte solution has a bromide ion concentration of less than 1000 ppm. The concentration of potassium ions in the electrolyte solution is less than 50 ppm, the concentration of sodium ions in the electrolyte solution is less than 50 ppm, the concentration of water in the electrolyte solution is less than 20 ppm, and/or the concentration of ammonium ions in the electrolyte solution is greater than 1ppm.

Other features and advantages of the present invention will be set forth in the description which follows, and from the description or <RTIgt; The knowledge will readily understand that some of the features and advantages are obvious.

It is to be understood that the foregoing general description and the embodiments of the invention are intended to be illustrative of the embodiments of the invention. The drawings are included to provide a further understanding of the invention, and the drawings are incorporated in The drawings illustrate various embodiments of the invention and, together with

10‧‧‧ button battery

12‧‧‧ Collector

14‧‧‧Sealing components

16‧‧‧Electrode

18‧‧‧ partition board

20‧‧‧Electrolyte solution

1 is a schematic view of a button battery according to an embodiment; Figure 2 is a CV curve of an electrolyte solution prepared using a stoichiometric reactant; and Figure 3 is a CV curve of an electrolyte solution prepared using a stoichiometric excess of ammonium tetrafluoroborate.

A process for making a quaternary ammonium tetrafluoroborate involves reacting one or more quaternary ammonium halides with ammonium tetrafluoroborate in an organic solvent. The reaction product is a quaternary ammonium tetrafluoroborate and ammonium bromide. The quaternary ammonium tetrafluoroborate is soluble in an organic solvent, and ammonium bromide forms a precipitate. The precipitated NH ₄ Br can be filtered to form a solution in which, for example, TEA-TFB is dissolved in an organic solvent such as acetonitrile. In the examples, the complete reaction is carried out under constant agitation at about room temperature.

In contrast to several known synthetic routes using metal tetrafluoroborate as a reactant, the process uses ammonium tetrafluoroborate as the reactant. Although impurities derived from conventionally used metal compounds contaminate the electrolyte and reduce the performance of the element by the Faraday reaction, residual ammonium ions from the ammonium tetrafluoroborate reactant are not detrimental to the performance of the capacitor.

The ammonium tetrafluoroborate reactant may have a moisture content of less than 1000 ppm (eg, less than 500 ppm or less than 100 ppm) and a total inorganic (eg, metal) impurity content of less than 4000 ppm (eg, less than 3000 ppm or less than 2000 ppm). Exemplary inorganic or metallic impurities (which may be minimized in ammonium tetrafluoroborate) include sodium, potassium, calcium, iron, magnesium, phosphorus, cobalt, nickel, chromium, lead, arsenic, aluminum, and zinc. In one example, each metal ion concentration in the electrolyte solution is less than 1 ppm.

The properties of the ammonium tetrafluoroborate (ATFB or TFB) reactants are summarized in Table 1. Analytical techniques for measuring related 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-bis-pyrrolidinium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, triethylamine Alkyl ammonium bromide, trimethyl ethyl ammonium bromide and dimethyl diethyl ammonium bromide. In addition to the disclosed bromides, the ammonium halides can also include ammonium chlorides.

Corresponding quaternary ammonium tetrafluoroborate includes spiro-bis-pyrrolidinium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetra Butyl ammonium tetrafluoroborate, triethylmethyl ammonium tetrafluoroborate, trimethylethyl ammonium tetrafluoroborate and dimethyldiethyl ammonium tetrafluoroborate.

The quaternary ammonium halide reactant may have a moisture content of less than 10,000 ppm (eg, less than 2000 ppm or less than 1000 ppm) and less than 50 ppm The total content of inorganic impurities (for example less than 20 ppm or less than 10 ppm). (a) tetraethylammonium bromide (TEA-Br), (b) triethylmethylammonium bromide (TEMA-Br) and (c) triethylmethylammonium chloride (TEMA-Cl) The properties are summarized in Table 2.

In various embodiments, exemplary organic solvents include bipolar aprotic solvents such as propylene carbonate (PC), butylene carbonate (BC), γ-butyrolactone, acetonitrile (ACN), propionitrile (PN), and Methoxyacetonitrile. In the solvent, the initial moisture content can be less than 200 ppm (eg, less than 100 ppm or less than 50 ppm). For solvents, gas chromatography-mass spectrometry (GC-MS) can be used. Or nuclear magnetic resonance (NMR) to determine the purity.

The acetonitrile solvent properties are summarized in Table 3.

In an embodiment, a quaternary ammonium halide can be combined with a stoichiometric excess of ammonium tetrafluoroborate. Thus, the electrolyte solution can be formed using a stoichiometric amount of ammonium tetrafluoroborate or by using up to 150% (in moles) of excess ammonium tetrafluoroborate. The molar ratio of the quaternary ammonium halide to ammonium tetrafluoroborate can range from 1:1 to 1:1.5 (eg 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5) . The resulting solution may include an excess of BF ₄ and NH ₄ ions by using an excess of ammonium tetrafluoroborate. Excess ammonium ions from ammonium tetrafluoroborate can beneficially remove halide ions during the synthesis. Halide ions can also aid in the unwanted Faraday reaction in the resulting electrolyte.

For example, TEMA-TFB dissolved in ACN 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 amount of these reactants that dissolve and become ions in solution can react to form a product. Therefore, the synthesis is limited by mass transfer, and a considerable reaction time can be taken to complete the reaction.

The electrolyte solution according to an embodiment comprises a quaternary ammonium tetrafluoroborate dissolved in a solvent, wherein a chloride ion concentration in the electrolyte solution is less than 1 ppm, and a bromide ion concentration in the electrolyte solution is less than 1000 ppm (for example) Less than 800, less than 700 ppm or less than 600 ppm); the ammonium ion concentration in the electrolyte solution is greater than 1 ppm, and the potassium ion concentration in the electrolyte solution is less than 50 ppm (eg, less than 40 ppm, less than 30 ppm, or less than 10 ppm), The sodium ion concentration in the electrolyte solution is less than 50 ppm (eg, less than 30 ppm or less than 10 ppm), and/or the water concentration in the electrolyte solution is less than 20 ppm (eg, less than 10 ppm). The characteristics of an exemplary electrolyte solution are summarized in Table 4, including the ion concentration as determined by inductively coupled plasma mass spectrometry (ICP-MS). An exemplary electrolyte solution is TEA-TFB, triethylmethylammonium tetrafluoroborate (TEMA-TFB) in acetonitrile. TEMA-TFB can be synthesized from TEMA-Br or from TEMA-Cl. Density is determined by mechanical oscillation.

The conductivity of the electrolyte solution at 25 ° C can be at least 45 mS/cm (eg, at least 45, 50, 55, or 60 mS/cm). The total concentration of the quaternary ammonium tetrafluoroborate in the electrolyte solution can range from 0.1 M to 2 M (eg, 0.1, 0.2, 0.5, 1, 1.2, 1.5 or 2 M). The electrolyte solution can appear as a clear "water white" and has a density of about 0.86-0.88 g/ml.

The electrolyte solution can be stored, for example, in a stainless steel tub and in an inert atmosphere at room temperature (e.g., dry nitrogen) and under positive pressure. In a particular storage method, the electrolyte is filled into an argon purged metal can, the polymer can is sealed using a polymer plug, and then the can is packaged in a nitrogen purged and evacuated shield package (West Monroe, LA). ) Inside the barrier lining.

Once formed, the electrolyte solution can be incorporated into the ultracapacitor. In a typical supercapacitor, a pair of electrodes are separated by a porous separator and the electrode/separator/electrode stack is infiltrated with an electrolyte solution. The electrode may comprise activated carbon that has been selectively mixed with other additives. By pressing the electrode material into a thin sheet, via a selective conductive adhesive layer and a selective fused carbon layer The sheet is laminated to a current collector to form an electrode. In addition to supercapacitors such as electronic double layer capacitors, the disclosed electrolytes can be incorporated into other electrochemical electrode/element structures, such as batteries or fuel cells.

Specific examples of the activated carbon that can be used include coconut shell activated carbon, petroleum coke activated carbon, pitch activated carbon, polyvinylidene chloride-based activated carbon, polyacene-based activated carbon, and phenolic resin-based activated carbon. Polyacrylonitrile-based activated carbon and activated carbon from natural sources such as coal, charcoal or other natural organic sources. Various aspects of a suitable porous or activated carbon material are disclosed in commonly-owned U.S. Patent Application Serial Nos. 12/970,028, the entire disclosure of each of which is incorporated herein by reference.

Activated carbon can be characterized by a high surface area. High surface area electrodes can enable high energy density devices. By high surface area activated carbon is meant activated carbon having a surface area of at least 100 m ² /g (eg, at least 100, 500, 1000 or 1500 m ² /g).

The electrodes used to form the supercapacitor may be disposed identically or differently from each other. In an embodiment, at least one of the electrodes comprises activated carbon. Electrodes comprising a majority of activated carbon by weight are referred to herein as activated carbon electrodes. In an embodiment, the activated carbon electrode comprises greater than about 50% by weight activated carbon (eg, at least 50, 60, 70, 80, 90, or 95% by weight of activated carbon).

In an embodiment, the activated carbon comprises pores having a size of ≦1 nm, the pores providing a combined pore volume of ≧0.3 cm ³ /g; pores having a size ranging from >1 nm to ≦2 nm, the pores providing ≧0.05 cm ³ /g Binding pore volume; and any pore size > 2 nm, which provides a combined pore volume of <0.15 cm ³ /g.

In addition to activated carbon, additives such as a binder and a conductivity promoter may be used to control the properties of the electrode. The electrode can include one or more binders. The binder can function to provide mechanical stability of the electrode by promoting agglomeration in the loosely assembled particulate material. The binder may comprise a polymer, a copolymer or a similar high molecular weight material capable of binding activated carbon (and other optional components) together to form a porous structure. Specific exemplary 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 of the foregoing. In the examples, PTFE can be used as a binder. In a further embodiment, fibrillated PTFE can be used as a binder. By way of example, the electrode can include up to about 20% by weight of a binder (eg, up to about 5, 10, 15, or 20% by weight).

The electrode may also include one or more conductivity enhancers. The 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, graphene, and combinations thereof. In the examples, carbon black can be used as a conductivity promoter. In an embodiment, the electrode can include up to about 10% by weight of a conductivity promoter. For example, the electrode can include from about 1% to about 10% by weight of a conductivity promoter (eg, 1, 2, 4, or 10% by weight).

An exemplary supercapacitor can include one activated carbon electrode or two activated carbon electrodes. For example, one electrode may include most of the activated carbon while the other electrode may include most of the graphite.

The electrolyte solution can be characterized by measurement of the electrolyte solution itself and by measurement of a test cell incorporating the electrolyte solution.

An example of an EDLC (button battery) is shown in Fig. 1. The button battery 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 element 14 around the periphery of the electrode are provided such that the electrode 16 remains in contact with the current collector 12 . A partition plate 18 is disposed between the two electrodes 16 . The electrolyte solution 20 is housed between two sealing elements.

The activated carbon-based electrode having a thickness in the range of about 50 micrometers to 300 micrometers may be prepared by rolling and compacting the powder mixture, the powder mixture comprising 80% by weight to 90% by weight of microporous activated carbon, 0% by weight to 10 % by weight of carbon black and 5% by weight to 20% by weight of a binder (for example a fluorocarbon binder such as PTFE or PVDF). Alternatively, a liquid may be used to form the powder mixture into a paste which may be compacted into tablets and dried. The activated carbon containing sheet can be calendered, stamped or otherwise patterned and laminated to a conductive adhesive layer to form an electrode.

Button cells are made using activated carbon electrodes. The activated carbon electrode was produced by first mixing activated carbon and carbon black in a ratio of 85:5. PTFE was added to make a carbon:carbon black: PTFE ratio of 85:5:10. The powder mixture was added to isopropanol, mixed, and then dried. The dried material was compacted into a 10 mil thick preform. The preform was then laminated on a conductive adhesive layer (50% by weight of graphite, 50% by weight of carbon black) formed on a current collector coated with fused carbon.

For the button battery, the current collector is formed of a platinum foil, and the separator is formed of cellulose paper. The activated carbon electrode and separator are immersed in the electrolyte prior to assembly. A thermoset polymer ring is formed on the periphery of the assembly to seal the cell, which is filled with an organic electrolyte, such as tetraethylammonium-tetrafluoroborate (TEA-TFB) dissolved in acetonitrile. Add an additional drop of electrolyte to the battery before sealing the battery.

Electrochemical experiments were used to test batteries, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and constant current charge/discharge. Cyclic voltammetry experiments were performed at a scan rate of 20 millivolts per second over a wide range of potential windows from 0 to 4.5 volts. The EIS test involves measuring the impedance while applying an AC disturbance with an amplitude of 10 mV at a constant DC voltage of 0 V over a frequency range of 0.01-10,000 Hz. The constant current charge/discharge experiment was carried out at a current amplitude of 10 mA.

The energy density of the device is calculated using the integral energy method. The constant current data (the data whose potential changes with time) is numerically integrated and multiplied by the discharge current to obtain the energy (Ws) delivered by the device between the two potentials V ₁ and V ₂ .

The capacitance of the _device (C _device , in Farads) can be calculated from the energy according to the following relationship:

The specific capacitance (F/cm ³ ) is then calculated by dividing the capacitance of the device by the total volume of the carbon electrode.

The voltage regulation was measured by a series of cyclic voltammetry (CV) experiments performed between several different voltage windows (the maximum voltage that the device can withstand without significant Faraday reaction). From the CV data, use the following formula to calculate the Faraday fraction:

The charge (Q) during the anode and cathode scans was calculated by integrating the CV curve and dividing the result by the scan rate at which the CV was performed. The voltage regulation system is defined as a potential having a Faraday fraction of about 0.1.

The energy density under voltage regulation (the maximum voltage that the device can withstand without significant Faraday reaction) is calculated using the following relationship, where C _device is the device capacitance (in Farad), V ₁ is voltage regulation, and V ₂ is V ₁ /2, and the volume is the volume of the device in liters:

Other aspects of the present disclosure are set forth in the following non-limiting examples which disclose the exemplary synthesis of TEA-TFB from ammonium tetrafluoroborate and tetraethylammonium bromide in acetonitrile.

Example 1

31.3329 g of tetraethylammonium bromide (TEA-Br) was added to 100 ml of acetonitrile, and the suspension was stirred for 1 hour, after which 15.642 g of ammonium tetrafluoroborate (NH ₄ BF ₄ ) was added. The amount of reactant corresponds to a stoichiometric amount. The suspension was stirred and the temperature of the mixture was maintained at 25 ° C throughout the synthesis.

The suspension was filtered to remove the precipitate. The conductivity of the electrolyte solution was 64 mS/cm. The obtained electrolyte solution was placed in a button battery using activated carbon having a surface area of 1800 m ² /g as described above.

The button battery has an energy density of 15 Wh/l. However, referring to Figure 2, it is seen that the electrolyte has a distinct Faraday reaction. Bromide in electrolyte solution The sub-content was determined to be 7123 ppm by ion chromatography. The bromide ion causes a Faraday reaction and undesirably increases the ESR of the battery with other halide ions and shortens the cycle life.

Example 2

31.3329 g of tetraethylammonium bromide was added to 100 ml of acetonitrile, and the suspension was stirred for 1 hour, after which 25.642 g of ammonium tetrafluoroborate was added. The amount of reactant corresponds to a stoichiometric excess of ammonium tetrafluoroborate. The suspension was stirred and the temperature was maintained at 25 °C as in Example 1.

The suspension was filtered to remove the precipitate. The conductivity of the electrolyte solution was 64 mS/cm. The obtained electrolyte solution was placed in a button battery using activated carbon having a surface area of 1800 m ² /g as described above.

The button battery has an energy density of 17 Wh/l. Referring to Figure 3, the CV curve shows no Faraday reaction. The bromide ion content in the electrolyte solution was determined to be 751 ppm by ion chromatography. The chloride ion content was less than 0.05 ppm and the ammonium ion concentration was 245 ppm.

Example 3

An electrolyte solution having the same total amount of reactants as in Example 2 was prepared by gradually adding the reactants. As defined herein, the stepwise addition of reactants means that at least one (preferably two) reactants are introduced into the mixture before and after introduction of the other reactants. Thus, the stepwise addition of reactants A and B can include introducing reactants in the following exemplary sequence: ABA, BAB, ABAB, BABA, ABABA, BABAB, and the like.

The following materials were added sequentially in 100 ml of acetonitrile under constant stirring at 25 ° C for 1 hour between the addition of the reactants: 5 g of NH ₄ BF ₄ , 10 g of TEA-Br, 5 g of NH ₄ BF ₄ , 10 g of TEA-Br, 5.642 g of NH ₄ BF ₄ , 11.332 g of TEA-Br and 10 g of NH ₄ BF ₄ . After the final addition, the solution was stirred overnight, then filtered through a Whitman 42, 110 mm paper and then filtered again with a 0.02 um syringe filter.

Example 4

591 g of triethylmethylammonium bromide, 347 g of ammonium tetrafluoroborate (10% excess relative to the stoichiometric amount) and 2 liters of acetonitrile were sequentially added to the heated reactor purged with dry nitrogen. The reactor is fluid powered similar to a commercial reactor in terms of impeller structure, baffle usage, L/D and other geometric ratios. The resulting suspension was stirred with constant stirring. The temperature of the suspension and the vessel was maintained at 25 °C. The progress of the reaction was monitored using an ion selective electrode method (ISE) by measuring the concentration of bromide anions in the mixture. The reaction was stopped when the bromide ion concentration was reduced to less than 600 ppm. The suspension was filtered to remove the precipitate. The resulting solution was dried using a 3 angstrom molecular sieve to a total water content of less than 10 ppm. In a related method, the progress of the reaction can be monitored by measuring the concentration of fluoroborate (BF ₄ ^- ) or chloride (Cl ^- ) ions. For the electrolytic solution of 1.2M, borne in mind that, with the progress of the reaction, Br ^- and Cl ^- in reducing the concentration of ions and BF ₄ ^- ion concentration increased, for chloride ions and fluoroborate respective ISE endpoint concentration (expressed The reaction was completed) as BF ₄ ^- > 115,000 ppm and Cl ^- < 200 ppm.

Example 5

An electrolyte solution was prepared using ammonium tetrafluoroborate and spiro-bis-pyrrolidinium bromide dissolved in acetonitrile. The spiro-bis-pyrrolidinium bromide is synthesized from 1,4-dibromobutane, ammonium hydrogencarbonate, and controlled addition of pyrrolidine. In addition to ammonium bromide, The synthesis of the reactants also involves the release of water and carbon dioxide, which can be separated as a precipitate.

The synthesis parameters include the rate of addition of pyrrolidine and the temperature of the solution (T1) during the addition of pyrrolidine, the reaction temperature (T2) of the reaction to form the spiro-bis-pyrrolidinium bromide reactant, and the spiro-bis-pyrrolidine. The reaction temperature (T3) of bismuth bromide combined with ammonium tetrafluoroborate to form spiro-bispyrrolidinium tetrafluoroborate (SBP-TBF).

After the synthesis, the conductivity of the obtained electrolyte solution was measured. The yellow color observed is the result of treatment with molecular sieves. A summary of the reaction conditions and conductivity is shown in Table 5.

Referring to Table 5, in the rapid addition, pyrrolidine was injected from the pipette into the reaction mixture, and in the slow addition, the pyrrolidine was added dropwise via the addition funnel. Applicants have discovered that higher conductivity can be achieved in the final product by slightly increasing the temperature and reaction of the pyrrolidine addition to form the temperature of the spiro-bis-pyrrolidinium bromide intermediate.

In various embodiments, the temperature (T1) of the mixture during pyrrolidine addition may range from about 25 ° C to 35 ° C, while forming spiro-bis-pyrrolidine The temperature (T2) of the mixture during the reaction of hydrazine bromide may range from about 30 °C to 40 °C. The final reaction temperature (T3) of the spiro-bis-pyrrolidinium bromide with ammonium tetrafluoroborate may be about 20 ° C (eg, about 20 ° C or about 25 ° C). The SBP-TBF electrolyte can be more electrochemically stable than the TEA-TFB electrolyte, especially at a negative potential.

The electrolyte solution in which SBP-TBF was dissolved in acetonitrile and TEA-TFB in acetonitrile was evaluated in a 2.7 V and 2.8 V symmetrical test cell and in a 2.7 V tuned test cell. In the symmetrical test cell, the same activated carbon material was used for each of the positive and negative electrodes, and in the tuned test cell, the activated carbon material doped with the positive electrode was different from the activated carbon material doped with the negative electrode. Specifically, in order to accommodate the respective ion sizes of the positive and negative ions that will interact with the activated carbon at the negative and positive electrodes, respectively, in the tuned cell, the pore size distribution of the carbon in the positive electrode (interacting with the generally larger electrolyte cation) A pore that tends to be larger than the pore size distribution of carbon in the negative electrode (interacting with a generally smaller electrolyte anion).

In one example, the capacitance of a 1.5 M electrolyte solution of SBP-TBF dissolved in acetonitrile was evaluated in both symmetrical and tuned cells. In a symmetrical battery, the initial capacitance at 2.7V is between about 425 farads and 450 farads. After 100 hours, the capacitance of the symmetrical battery was reduced to a range of from about 375 farads to 385 farads and decreased to a range of about 350 farads to 375 farnes after 400 hours. In a tuned battery, the initial capacitance at 2.7V is between about 575 farads and 600 farads. After 100 hours, the capacitance of the tuning battery was reduced to within the range of about 500 farads to 525 farads.

Table 6. Characteristics of 3 angstrom molecular sieves

An organic sample of the electrolyte can be diluted to a quasi-aqueous solution using an ion selective electrode (ISE) method. For example, dilution of 0.25 g of TEMA-TFB dissolved in ACN in 25 ml of deionized water will result in a quasi-aqueous solution that can measure the concentration of bromide ions via an ion selective electrode method. A millivolt (mV) reading can then be correlated to a calibration curve prepared using a known concentration of aqueous bromide solution to determine the bromide content in the electrolyte sample. The ionic strength modifiers can be sodium nitrate (NaNO ₃₎ as an aqueous solution added to the solution to reduce any interference from other ions. The results show very consistent results with ion chromatography. The ion selective electrode method is less capital intensive, specific, and provides fast processing results and quality control of electrolyte synthesis.

The singular <RTI ID=0.0>"1""""""""""" Thus, for example, reference to "a metal" includes examples of two or more such "metals" unless the context clearly dictates otherwise.

Ranges may be expressed herein as "about" a particular value, and/or to "about" another particular value. When such a range is expressed, the examples include from that particular value and/or to other specific values. Similarly, when a value is expressed as an approximation, it will be understood by using the antecedent "about" that the particular value forms another aspect. It will be further understood that the endpoints of each range are not It makes sense to relate to another endpoint or to be independent of another endpoint.

Unless otherwise stated, it is not intended that any method presented herein be interpreted as a step that is required to perform the method in any particular order. Thus, there is no intention to infer any particular order when the method claims are not in the order in which the steps of the method are actually described, or in the claims or the description.

It is also noted that the statements herein refer to elements of the invention that are "set" or "adapted" to function in a particular manner. In this regard, such elements are "set" or "adapted" to the particular nature or function in a particular manner, and such statements are structurally stated in relation to the stated use. More specifically, the manner in which an element referred to herein is "set" or "adapted" to mean the physical state of the element is considered to be a clear statement of the structural characteristics of the element.

It will be apparent to those skilled in the art that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention. The modifications, sub-combinations, and variations of the disclosed embodiments of the present invention are considered to be within the scope of the appended claims. Everything within the scope of the equivalent of the patent application scope.

10‧‧‧ button battery

12‧‧‧ Collector

14‧‧‧Sealing components

16‧‧‧Electrode

18‧‧‧ partition board

20‧‧‧Electrolyte solution

Claims (18)

A method of forming an electrolyte solution, the method comprising the steps of: combining ammonium tetrafluoroborate and a quaternary ammonium halide in a liquid solvent to form a quaternary ammonium tetrafluoroborate and an ammonium monohalide; The ammonium halide is removed by a solvent to form an electrolyte solution. The method of claim 1, wherein the molar ratio of ammonium tetrafluoroborate to the quaternary ammonium halide is from 1:1 to 1.5:1. The method of claim 1, wherein the quaternary ammonium halide is selected from the group consisting of spiro-bis-pyrrolidinium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide. a group consisting of tetrabutylammonium bromide, triethylmethylammonium bromide, trimethylethylammonium bromide, and dimethyldiethylammonium bromide. The method of claim 3, further comprising the step of providing the snail by mixing 1,4-dibromobutane, ammonium hydrogencarbonate and pyrrolidine at a temperature between 25 ° C and 40 ° C. Bis-pyrrolidinium bromide. The method of claim 1, wherein the solvent is selected from the group consisting of propylene carbonate, butylene carbonate, butyrolactone, acetonitrile, propionitrile, and methoxyacetonitrile. The method of claim 1, wherein the step of combining and the removing The steps were carried out at about 25 °C. The method of claim 1, wherein the step of combining is carried out under constant agitation. The method of claim 1, wherein the step of combining comprises the step of gradually adding the ammonium tetrafluoroborate and the quaternary ammonium halide to the liquid solvent. The method of claim 1, wherein the concentration of the quaternary ammonium tetrafluoroborate in the solvent is from 0.1 to 2 vol. The method of claim 1, wherein the electrolyte solution has a conductivity of at least 35 mS/cm at 25 °C. The method of claim 1, wherein one of the electrolyte solutions has a chloride ion concentration of at most 1 ppm; one of the electrolyte solutions has a bromide ion concentration of at most 1000 ppm; and one of the electrolyte solutions has a concentration of ammonium ions greater than 1ppm. The method of claim 1, wherein one of the electrolyte solutions has a potassium ion concentration of at most 50 ppm; and one of the electrolyte solutions has a sodium ion concentration of at most 50 ppm; One of the electrolyte solutions has a water concentration of at most 20 ppm. An electrolyte solution comprising a quaternary ammonium tetrafluoroborate dissolved in a solvent, wherein one of the electrolyte solutions has a chloride ion concentration of at most 1 ppm; and one of the electrolyte solutions has a bromide ion concentration of at most 1000 ppm; One of the ammonium ion concentrations in the electrolyte solution is greater than 1 ppm. The electrolyte solution according to claim 13, wherein one of the electrolyte solutions has a potassium ion concentration of at most 50 ppm; the electrolyte solution has a sodium concentration of at most 50 ppm; and one of the electrolyte solutions has a water concentration of at most 20 ppm. The electrolyte solution according to claim 13, wherein the quaternary ammonium tetrafluoroborate is selected from the group consisting of spiro-bis-pyrrolidinium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetra Fluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, trimethylethylammonium tetrafluoroborate and dimethyldiethyl a group consisting of ammonium tetrafluoroborate. The electrolyte solution according to claim 13, wherein the solvent is selected from the group consisting of propylene carbonate, butylene carbonate, butyrolactone, acetonitrile, propionitrile and methoxyacetonitrile. The electrolyte solution according to claim 13, wherein the concentration of the quaternary ammonium tetrafluoroborate in the solvent is from 0.1 to 2 mols. The electrolyte solution according to claim 13, wherein each of the individual metal ions selected from the group consisting of magnesium, iron, cobalt, nickel, chromium, calcium, lead, arsenic, zinc, and aluminum is in the electrolyte solution. One of the concentrations is at most 5 ppm.