Halogenated compounds for energy storage device formulations

Abstract

Performance improvers and formulations for energy storage devices are disclosed. The performance improvers include halogenated aromatic heterocyclic compounds that can be used to improve the performance of energy storage devices (e.g., capacitors) operating at voltages above 3V (e.g., 3.2 V).

Description

[0001] Citation of prior application

[0002] Pursuant to 37 CFR 1.57 and Sections 4.18 and 20.6, any and all applications for which foreign or domestic priority claims are indicated in the Application Data Sheet or PCT request filed with this application are incorporated herein by reference, including US Provisional Application No. 63 / 363,141 filed on April 18, 2022. Technical Field

[0003] The present invention relates generally to energy storage devices, and particularly to performance enhancers, more particularly halogenated compounds, for use in energy storage devices. Background Art

[0004] Electrical energy storage cells are widely used to provide power to electronic, electromechanical, electrochemical and other useful devices. Such batteries include primary chemical batteries, secondary (rechargeable) batteries, fuel cells and various capacitors, including supercapacitors. Increasing the operating voltage and temperature of energy storage devices (including capacitors) would be desirable for enhancing energy storage, increasing power capabilities and broadening real-world use cases.

[0005] However, at higher operating temperatures and voltages, energy storage devices may undergo undesirable processes that lead to performance degradation or outright battery failure. Such processes may include chemical and electrochemical reactions of the electrolyte and / or other components of the device.

[0006] Over the lifetime of an energy storage device, degradation in device performance can manifest as capacitance decay, increase in the device's equivalent series resistance (ESR), self-discharge, pseudocapacitance, and / or gas formation. Therefore, there is a need for energy storage devices with improved stability under elevated voltage and operating temperature conditions. Summary of the invention

[0007] For the purpose of summarizing the present disclosure and the advantages achieved over the prior art, certain objects and advantages of the present disclosure are described herein. Not all of these objects or advantages may be achieved in any specific embodiment. Thus, for example, it will be appreciated by those skilled in the art that the present invention may be embodied or implemented in a manner that achieves or optimizes one advantage or a group of advantages taught herein without necessarily achieving other objects or advantages taught or suggested herein.

[0008] In one aspect, an electrolyte is disclosed. The electrolyte comprises: a salt; a solvent; and a performance modifier, wherein the performance modifier comprises a halogenated heteroaryl compound.

[0009] In some embodiments, the halogenated heteroaryl compound comprises a compound having the structure: (I) wherein X1 , X 2 , X 3 , X 4 and X 5 are each independently H or halogen, provided that X 1 , X 2 , X 3 , X 4 and X 5 At least one of is a halogen. In some embodiments, the halogen is selected from the group consisting of: -F, -Cl, -Br, and -I.

[0010] In some embodiments, the compound of formula (I) is a compound selected from the group consisting of:

[0011] The electrolyte of any one of claims 2 to 4, wherein the compound of formula (I) is selected from the group consisting of: In some embodiments, the compound of formula (I) is In some embodiments, the compound of formula (I) is In some embodiments, the compound of formula (I) is

[0012] In some embodiments, the electrolyte includes about 0.1 wt % to about 30 wt % of a performance improver. In some embodiments, the electrolyte includes about 0.5 wt % to about 15 wt % of a compound of formula (I). In some embodiments, the salt includes a compound selected from the group consisting of tetraethylammonium salts, triethylmethylammonium salts, methyltriethylammonium salts, tetrabutylammonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, tetrahexylphosphonium salts, lithium salts, trimethylethylammonium (TMEA) salts, diethyldimethylammonium (DEDMA) salts, diethyl-methylmethoxyethylammonium (DEME) salts, tetramethylammonium (TMA) salts, piperidine-1-spiro-1'-pyrrolidinium (SPP) salts, spiro-(1 ,1')-bipyrrolidinium (SBP) salts, 1,1-dimethylpyrrolidinium (DMP) salts, dimethylammonium (DMA) salts, 1-ethyl-1-methylpyrrolidinium (EMP) salts, 1-methyl-1-propylpyrrolidinium (MPP) salts, 1-butyl-1-methylpyrrolidinium (BMP) salts, 1-ethyl-3-methylimidazolium (EMI) salts, 1-methyl-3-propylimidazolium (PMI) salts, 1-butyl-3-methylimidazolium (BMI) salts, and combinations thereof. In some embodiments, the solvent includes a compound selected from the group consisting of acetonitrile, γ-butyrolactone, dimethoxyethane, N,N-dimethylformamide, hexamethylphosphoric triamide, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, dimethyl sulfite, cyclopentane, nitromethane, dioxolane, ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), capronitrile, valeronitrile, butyronitrile, propionitrile, methyl ethyl sulfone, methyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl sec-butyl sulfone, butyl isobutyl sulfone, and combinations thereof.

[0013] In another aspect, an energy storage device is disclosed. The energy storage device includes: a cathode; an anode; a separator disposed between the cathode and the anode; an electrolyte comprising a salt, a solvent, and a performance improver; and a housing, wherein the cathode, the anode, the separator, and the electrolyte are disposed within the housing.

[0014] In another aspect, an energy storage device is disclosed. The energy storage device includes: a cathode; an anode; a separator disposed between the cathode and the anode; an electrolyte; and a housing, wherein the cathode, the anode, the separator, and the electrolyte are disposed in the housing.

[0015] In some embodiments, the energy storage device is a capacitor. In some embodiments, the energy storage device is configured to maintain at least about 80% of its initial capacitance when operating at about 3.2V for a period of about 1000 hours at a temperature of about 65°C. In some embodiments, the energy storage device is configured to grow at most about 4% of its initial length when operating at about 3.2V for a period of about 1000 hours at a temperature of about 65°C. In some embodiments, the energy storage device is configured to maintain at most about 175% of its initial DC-ESR when operating at about 3.2V for a period of about 1000 hours at a temperature of about 65°C. In some embodiments, the energy storage device is configured to maintain at most about 175% of its initial AC-ESR when operating at about 3.2V for a period of about 1000 hours at a temperature of about 65°C.

[0016] In another aspect, a method for manufacturing an energy storage device is disclosed. The method includes: placing a cathode, an anode, a separator, an electrolyte, and a performance improver in a housing, wherein the performance improver comprises a structure A compound of formula (II) wherein X 1 , X 3 and X 5 are each independently H or halogen, provided that X 1 , X 3 and X 5 At least one of them is a halogen.

[0017] In another aspect, a method for manufacturing an energy storage device is disclosed. The method includes: placing a cathode, an anode, a separator, an electrolyte, and a performance improver in a housing, wherein the performance improver comprises a halogenated heteroaryl compound.

[0018] In some embodiments, prior to the disposing step, at least one of the cathode and the anode comprises a performance enhancer. In some embodiments, prior to the disposing step, the electrolyte comprises a performance enhancer.

[0019] In another aspect, an electrode film is disclosed. The electrode film comprises: an active material; a binder; and a performance improver, wherein the performance improver comprises a halogenated heteroaryl compound.

[0020] All of these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed disclosure of preferred embodiments with reference to the accompanying drawings, and the invention is not limited to any specific preferred embodiment disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A perspective view of an energy storage device according to one embodiment is shown.

[0022] Figure 2A Shows Figure 1 Exploded view of the energy storage device.

[0023] Figure 2B Shows Figure 2A Exploded view of the electrode unit.

[0024] Figure 3A Shown is a line graph detailing the change in capacitance over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device and a comparative energy storage device.

[0025] Figure 3B Shown is a line graph detailing the change in cell length over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device and a comparative energy storage device.

[0026] Figure 3C Shown is a line graph detailing the change over time of a direct current equivalent series resistance (DC-ESR) of an energy storage device having a performance improver according to some embodiments compared to a control energy storage device and a comparative energy storage device.

[0027] Figure 4A Shown is a line graph detailing the change in cell length over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0028] Figure 4B Shown is a line graph detailing the change in capacitance over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0029] Figure 4C Shown is a line graph detailing the change in direct current equivalent series resistance (DC-ESR) over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0030] Figure 4D Shown is a line graph detailing the change in AC equivalent series resistance (AC-ESR) over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0031] Figure 5A Shown is a line graph detailing the change in cell length over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0032] Figure 5B Shown is a line graph detailing the change in capacitance over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0033] Figure 5CShown is a line graph detailing the change in direct current equivalent series resistance (DC-ESR) over time for an energy storage device having a performance improver according to some embodiments compared to a control energy storage device.

[0034] Fig. 6A Shown is a line graph detailing the change in cell length over time for energy storage devices having various amounts of performance improvers according to some embodiments compared to a control energy storage device.

[0035] Figure 6B Shown is a line graph detailing the change in capacitance over time for energy storage devices having various amounts of performance improvers according to some embodiments compared to a control energy storage device.

[0036] Figure 6C Shown is a line graph detailing the change in AC equivalent series resistance (AC-ESR) over time for energy storage devices having various amounts of performance improvers according to some embodiments compared to a control energy storage device.

[0037] Fig.6D Shown is a line graph detailing the change in direct current equivalent series resistance (DC-ESR) over time for energy storage devices having various amounts of performance improvers according to some embodiments compared to a control energy storage device.

[0038] These and other features, aspects, and advantages of the present disclosure are described with reference to the accompanying drawings of certain embodiments, which are intended to illustrate certain embodiments and not to limit the present invention. DETAILED DESCRIPTION

[0039] Although certain embodiments and examples are disclosed herein, it will be appreciated by those skilled in the art that the invention extends beyond the specifically disclosed embodiments and / or uses and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the invention disclosed herein should not be limited by any specific embodiments described herein.

[0040] Disclosed are halogenated heteroaryl performance improvers for use in energy storage devices (e.g., capacitors and / or batteries). In some embodiments, the energy storage device includes one or more halogenated heteroaryl performance improver compounds provided herein. In some embodiments, the energy storage device including such performance improvers exhibits improved performance, such as reduced gas generation, improved capacitance reduction rate, and improved resistance increase rate. In some embodiments, improved energy storage device performance can be achieved at an operating voltage of at least or greater than 3V (e.g., about 3.2V) and / or at an operating temperature of at most or less than 65°C (e.g., at most about 65°C) or at an operating temperature of at least or greater than 65°C (e.g., at least about 65°C).

[0041] In some embodiments, the halogenated heteroaryl performance improver compound may include a nitrogen-containing aromatic heterocycle having at least one halogen atom bonded to an aromatic ring. In some embodiments, the nitrogen-containing aromatic heterocycle may be, for example, pyridine, pyrimidine, pyrazine, or pyridazine. Additional details about the halogenated heteroaryl compound may be found herein.

[0042] definition

[0043] As used herein, the terms "battery" and "capacitor" are to be given their ordinary and customary meanings to persons of ordinary skill in the art. The terms "battery" and "capacitor" are not mutually exclusive. A capacitor or battery may refer to a single electrochemical cell that may operate alone or as a component of a multi-battery system.

[0044] As used herein, capacitance (F - Farads) is a measure of energy storage in Joules, C = Q / V.

[0045] As used herein, voltage is the maximum operating voltage for a single capacitor. The rated voltage is the voltage at which the performance data is measured. These capacitors may experience voltages exceeding the rated voltage. The effect depends on the time and temperature during the exposure.

[0046] As used herein, surge voltage is the maximum voltage at which an ultracapacitor can operate for a short period of time with minimal damage or battery opening.

[0047] As used herein, internal resistance can be measured by direct current equivalent series resistance (DC-ESR) and / or alternating current equivalent series resistance (AC-ESR). R And in V R The DC-ESR was measured at an amplitude of 5 to 10 mV and a frequency of 50 to 1 kHz.

[0048] Energy storage device

[0049] As provided herein, the energy storage device can be a capacitor, a hybrid capacitor (e.g., a lithium ion capacitor (LIC)), a supercapacitor, an ultracapacitor, and / or a battery. The energy storage device can be characterized by an operating voltage. The performance improvers described herein (e.g., halogenated heteroaryl performance improvers) and electrolytes and / or electrodes comprising the performance improvers described herein can be used in various embodiments with any of a variety of energy storage devices (e.g., one or more batteries, capacitors, capacitor-battery hybrids, fuel cells, or other energy storage systems or devices and combinations thereof). In some embodiments, the performance improvers described herein, electrolytes comprising performance improvers, and / or electrodes / electrode films comprising performance improvers can be implemented in lithium ion capacitors, lithium ion batteries, or supercapacitors.

[0050] The energy storage device includes one or more electrodes. The electrode generally includes an electrode film and a current collector. The electrode film can be formed by a mixture of one or more binders and an active electrode material. In some embodiments, the electrode and / or electrode film further includes a performance improver (e.g., a halogenated heteroaryl performance improver). One or more binders can be selected from fluorinated binders (e.g., polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), PVDF copolymers), ultra-high molecular weight polyethylene (UHMWPE), poly(ethylene oxide) (PEO), carboxymethyl cellulose (CMC), poly(acrylic acid) (PAA), poly(acrylic acid) (PAAX; wherein X = Li, Na, K, NH4), poly(vinyl alcohol) (PVA), polyvinyl acetate (PVAc), poly(vinyl alcohol)-poly(acrylic acid) (PAA-PVA), poly(vinyl alcohol)-poly(ethyleneimine) (P VA-PEI), poly(acrylic acid)-sodium carboxymethyl cellulose (PAA-CMC), poly(sodium acrylate)-grafted carboxymethyl cellulose (NaPAA-g-CMC), poly(acrylic acid)-diallyl ether (PAA-diallyl ether), carboxymethyl chitosan (C-chitosan), chitosan-glutaraldehyde (CS-GA), alginates (e.g., sodium alginate, calcium alginate), alginate-carboxymethyl chitosan, catechol conjugated poly(acrylic acid) (PAA-C), β-cyclodextrin polymers, carbonyl-β-cyclodextrin, β-cyclodextrin polymers with quaternary ammonium cations (β-CDp-N +), gum arabic (GA), gum arabic-polyacrylic acid (GA-PAA), gellan gum, xanthan gum (XG), guar gum (GG), xanthan gum-guar gum (XG-GG), locust bean gum (LBG), poly(3,4-ethylenedioxythiophene):poly(styrene 4-sulfonate) (PEDOT:PSS), karaya gum (KG), polyacrylic acid latex (e.g., LA132), poly(acrylamide)-co-diallyldimethylammonium chloride (AMAC), polyamidoamine (PAMAM), gelatin, styrene butyl rubber (SBR), polyvinyl pyrrolidone, polyacrylonitrile, polyvinyl alcohol polyolefin, polyimide, polyetherketone, polyepoxide, polyurethane, or other suitable fiberizable materials, or combinations thereof.

[0051] In some embodiments, the active electrode material is selected from activated carbon, lithiated carbon, lithium metal oxides and metal oxides. In some embodiments, the active electrode material may include a carbon-based material. The carbon-based material may be selected from activated carbon, graphene-based carbon (e.g., graphene), graphite-based carbon (e.g., graphite), carbon nanotubes, and combinations thereof. The lithiated carbon-based material may be selected from lithiated activated carbon, lithiated graphene-based carbon (e.g., lithiated graphene), lithiated graphite-based carbon (e.g., lithiated graphite), lithiated carbon nanotubes, and combinations thereof. In some embodiments, the metal oxide has the formula M x O y . In some embodiments, the metal "M" of the metal oxide is selected from Fe, Mn, Ni, Mo, Cu, Co, Al, Ti, V and Cr, or a combination thereof. In some embodiments, the lithium metal oxide is selected from lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel cobalt manganese oxide (NCM or NMC), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), lithium iron manganese phosphate (LFMP), lithium cobalt phosphate (LCP), lithium fluoroferric sulfate (LFSF), lithium vanadium fluorosulfate (LVSF), lithium titanium oxide (LTO), lithium titanium sulfide (LTS), lithium nickel cobalt manganese oxide (HE-NCM), lithium manganese oxide (HV-spinel) and lithium silicon oxide (LSO). In some embodiments, the electrode film further includes a conductive additive. In some embodiments, the conductive additive is selected from conductive carbon (e.g., carbon black).

[0052] The energy storage device provided herein can have any suitable configuration, such as planar, spirally wound, button-shaped or bag-shaped. The energy storage device provided herein can be a component of the following system: for example, a power generation system, an uninterruptible power supply system (UPS), a photovoltaic power generation system, an energy recovery system for example in industrial machinery and / or transportation. The energy storage device provided herein can be used to power various electronic devices and / or motor vehicles including the following: hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV) and / or electric vehicles (EV).

[0053] Limiting gas generation during the operation of energy storage devices is an important operating parameter. Gas production is undesirable because the sealed battery will become pressurized, thereby reducing battery efficiency and generating potential dangers. Such devices generally have a housing, such as a metal container or can, which may withstand significant internal pressure accumulation caused by gas formation. However, operating at high voltage or high temperature may produce too much gas, thereby generating an overpressure condition. For example, the overpressure condition can be alleviated by opening a safety vent that releases the accumulated pressure. However, opening such a vent may make the device inoperable. Relative to other devices that are spirally bound or have a rigid container, gas formation may also prevent the use of a bag-like or other non-rigid container configuration, or may reduce the increased active material density that will be provided by the bag-like configuration. Therefore, the mitigation of gas formation may be desirable. In some embodiments, the performance improver provided herein can reduce gas generation in an energy storage device.

[0054] The energy storage devices disclosed herein can be advantageously characterized by an equivalent series resistance that is reduced during the life of the device, which can provide a device with an increased power density. In some embodiments, the capacitors described herein can be characterized by reduced capacitance losses during the life of the device. Further improvements that can be achieved in various embodiments include improved device performance, including improved capacitance stability and reduced capacitance decay.

[0055] Even when operating under increased voltage, increased temperature, extended life and / or extended cycle, the disclosed performance improvers can be used to achieve such favorable improved performance in energy storage devices, such as reduced gas generation, improved capacitance reduction rate and improved resistance increase rate. In some embodiments, the performance improvers described herein are used to reduce the secondary electrochemical reactions of the performance improvers, electrolytes and / or electrodes in the energy storage device. In some embodiments, the energy storage device is configured to have an operating voltage of, about, at least or at least about 2V, 2.1V, 2.2V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V, 3V, 3.1V, 3.2V, 3.3V, 3.4V, 3.5V, 3.6V, 3.7V, 3.8V or 4V, or any range of values ​​therebetween. For example, in some embodiments, the energy storage device may have an operating voltage of about 2.2V to about 3.8V, about 3.2V to about 3.3V, or about 3.0V to about 3.3V. In other examples, in some embodiments, the energy storage device may have an operating voltage of at least 3.2V, at least 3.0V, or at least 2.7V. In some embodiments, the energy storage device is configured to have an operating temperature of, about, at most, or at most about 0°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C, or any range of values ​​therebetween. In some embodiments, the energy storage device is configured to operate at any selected operating voltage and / or temperature described herein. For example, in some embodiments, the energy storage device is configured to operate continuously at 2.7V at 25-85°C, 2.8V at 25-85°C, 2.9V at 25-85°C, 3V at 25-85°C, 3.1V at 25-85°C, 3.2V at 25-85°C, 3.3V at 25-85°C, 3.4V at 25-85°C, 3.5V at 25-85°C, 3.6V at 25-85°C, 3.7V at 25-85°C, 3.8V at 25-85°C, 3.9V at 25-85°C, 4.0V at 25-85°C, or 4.1V at 25-85°C. In some embodiments, the energy storage device is configured to operate at about 3.2V and about 85°C, about 3.2V and about 80°C, about 3.3V and about 75°C, about 3.2V and about 75°C, about 3.1V and about 75°C, about 3V and about 75°C, about 3.2V and about 65°C, about 3.3V and about 65°C, or about 3.2V and about 25°C.

[0056] The energy storage device may include one or more of the technologies described herein (e.g., halogenated heteroaryl performance improvers) to achieve improved performance. For example, in some embodiments, the energy storage device is configured to maintain a capacitance of at least about 70% of its initial capacitance, up to 6% of its initial length, up to 400% of its initial DC equivalent series resistance (DC-ESR), and / or up to 250% of its initial AC equivalent series resistance (AC-ESR) when operated at a voltage of 3.2V and at a temperature of 65°C, about 65°C, at least 65°C, or at least about 65°C for a period of about 1000 hours. In some embodiments, the energy storage device is configured to maintain a capacitance of at least about 80% of its initial capacitance, up to 4% of its initial length, up to 200% of its initial DC-ESR, and / or up to 200% of its initial AC-ESR when operated at a voltage of 3.2V and at a temperature of 75°C, about 75°C, at least 75°C, or at least about 75°C for a period of about 150 hours.

[0057] In some embodiments, the energy storage device is configured to maintain at least or about 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, or 99% of its initial capacitance when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C for a period of 1000 hours, about 1000 hours, at least 1000 hours, or at least about 1000 hours. In some embodiments, the energy storage device is configured to maintain at least or about 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, or 99% of its initial capacitance when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C for a period of 2000 hours, about 2000 hours, at least 2000 hours, or at least about 2000 hours. In some embodiments, the energy storage device is configured to maintain at least or about 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, or 99% of its initial capacitance when operated at 3.2V or about 3.2V for a period of 10 years, about 10 years, at least 10 years, or at least about 10 years at 25°C, about 25°C, at least 25°C, or at least about 25°C. In some embodiments, the energy storage device is configured to maintain at least or about 75%, 80%, 85%, 90%, 92%, 95%, 98%, or 99% of its initial capacitance when operated at 3.2V or about 3.2V for a period of 150 hours, about 150 hours, at least 150 hours, or at least about 150 hours at 75°C, about 75°C, at least 75°C, or at least about 75°C.

[0058] In some embodiments, the energy storage device is configured to grow at most or about 10%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% of its initial length when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C for a period of 1000 hours, about 1000 hours, at least 1000 hours, or at least about 1000 hours. In some embodiments, the energy storage device is configured to grow at most or about 10%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% of its initial length when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C for a period of 2000 hours, about 2000 hours, at least 2000 hours, or at least about 2000 hours. In some embodiments, the energy storage device is configured to grow at most or about 10%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% of its initial length when operated at 3.2V or about 3.2V for a period of 10 years, about 10 years, at least 10 years, or at least about 10 years at 25°C, about 25°C, at least 25°C, or at least about 25°C. In some embodiments, the energy storage device is configured to grow at most or about 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% of its initial length when operated at 3.2V or about 3.2V for a period of 150 hours, about 150 hours, at least 150 hours, or at least about 150 hours at 75°C, about 75°C, at least 75°C, or at least about 75°C.

[0059] In some embodiments, the energy storage device is configured to maintain at most or at most about 500%, 450%, 400%, 350%, 300%, 250%, 200%, 175%, 150%, or 100% of its initial DC-ESR when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C at 3.2V or about 3.2V for a period of 1000 hours, about 1000 hours, at least 1000 hours, or at least about 1000 hours. In some embodiments, the energy storage device is configured to maintain at most or at most about 500%, 450%, 400%, 350%, 300%, 250%, 200%, 175%, 150%, or 100% of its initial DC-ESR when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C at 3.2V or about 3.2V for a period of 2000 hours, about 2000 hours, at least 2000 hours, or at least about 2000 hours. In some embodiments, the energy storage device is configured to maintain at most or at most about 500%, 450%, 400%, 350%, 300%, 250%, 200%, 175%, 150%, or 100% of its initial DC-ESR when operated at or about 3.2V for a period of 10 years, about 10 years, at least 10 years, or at least about 10 years at 25°C, about 25°C, at least 25°C, or at least about 25°C. In some embodiments, the energy storage device is configured to maintain at most or at most about 300%, 250%, 200%, 175%, 150%, 125%, 100%, 75%, 50%, or 25% of its initial DC-ESR when operated at 3.2V or about 3.2V for a period of 150 hours, about 150 hours, at least 150 hours, or at least about 150 hours at 75°C, about 75°C, at least 75°C, or at least about 75°C.

[0060] In some embodiments, the energy storage device is configured to maintain at most or at most about 300%, 250%, 200%, 175%, 150%, 125%, 100%, 75%, 50%, or 25% of its initial AC-ESR when operated at 65°C, about 65°C, at least 65°C, or at least about 65°C at 3.2V or about 3.2V for a period of 1000 hours, about 1000 hours, at least 1000 hours, or at least about 1000 hours. In some embodiments, the energy storage device is configured to maintain at most or at most about 300%, 250%, 200%, 175%, 150%, 125%, 100%, 75%, 50%, or 25% of its initial AC-ESR when operated at 3.2V or about 3.2V for a period of 2000 hours, about 2000 hours, at least 2000 hours, or at least about 2000 hours at 65°C, about 65°C, at least 65°C, or at least about 65°C. In some embodiments, the energy storage device is configured to maintain at most or at most about 300%, 250%, 200%, 175%, 150%, 125%, 100%, 75%, 50%, or 25% of its initial AC-ESR when operated at or about 3.2V for a period of 10 years, about 10 years, at least 10 years, or at least about 10 years at 25°C, about 25°C, at least 25°C, or at least about 25°C. In some embodiments, the energy storage device is configured to maintain at most or at most about 300%, 250%, 200%, 175%, 150%, 125%, 100%, 75%, 50%, or 25% of its initial AC-ESR when operated at 3.2V or about 3.2V for a period of 150 hours, about 150 hours, at least 150 hours, or at least about 150 hours at 75°C, about 75°C, at least 75°C, or at least about 75°C.

[0061] In some embodiments, the energy storage device can be operated at a constant current charge and discharge from an operating voltage to half the operating voltage at an operating temperature. For example, the energy storage device (e.g., a capacitor) can be operated from 3.2V to 1.6V at a temperature of 25°C, 65°C, or 75°C.

[0062] Figure 1 An energy storage device 100 according to one embodiment is shown. Figure 2A yes Figure 1 An exploded view of the energy storage device 100 is shown. Figure 2B yes Figure 2AExploded view of an electrode unit 10. The energy storage device 100 may be an electric double layer device, such as an electric double layer capacitor (EDLC) or a supercapacitor. The energy storage device 100 includes an electrode unit 10, a first terminal 21, a second terminal 22, a housing 30, and a closure 40. The electrode unit 10 includes a first collector sheet 11, a second collector sheet 12, and a separator sheet 13. The electrode unit 10 may be a winding type, in which the first collector sheet 11 and the second collector sheet 12 are wound while being separated from each other by a separator sheet 13. The first terminal 21 and the second terminal 22 are connected to the first collector sheet 11 and the second collector sheet 12, respectively.

[0063] The first collector sheet 11 and the second collector sheet 12 may be used as a positive electrode collector and a negative electrode collector, respectively. In the present embodiment, the first terminal 21 is connected to the first collector sheet 11 (used as a positive electrode collector) and functions as a positive terminal. In addition, the second terminal 22 is connected to the second collector sheet 12 (used as a negative electrode collector) and functions as a negative terminal. Each of the first collector sheet 11 and the second collector sheet 12 may be made of an aluminum foil on which an electrode active material is coated. The electrode active material may be a conductive paste mainly containing activated carbon. In some embodiments, such as Figure 2A and Figure 2B As shown, each of the first terminal 21 and the second terminal 22 includes an aluminum terminal A.

[0064] The housing 30 receives and accommodates the electrode unit 10. The closure 40 covers the top portion of the housing 30. The electrode unit 10 is impregnated with an electrolyte and is placed in the housing 30.

[0065] Electrolytes

[0066] As described herein, the energy storage device includes an electrolyte capable of transmitting ions between the positive electrode and the negative electrode. The electrolyte can be a solution having a solvent, a salt and a performance improver (e.g., an additive), wherein the salt provides an ionic substance for ionic conduction and contact between the positive electrode and the negative electrode. Suitable electrolytes can also exhibit low viscosity and / or high ionic conductivity, thereby being able to reduce the capacitor internal resistance and increase the capacitor voltage during the charging and discharging of the capacitor. For example, the increased solubility of salt in a solvent can increase the ionic conductivity between the positive electrode and the negative electrode. Suitable electrolytes can exhibit chemical and / or electrochemical stability under the operating conditions of the energy storage device, and can be able to withstand repeated charge and discharge cycles of supercapacitors.

[0067] In some embodiments, solvent can include liquid solvent.Solvent provided herein does not need to dissolve each component of electrolyte, and does not need to completely dissolve any component of electrolyte.In other embodiments, solvent can be organic solvent.In some embodiments, solvent can include one or more functional groups selected from carbonate, ether and / or ester.In some embodiments, solvent can include carbonate (for example, cyclic carbonate, non-cyclic carbonate). In some embodiments, the solvent is selected from acetonitrile, γ-butyrolactone, dimethoxyethane, N,N-dimethylformamide, hexamethylphosphoric triamide, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, dimethyl sulfite, cyclopentane, nitromethane, dioxolane, ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), capronitrile, valeronitrile, butyronitrile, propionitrile, methyl ethyl sulfone, methyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl sec-butyl sulfone, butyl isobutyl sulfone, and combinations thereof.

[0068] In some embodiments, the salt is selected from tetraethylammonium salts (e.g., tetraethylammonium tetrafluoroborate, tetraethylammonium iodide, tetraethylammonium hexafluorophosphate, tetraethylammonium bis(trifluoromethanesulfonyl)imide (TFSI), tetraethylammonium bis(fluorosulfonyl)imide (FSI), triethylmethylammonium salts (e.g., triethylmethylammonium tetrafluoroborate, triethylmethylammonium iodide, triethylmethylammonium hexafluorophosphate, triethylmethylammonium bis(trifluoromethanesulfonyl)imide (TFSI), triethylmethylammonium bis(fluorosulfonyl)imide (FSI)), methyltriethylammonium salts (e.g., methyltriethylammonium tetrafluoroborate), tetrabutylammonium salts (e.g., tetrabutylammonium tetrafluoroborate), tetraethylphosphonium salts (e.g., tetraethylphosphonium tetrafluoroborate, tetraethylphosphonium hexafluorophosphate, Phosphonium salts (e.g., tetraethylphosphonium trifluoromethanesulfonate), tetrapropylphosphonium salts (e.g., tetrapropylphosphonium tetrafluoroborate), tetrabutylphosphonium salts (e.g., tetrabutylphosphonium tetrafluoroborate), tetrahexylphosphonium salts (e.g., tetrahexylphosphonium tetrafluoroborate), lithium salts (e.g., lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate), trimethylethylammonium (TMEA) salts (e.g., trimethylethylammonium tetrafluoroborate, trimethylethylammonium hexafluorophosphate, trimethylethylammonium bis(trifluoromethanesulfonyl)imide, trimethylethylammonium bis(fluorosulfonyl)imide), diethyldimethylammonium (DEDMA) salts (e.g., diethyldimethylammonium tetrafluoroborate, diethyldimethylammonium hexafluorophosphate, , diethyldimethylammonium bis(trifluoromethanesulfonyl)imide, diethyldimethylammonium bis(fluorosulfonyl)imide), diethyl-methylmethoxyethylammonium (DEME) salts (e.g., diethyl-methylmethoxyethylammonium tetrafluoroborate, diethyl-methylmethoxyethylammonium hexafluorophosphate, diethyl-methylmethoxyethylammonium bis(trifluoromethanesulfonyl)imide, diethyl-methylmethoxyethylammonium bis(fluorosulfonyl)imide), tetramethylammonium (TMA) salts (e.g., tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bis(trifluoromethanesulfonyl)imide), tetramethylammonium bis(fluorosulfonyl)imide), piperidine-1-spiro-1'-pyrrolidinium (SPP) salts (e.g., piperidine-1-spiro- 1'-pyrrolidinium tetrafluoroborate, piperidine-1-spiro-1'-pyrrolidinium hexafluorophosphate, piperidine-1-spiro-1'-pyrrolidinium bis(trifluoromethanesulfonyl)imide, piperidine-1-spiro-1'-pyrrolidinium bis(fluorosulfonyl)imide), spiro-(1,1')-bipyrrolidinium (SBP) salts (e.g., spiro-(1,1')-bipyrrole alkylium tetrafluoroborate, spiro-(1,1')-bipyrrolidinium iodide, spiro-(1,1')-bipyrrolidinium hexafluorophosphate, spiro-(1,1')-bipyrrolidinium bis(trifluoromethylsulfonyl)imide, spiro-(1,1')-bipyrrolidinium bis(fluorosulfonyl)imide), 1,1-dimethylpyrrolidinium (DMP) salts (e.g., 1,1-dimethylpyrrolidinium tetrafluoroborate, 1,1-dimethylpyrrolidinium hexafluorophosphate, 1,1-dimethylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1,1-dimethylpyrrolidinium bis(fluorosulfonyl)imide), dimethylammonium (DMA) salts (e.g., dimethylammonium tetrafluoroborate, dimethylammonium hexafluorophosphate, dimethylammonium bis(trifluoromethylsulfonyl)imide, dimethylammonium bis(fluorosulfonyl)imide), 1-ethyl-1-methylpyrrolidinium (EMP) salts (e.g., 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-ethyl-1-methylpyrrolidinium hexafluorophosphate, 1,1-dimethylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1,1-dimethylpyrrolidinium bis(fluorosulfonyl)imide), 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide), 1-methyl-1-propylpyrrolidinium (MPP) salts (e.g., 1-methyl-1-propylpyrrolidinium tetrafluoroborate, 1-methyl-1-propylpyrrolidinium hexafluorophosphate, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide), 1-butyl-1-methylpyrrolidinium (BMP) salts (e.g., 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide), 1-ethyl-3-methylimidazolium (EMI) salts (e.g., 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), 1-methyl-3-propylimidazolium (PMI) salts (e.g., 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), For example, 1-methyl-3-propylimidazolium tetrafluoroborate, 1-methyl-3-propylimidazolium hexafluorophosphate, 1-methyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-propylimidazolium bis(fluorosulfonyl)imide), 1-butyl-3-methylimidazolium (BMI) salts (e.g., 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide), and combinations thereof. In some embodiments, the electrolyte is a solution comprising a salt dissolved in a solvent. In some embodiments, the concentration of the salt in the electrolyte is or is about 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1 M, 1.1 M, 1.2 M, 1.3 M, 1.5 M, 1.6 M, 1.8 M, or 2 M, or any range of values ​​therebetween.

[0069] The electrolyte further comprises a performance improver, wherein the performance improver comprises a halogenated heteroaryl compound. In some embodiments, the electrolyte comprises a total performance improver of, about, at most, or at most about 35 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt%, or any range of values ​​therebetween. In some embodiments, the electrolyte comprises a weight percentage of, about, up to, or up to about 25 wt%, 20 wt%, 15 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.2 wt%, or 0.1 wt%, or any range of values ​​therebetween, of each performance modifier (e.g., halogenated heteroaryl compound).

[0070] Halogenated performance improvers

[0071] As described herein, the electrolyte includes a performance improver comprising a halogenated heteroaryl compound. In some embodiments, the halogenated heteroaryl compound may include a nitrogen-containing aromatic heterocycle having at least one halogen atom bonded to an aromatic ring. In some embodiments, the nitrogen-containing aromatic heterocycle may be, for example, pyridine, pyrimidine, pyrazine, or pyridazine.

[0072] Without wishing to be bound by theory, it is believed that the surface of the activated carbon electrode of the energy storage device includes various oxygen-containing functional groups, such as carbonyl and carboxyl functional groups. These oxygen-containing surface functional groups can be highly reactive and can undergo reactions with electrolytes at high voltages and temperatures. It is believed that halogenated heteroaryl compounds can replace oxygen-containing functional groups at the electrode surface. In addition, halogenated heteroaryl compounds can be stabilized by a resonance effect, which minimizes the possibility of subsequent displacement of the halogenated heteroaryl compound from the surface of the electrode (e.g., an activated carbon electrode).

[0073] In some embodiments, the halogenated heteroaryl compound may be a compound of Formula (I) or Formula (II) having the following structure:

[0074]

[0075] In some embodiments, X 1 , X 2 , X 3 , X 4 and X 5 (For example, for each X of formula (II) 1 , X 3 and X5 ) are each independently H or halogen, provided that X 1 , X 2 , X 3 , X 4 and X 5 At least one of is a halogen. In some embodiments, the halogen can be selected from fluorine, chlorine, bromine or iodine. In some embodiments, the compound of formula (I) is not pyridine. In some embodiments, X 1 is H or halogen. In some embodiments, X 1 is H, fluorine, chlorine, bromine, or iodine. 1 X is fluorine, chlorine, bromine, or iodine. 1 X is H, chlorine, bromine, or iodine. 1 X is H, fluorine, bromine, or iodine. 1 X is H, fluorine, chlorine, or iodine. 1 X is H, fluorine, chlorine, or bromine. 2 is H or halogen. In some embodiments, X 2 is H, fluorine, chlorine, bromine, or iodine. 2 X is fluorine, chlorine, bromine, or iodine. 2 X is H, chlorine, bromine, or iodine. 2 X is H, fluorine, bromine, or iodine. 2 X is H, fluorine, chlorine, or iodine. 2 X is H, fluorine, chlorine, or bromine. 3 is H or halogen. In some embodiments, X 3 is H, fluorine, chlorine, bromine, or iodine. 3 X is fluorine, chlorine, bromine, or iodine. 3 X is H, chlorine, bromine, or iodine. 3 X is H, fluorine, bromine, or iodine. 3 X is H, fluorine, chlorine, or iodine. 3 X is H, fluorine, chlorine, or bromine. 4 is H or halogen. In some embodiments, X 4 X is H, fluorine, chlorine, bromine, or iodine. 4 X is fluorine, chlorine, bromine, or iodine. 4 X is H, chlorine, bromine, or iodine. 4X is H, fluorine, bromine, or iodine. 4 X is H, fluorine, chlorine, or iodine. 4 X is H, fluorine, chlorine, or bromine. 5 is H or halogen. In some embodiments, X 5 X is H, fluorine, chlorine, bromine, or iodine. 5 X is fluorine, chlorine, bromine, or iodine. 5 X is H, chlorine, bromine, or iodine. 5 X is H, fluorine, bromine, or iodine. 5 X is H, fluorine, chlorine, or iodine. 5 is H, fluorine, chlorine, or bromine.

[0076] For example, in some embodiments, the compound of formula (I) may include

[0077]

[0078] In some embodiments, the halogenated heteroaryl compound is added to the electrolyte of the energy storage device. In some embodiments, more than one species of the halogenated heteroaryl compound may be present in the electrolyte. In some embodiments, the halogenated heteroaryl compound is added to at least one electrode or electrode film of the energy storage device. In some embodiments, more than one species of the halogenated heteroaryl compound may be present in at least one electrode or electrode film. In some embodiments, the electrode or electrode film containing the halogenated heteroaryl compound is placed in an electrolyte solution.

[0079] Example

[0080] Exemplary embodiments of the present disclosure, including methods, materials, and / or resulting products, are disclosed in the following examples.

[0081] In this article and in Figures 3A-6D The capacitor described in the invention includes electrodes formed from aluminum foil, wherein the electrode film includes an active material: activated carbon; a binder mixture: a mixture of styrene-butadiene rubber, poly(tetrafluoroethylene), carboxymethyl cellulose and poly(vinyl pyrrolidone), and a conductive material: carbon black; a solvent: acetonitrile; and a quaternary ammonium salt.

[0082] Example 1

[0083] Figures 3A-3CThe changes in capacitance, cell length, and DC-ESR of capacitors tested at 3.2 V and 75 °C for 156 hours are shown, respectively, comparing capacitors having 1) a control electrolyte (i.e., “no additive”), 2) an electrolyte having 5 wt.% benzonitrile as a performance modifier, and 3) 5 wt.% halogenated heteroaromatic compound 2-fluoropyridine as a performance modifier. Figures 3A-3C It was shown that capacitors including 2-fluoropyridine as a performance improver exhibited reduced gas generation when compared to control or benzonitrile performance improver devices ( Figure 3B ), increased capacitance retention ( Figure 3A ) and DC-ESR inhibition ( Figure 3C ).

[0084] Example 2

[0085] Figures 4A-4D The changes in cell length, capacitance, DC-ESR, and AC-ESR of capacitors tested at 3.2 V and 65 ° C for 1000 hours are shown, respectively, comparing capacitors having 1) a control electrolyte (i.e., "N1") and 2) an electrolyte having 3 wt.% of a halogenated heteroaromatic compound 2-fluoropyridine as a performance improver ("N2"). Figures 4A-4D It was shown that the capacitor including 3 wt.% of 2-fluoropyridine as a performance improver showed reduced gas generation when compared to the device without added performance improver ( Figure 4A ), improved capacitance reduction rate ( Figure 4B ) and improved resistance increase rate ( Figure 4C and 4D ).

[0086] Example 3

[0087] Figures 5A-5C The changes in cell length, capacitance, and DC-ESR of capacitors with different heteroaryl performance modifiers tested at 3.2 V and 75° C. for 156 hours are shown, respectively, where the capacitors were tested with 1) a control electrolyte (i.e., "no additive") and an electrolyte with 2) a halogenated heteroaryl compound 2-fluoropyridine, 3) a halogenated heteroaryl compound 3-fluoropyridine, or 4) a halogenated heteroaryl compound 2,6-difluoropyridine as a performance modifier. All capacitors with heteroaryl performance modifiers showed reduced gas generation ( Figure 5A ), improved capacitance reduction rate ( Figure 5B ) and improved resistance increase rate ( Figure 5C ).

[0088] Example 4

[0089] Figures 6A-6DThe changes in cell length, capacitance, DC-ESR, and AC-ESR of capacitors tested for 156 hours at 3.2 V and 75° C. with different concentrations of a halogenated heteroaryl compound 2-fluoropyridine performance modifier (i.e., “A12”) are shown, respectively, where the capacitors were tested with 1) a control electrolyte (i.e., “no additive”) and an electrolyte having 2) 1 wt.%, 3) 2 wt.%, 4) 3 wt.%, 5) 5 wt.%, 6) 7 wt.%, and 7) 10 wt.% of 2-fluoropyridine. When compared to devices without added performance modifiers, capacitors with 2-fluoropyridine performance modifiers between about 1 wt.% and about 10 wt.% showed reduced gas generation ( Fig. 6A ) and improved capacitance reduction rate ( Figure 6B Capacitors having between about 1 wt.% and about 7 wt.% of a 2-fluoropyridine performance modifier exhibited an improved rate of resistance increase when compared to devices without the added performance modifier ( Figure 6C and 6D ).

[0090] Although certain embodiments have been described, these embodiments are provided by way of example only and are not intended to limit the scope of the present disclosure. In fact, the novel methods and systems disclosed herein may be embodied in various other forms. In addition, various omissions, substitutions, and changes may be made to the systems and methods described herein without departing from the spirit of the present disclosure. The attached claims and their equivalents are intended to cover such forms or modifications that fall within the scope and spirit of the present disclosure.

[0091] Features, materials, properties or groups described in conjunction with a specific aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless incompatible therewith. All features disclosed in this specification (including any attached claims, abstracts and drawings), and / or all steps of any disclosed method or process, may be combined in any combination, except for at least some mutually exclusive combinations of such features and / or steps. The protection is not limited to the details of any of the foregoing embodiments. The protection extends to any new feature or any new combination of the features disclosed in this specification (including any attached claims, abstracts and drawings), or to any new step or any new combination of the steps of any disclosed method or process.

[0092] In addition, certain features disclosed in the present disclosure in the context of separate implementations may also be implemented in combination in a single implementation. Conversely, various features disclosed in the context of a single implementation may also be implemented in multiple implementations, either individually or in any suitable subcombination. In addition, while the features may be described above as functioning in certain combinations, in some cases, one or more features from a claimed combination may be removed from the combination, and the combination may be claimed as a subcombination or a variation of a subcombination.

[0093] In addition, although operations may be depicted in the drawings or disclosed in the specification in a particular order, such operations do not need to be performed in the particular order shown or in a sequential order, or all operations are performed to achieve the desired result. Other operations not depicted or disclosed may be combined in the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously, or between any described operations. And, in other implementations, these operations may be rearranged or reordered. It should be understood by those skilled in the art that, in some embodiments, the actual steps taken in the process shown and / or disclosed may be different from those shown in the figure. Depending on the embodiment, some of the above steps may be removed and other steps may be added. In addition, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. Moreover, the separation of various system components in the above embodiments should not be understood as requiring such separation in all embodiments, and it should be understood that the components and systems may generally be integrated together in a single product or packaged into multiple products. For example, any components for the energy storage system described herein may be provided separately, or integrated together (e.g., packaged together, or attached together) to form an energy storage system.

[0094] For the purposes of this disclosure, certain aspects, advantages, and novel features are disclosed herein. Not all such advantages may be realized according to any specific embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure may be embodied or implemented in a manner that realizes one advantage or a group of advantages as taught herein without necessarily realizing other advantages that may be taught or suggested herein.

[0095] Conditional language, such as "may," "should," "might," or "should," unless expressly stated otherwise or understood otherwise in the context of use, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements, and / or steps. Thus, such conditional language is generally not intended to imply that features, elements, and / or steps are in any way required by one or more embodiments, or that one or more embodiments necessarily include logic for determining, with or without user input or prompting, whether such features, elements, and / or steps are included or to be performed in any particular embodiment.

[0096] Unless specifically stated otherwise, conjunction language, such as the phrase "at least one of X, Y, and Z," is otherwise understood in context as generally used to convey that an item, term, etc. can be X, Y, or Z. Thus, such conjunction language is generally not intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.

[0097] Language of degree used herein, such as the terms “approximately,” “about,” “generally,” and “substantially” as used herein, means a value, amount, or characteristic that approaches the stated value, amount, or characteristic and still performs the desired function or achieves the desired result.

[0098] The scope of the present disclosure is not intended to be limited by the specific disclosure of the embodiments in this section or elsewhere in this specification, and may be limited by the claims provided in this section or elsewhere in this specification or provided in the future. The language of the claims should be interpreted broadly based on the language employed in the claims and not limited to the embodiments described in this specification or during the prosecution of this application, which embodiments should be interpreted non-exclusively.

[0099] Although certain embodiments are described, these embodiments are provided by way of example only and are not intended to limit the scope of the present disclosure. In fact, the novel methods and systems disclosed herein can be embodied in various other forms. In addition, various omissions, substitutions and changes can be made to the systems and methods described herein without departing from the spirit of the present disclosure. The attached claims and their equivalents are intended to cover such forms or modifications that fall within the scope and spirit of the present disclosure. Therefore, the scope of the present invention is limited only by reference to the attached claims.

Claims

1. An electrolyte comprising: Salt; Solvents; and A performance improver, wherein the performance improver comprises a halogenated heteroaryl compound.

2. The electrolyte according to claim 1, wherein The halogenated heteroaryl compound includes a compound of formula (I) having the following structure: Among them, X 1 , X 2 , X 3 , X 4 and X 5 are each independently H or halogen, provided that X 1 , X 2 , X 3 , X 4 and X 5 At least one of them is a halogen.

3. The electrolyte according to claim 2, wherein The halogen is selected from the group consisting of -F, -Cl, -Br and -I.

4. The electrolyte according to any one of claims 2 to 3, wherein The compound of formula (I) is a compound selected from the group consisting of:

5. The electrolyte according to any one of claims 2 to 4, wherein The compound of formula (I) is selected from the group consisting of:

6. The electrolyte according to any one of claims 2 to 5, wherein The compound of formula (I) is 7. The electrolyte according to any one of claims 2 to 5, wherein The compound of formula (I) is 8. The electrolyte according to any one of claims 2 to 5, wherein The compound of formula (I) is 9. The electrolyte according to any one of claims 1 to 8, wherein The electrolyte includes about 0.1 wt % to about 30 wt % of the performance improver.

10. The electrolyte according to any one of claims 1 to 9, wherein The electrolyte comprises about 0.5 wt % to about 15 wt % of the compound of formula (I).

11. The electrolyte according to any one of claims 1 to 10, wherein The salt includes a compound selected from the group consisting of tetraethylammonium salt, triethylmethylammonium salt, methyltriethylammonium salt, tetrabutylammonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, tetrahexylphosphonium salt, lithium salt, trimethylethylammonium (TMEA) salt, diethyldimethylammonium (DEDMA) salt, diethyl-methylmethoxyethylammonium (DEME) salt, tetramethylammonium (TMA) salt, piperidine-1-spiro-1'-pyrrolidinium (SPP) salt, spiro-(1,1') -bipyrrolidinium (SBP) salts, 1,1-dimethylpyrrolidinium (DMP) salts, dimethylammonium (DMA) salts, 1-ethyl-1-methylpyrrolidinium (EMP) salts, 1-methyl-1-propylpyrrolidinium (MPP) salts, 1-butyl-1-methylpyrrolidinium (BMP) salts, 1-ethyl-3-methylimidazolium (EMI) salts, 1-methyl-3-propylimidazolium (PMI) salts, 1-butyl-3-methylimidazolium (BMI) salts, and combinations thereof.

12. The electrolyte according to any one of claims 1 to 11, wherein The solvent includes a compound selected from the group consisting of acetonitrile, γ-butyrolactone, dimethoxyethane, N,N-dimethylformamide, hexamethylphosphoric triamide, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, dimethyl sulfite, cyclopentane, nitromethane, dioxolane, ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), capronitrile, valeronitrile, butyronitrile, propionitrile, methyl ethyl sulfone, methyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl sec-butyl sulfone, butyl isobutyl sulfone and combinations thereof.

13. An energy storage device, comprising: cathode; anode; a separator disposed between the cathode and the anode; The electrolyte according to any one of claims 1 to 12; as well as A housing, wherein the cathode, anode, separator and electrolyte are disposed within the housing.

14. The device according to claim 13, wherein: The energy storage device is a capacitor.

15. The device according to any one of claims 13-14, wherein: The energy storage device is configured to retain at least about 80% of its initial capacitance when operated at about 3.2 V at a temperature of about 65° C. for a period of about 1000 hours.

16. The device according to any one of claims 13 to 15, wherein: The energy storage device is configured to grow at most about 4% of its initial length when operated at about 3.2 V at a temperature of about 65° C. for a period of about 1000 hours.

17. The device according to any one of claims 13 to 16, wherein: The energy storage device is configured to maintain at most about 175% of its initial DC-ESR when operated at about 3.2 V at a temperature of about 65° C. for a period of about 1000 hours.

18. The device according to any one of claims 13 to 17, wherein: The energy storage device is configured to maintain at most about 175% of its initial AC-ESR when operated at about 3.2 V at a temperature of about 65° C. for a period of about 1000 hours.

19. A method for manufacturing an energy storage device, comprising: A cathode, an anode, a separator, an electrolyte, and a performance improver are disposed within a housing, wherein the performance improver comprises a halogenated heteroaryl compound.

20. The method according to claim 19, wherein: Prior to the disposing step, at least one of the cathode and the anode comprises the performance enhancer.

21. The method according to claim 19, wherein: Prior to the providing step, the electrolyte comprises the performance enhancer.

22. An electrode membrane comprising: Active materials; Adhesives; as well as A performance improver, wherein the performance improver comprises a halogenated heteroaryl compound.

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