Nonaqueous electrolytic composition and use thereof

Abstract

To provide a nonaqueous electrolytic solution which provides improved properties over nonaqueous electrolytic solutions of the prior art, a battery electrolyte formulation, a battery, a method of reducing the flash point of a battery and / or a battery electrolyte formulation, a method of powering an article, a method of improving a battery electrolyte formulation, and a method of preparing a battery electrolyte formulation.SOLUTION: A compound of formula 1 in the figure is used in a nonaqueous battery electrolyte formulation. (In the formula, R is, H, F, CF3, alkyl, or fluoroalkyl).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to non-aqueous electrolytes for energy storage devices, including batteries and capacitors, particularly for secondary batteries and devices known as supercapacitors. [Background technology]

[0002] There are two main types of batteries: primary and secondary. Primary batteries are also known as non-rechargeable batteries. Secondary batteries are also known as rechargeable batteries. A well-known type of secondary battery is the lithium-ion battery. Lithium-ion batteries have high energy density, no memory effect, and low self-discharge.

[0003] Lithium-ion batteries are commonly used in portable electronic devices and electric vehicles. In batteries, lithium ions move from the negative electrode to the positive electrode during discharge and back during charging.

[0004] Typically, the electrolyte contains additives in addition to a non-aqueous solvent and an electrolyte salt. The electrolyte is typically a mixture of organic carbonates, such as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, and dialkyl carbonate, containing a lithium ion electrolyte salt. Many lithium salts can be used as the electrolyte salt, and common examples include lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

[0005] The electrolyte must perform many distinct roles within the battery.

[0006] The electrolyte's primary role is to facilitate the flow of charge between the cathode and anode. This occurs by transporting metal ions within the battery to or from one or both of the anode and cathode, thereby chemically reducing or oxidizing them and releasing / adopting charge.

[0007] Thus, the electrolyte must provide a medium capable of solvating and / or supporting the metal ions.

[0008] Due to the use of lithium electrolyte salts and the exchange of lithium ions with lithium metal, which is highly reactive with water, as well as the sensitivity of other battery components to water, the electrolyte is typically non-aqueous.

[0009] In addition, the electrolyte must have suitable rheological properties to allow / enhance the flow of ions therein at the typical operating temperatures to which the battery is expected to function.

[0010] Additionally, the electrolyte must be as chemically inert as possible. This is particularly relevant in the context of the battery's expected lifespan, with regard to internal corrosion within the battery (such as of the electrodes and casing) and battery leakage issues. Also important to consider in chemical stability is flammability. Unfortunately, typical electrolyte solvents often contain flammable materials, which can pose a safety hazard.

[0011] This can be problematic because the battery can accumulate heat during discharge or discharged operation. This is especially true for high-density batteries such as lithium-ion batteries. Therefore, it is desirable for the electrolyte to exhibit low flammability along with other related properties such as a high flash point.

[0012] It is also desirable that the electrolyte not present any environmental concerns regarding disposability after use or other environmental concerns such as global warming potential. DISCLOSURE OF THE INVENTION

[0013] It is an object of the present invention to provide a non-aqueous electrolyte that offers improved properties over prior art non-aqueous electrolytes.

[0014] The listing or discussion of an apparently prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.

[0015] Usage According to a first aspect of the present invention there is provided the use of a compound of Formula 1 in a non-aqueous battery electrolyte formulation.

[0016] According to a second aspect of the present invention, there is provided the use of a non-aqueous battery electrolyte formulation comprising a compound of Formula 1 in a battery.

[0017] Configuration / Device Aspects According to a third aspect of the present invention, there is provided a battery electrolyte formulation comprising a compound of Formula 1.

[0018] According to a fourth aspect of the present invention, there is provided a formulation comprising a metal ion and a compound of formula 1, optionally in combination with a solvent.

[0019] According to a fifth aspect of the present invention, there is provided a battery comprising a battery electrolyte formulation comprising a compound of Formula 1.

[0020] Method aspects According to a sixth aspect of the present invention there is provided a method of reducing the flash point of a battery and / or battery electrolyte formulation comprising the addition of a formulation comprising a compound of Formula 1.

[0021] According to a seventh aspect of the present invention, there is provided a method of powering an article, comprising using a battery comprising a battery electrolyte formulation comprising a compound of Formula 1.

[0022] According to an eighth aspect of the present invention, there is provided a method of improving a battery electrolyte formulation, the method comprising either (a) at least partially replacing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula 1, and / or (b) supplementing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula 1.

[0023] According to a ninth aspect of the present invention, there is provided a method of preparing a battery electrolyte formulation, the method comprising combining a compound of Formula 1 with a lithium-containing compound.

[0024] According to a tenth aspect of the present invention, there is provided a method of preparing a battery electrolyte formulation, the method comprising mixing a composition comprising a compound of Formula 1 with a lithium-containing compound.

[0025] According to an eleventh aspect of the present invention, there is provided a method for improving battery capacity / charge transfer in a battery, which may improve battery life by using a compound of formula 1.

[0026] Compound of Formula 1 For all aspects of the present invention, preferred embodiments of Formula 1 are as follows: [ka] where R=H, F, CF3, alkyl or fluoroalkyl.

[0027] Preferably, "alkyl" means C1 to C6. "Fluoroalkyl" means an alkyl group that is partially or fully fluorinated.

[0028] Preferably, at least four R groups can be F, or Preferably, at least six R groups can be F, or Conveniently, all eight R groups may be F.

[0029] Additionally, there is a need for new methods of preparing compounds of formula 1 based on readily available raw materials and reagents from which compounds of formula 1 can be economically prepared in high purity.

[0030] Useful methods include, but are not limited to: 1) Chlorination and halogen exchange reactions, e.g., [ka] where M=metal, for example, alkali metal, alkaline earth metal or transition metal.

[0031] By repeating these steps, additional fluorine substituents can be incorporated.

[0032] 2) Reaction of carbonyl groups with sulfur tetrafluoride, e.g., [ka] by.

[0033] By using substrates containing multiple carbonyl groups, additional fluorine substituents can be incorporated. 3) Suitable polyol ethers, e.g. [ka] By closing the ring.

[0034] The catalyst is a Bronsted acid or base or a Lewis acid or base and can be in gas, liquid or solid form.

[0035] 4) electrophilic fluorine sources, e.g., [ka] By direct fluorination of suitable organic feedstocks using

[0036] Suitable fluorinating agents include elemental fluorine, neat or diluted, electrophilic fluorinating agents such as Selectfluor, etc. It will be appreciated that by using reagents such as these, multiple fluorines can be introduced by adjusting the reaction stoichiometry and conditions.

[0037] In a preferred embodiment, the compound represented by formula (I) is as follows: [ka]

[0038] This compound can be made by reaction of dione with SF4. [ka]

[0039] How to do this is taught in Muratov, NN; Burmakov, AI; Kunchenko, BV; Alekseeva, LA; Agupol'skii, LM; Zhurnal Organicheskoi Khimii (1982), 18(7), 1403-6.

[0040] advantage In an embodiment of the present invention, an electrolyte formulation has been found to be surprisingly advantageous.

[0041] The advantages of using compounds of Formula 1 in electrolyte solvent compositions manifest themselves in several ways: their presence can reduce the flammability of the electrolyte composition (e.g., as measured by flash point); their oxidative stability makes them useful for batteries required to operate in harsh conditions; at elevated temperatures, they are compatible with common electrode chemistries and may even improve the performance of these electrodes through their interaction with these electrodes.

[0042] Furthermore, electrolyte compositions containing compounds of Formula 1 may have excellent physical properties, including low viscosity and low melting but high boiling points, along with the associated benefit of little or no gassing during use. The electrolyte formulations may wet and spread surfaces very well, particularly fluorine-containing surfaces, which is hypothesized to be due to the beneficial relationship between their adhesive and cohesive strengths, resulting in low contact angles.

[0043] Furthermore, electrolyte compositions containing compounds of Formula 1 may have excellent electrochemical properties, including improved capacity retention, improved cyclability and capacity, and improved compatibility with other battery components, such as separators and current collectors. They may also have excellent electrochemical properties with all types of cathode and anode chemistries, including systems operating over a wide range of voltages and particularly at high voltages, and may contain additives such as silicon, and may reduce gas generation and associated battery pack swelling during use. Furthermore, the electrolyte formulations may exhibit good solvation of metal (e.g., lithium) salts and good interaction with any other electrolyte solvents present.

[0044] Preferred features relating to aspects of the present invention are as follows:

[0045] Preferences and options for a given aspect, feature or parameter of the invention should be considered as disclosed in combination with any and all preferences and options in all other aspects, features, and parameters of the invention, unless the context indicates otherwise.

[0046] Preferred compounds Preferred examples of compounds of the first embodiment of formula 1 [ka] Preferably, at least four R groups are F or Preferably, at least six R groups are F, or Conveniently, all eight R groups may be F.

[0047] In certain preferred embodiments, the two R groups attached to a given carbon in the dioxane ring can be the same substituent, i.e., H, F, CF3, or fluoroalkyl. Advantageously, two or more carbon atoms in the dioxane ring can have the same substituent attached to each carbon atom.

[0048] Electrolyte supplements The electrolyte formulation will preferably contain 0.1% to 99.9% by weight of the compound of formula 1, preferably 90.0% to 99.9% by weight of the compound of formula 1. Preferably, the compound of formula (I) is present in the electrolyte formulation in an amount of 1 to 30% by weight, more preferably 5 to 20% by weight, for example 5 to 15% or 10% by weight.

[0049] In one embodiment, optionally, the compound of formula (1) is present in the electrolyte formulation in an amount of 95% by weight or less, e.g., 75% by weight or less, e.g., 50% by weight or less, preferably 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less. More preferably, the compound of formula (1) is present in the electrolyte formulation in an amount of about 1% by weight to about 30% by weight, e.g., about 1% by weight to about 25% by weight, e.g., about 1% by weight to about 20% by weight or about 5% by weight to about 20% by weight, e.g., about 1% by weight to about 15% by weight, or about 5% by weight to about 15% by weight, about 1% by weight to about 10% by weight, or about 1% by weight to about 5% by weight.

[0050] metal salts The non-aqueous electrolyte solution further comprises a metal electrolyte salt, which is typically present in an amount of 0.1 to 20% by weight, based on the total mass of the non-aqueous electrolyte formulation.

[0051] Metal salts generally include salts of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

[0052] Preferably, the metal salt comprises a salt of lithium such as one selected from the group comprising lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N).

[0053] Most preferably, the metal salt comprises LiPF6. Thus, in a fourth and most preferred aspect of the invention, there is provided a formulation comprising LiPF6 and a compound of formula 1, optionally in combination with a solvent.

[0054] Other solvents The non-aqueous electrolyte may contain an additional solvent, preferred examples of which include fluoroethylene carbonate (FEC) and / or propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or ethylene carbonate (EC).

[0055] When present, the additional solvent comprises 0.1% to 99.9% by weight of the liquid component of the electrolyte.

[0056] additives The non-aqueous electrolyte may contain additives.

[0057] A suitable additive can act as a surface film-forming agent that forms an ion-permeable film on the surface of the positive or negative electrode, thereby preventing the decomposition reaction of the non-aqueous electrolyte and the electrolyte salt that occurs on the surface of the electrode and preventing the decomposition reaction of the non-aqueous electrolyte on the surface of the electrode.

[0058] Examples of film-forming additives include vinylene carbonate (VC), ethylene sulfite (ES), lithium bis(oxalato)borate (LiBOB), cyclohexylbenzene (CHB), and orthoterphenyl (OTP). The additives may be used alone or in combination of two or more.

[0059] When present, the additive is present in an amount of 0.1 to 3% by weight, based on the total mass of the non-aqueous electrolyte formulation.

[0060] battery Primary / secondary battery The battery may comprise a primary battery (non-rechargeable) or a secondary battery (rechargeable). Most preferably, the battery comprises a secondary battery.

[0061] Batteries containing non-aqueous electrolytes will generally include several components. The components that make up a preferred non-aqueous electrolyte secondary battery cell are described below. It should be understood that other battery components (such as a temperature sensor) may be present, and the following list of battery components is not intended to be exhaustive.

[0062] electrode Batteries generally contain a positive electrode and a negative electrode. The electrodes are usually porous, allowing metal ions (lithium ions) to enter and exit their structure in a process called intercalation or deintercalation.

[0063] In rechargeable batteries (secondary batteries), the term cathode refers to the electrode where reduction occurs during the discharge cycle. In lithium-ion cells, the positive electrode ("cathode") is the lithium-based electrode.

[0064] Positive electrode (cathode) The positive electrode generally consists of a positive current collector, such as a metal foil, and optionally has a positive active material layer on the positive current collector.

[0065] The positive electrode current collector can be a foil of a metal that is stable over the range of potentials applied to the positive electrode, or a film having a skin layer of a metal that is stable over the range of potentials applied to the positive electrode. Aluminum (Al) is a preferred metal that is stable over the range of potentials applied to the positive electrode.

[0066] The positive electrode active material layer generally contains a positive electrode active material and other components such as a conductive agent and a binder, and is generally obtained by mixing the components in a solvent, applying the mixture to a positive electrode current collector, and then drying and rolling.

[0067] The positive electrode active material can be lithium (Li) containing a transition metal oxide. The transition metal element can be at least one selected from the group consisting of scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and yttrium (Y). Among these transition metal elements, manganese, cobalt, and nickel are most preferred.

[0068] Furthermore, in certain embodiments, transition metal halides may be preferred.

[0069] Some of the transition metal atoms in the transition metal oxide can be replaced by atoms of non-transition metal elements. The non-transition elements can be selected from the group consisting of magnesium (Mg), aluminum (Al), lead (Pb), antimony (Sb), and boron (B). Among these non-transition metal elements, magnesium and aluminum are most preferred.

[0070] Preferred examples of the positive electrode active material include LiCoO2, LiNiO2, LiMn2O4, LiMnO2, LiNi 1-y Co y O2 (0 < y < 1), LiNi 1-y-z Co y Mn z O2 (0 < y + z < 1), and LiNi 1-y-z Co y Al z O2 (0 < y + z < 1), etc., lithium-containing transition metal oxides. From the viewpoints of cost and specific capacity, LiNi1-y-zCo y Mn z O2 (0 < y + z < 0.5) and LiNi 1-y-z Co y Al z O2 (0 < y + z < 0.5) are desirable. Since these positive electrode active materials contain a large amount of alkaline components, they promote the decomposition of the non-aqueous electrolyte and cause a decrease in durability. However, the non-aqueous electrolyte of the present disclosure is resistant to decomposition even when used in combination with these positive electrode active materials.

[0071] The positive electrode active material may be lithium (Li) containing a transition metal fluoride. The transition metal element may be at least one selected from the group consisting of scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and yttrium (Y). Of these transition metal elements, manganese, cobalt, and nickel are most preferred.

[0072] Some of the transition metal atoms in the transition metal fluoride may be replaced by atoms of a non-transition metal element. The non-transition element may be selected from the group consisting of magnesium (Mg), aluminum (Al), lead (Pb), antimony (Sb) and boron (B). Of these non-transition metal elements, magnesium and aluminum are most preferred.

[0073] A conductive agent can be used to enhance the electronic conductivity of the positive electrode active material layer. Preferred examples of the conductive agent include conductive carbon materials, metal powders, and organic materials. Specific examples include carbon materials such as acetylene black, ketjen black, and graphite, metal powders such as aluminum powder, and organic materials such as phenylene derivatives.

[0074] To ensure good contact between the positive electrode active material and the conductive agent, a binder may be used to enhance the adhesion of components such as the positive electrode active material to the surface of the positive electrode current collector. Preferred examples of binders include fluoropolymers and rubber polymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-isoprene copolymer, and ethylene-propylene-butadiene copolymer. The binder may be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).

[0075] Negative electrode (anode) The negative electrode generally comprises a negative electrode current collector such as a metal foil, and optionally has a layer of negative electrode active material on the negative electrode current collector.

[0076] The negative electrode current collector can be a metal foil. A suitable metal is copper (lithium-free). Copper is low-cost, easy to process, and has good electronic conductivity.

[0077] Typically, the negative electrode comprises carbon, such as graphite or graphene.

[0078] Silicon-based materials can also be used for the negative electrode. A preferred form of silicon is in the form of nanowires, which are preferably present on a support material. The support material can include metals (such as steel) or non-metals such as carbon.

[0079] The negative electrode may include an active material layer, which, if present, comprises the negative electrode active material and other components, such as a binder, and is generally obtained by mixing the components in a solvent, applying the mixture to a positive electrode current collector, followed by drying and rolling.

[0080] The negative electrode active material is not particularly limited as long as it can store and release lithium ions. Examples of suitable negative electrode active materials include carbon materials, metals, alloys, metal oxides, metal nitrides, and lithium-intercalated carbon and silicon. Examples of carbon materials include natural / artificial graphite and pitch-based carbon fiber. Preferred examples of metals include lithium (Li), silicon (Si), tin (Sn), germanium (Ge), indium (In), gallium (Ga), titanium, lithium alloys, silicon alloys, and tin alloys. Examples of lithium-based materials include lithium titanate (Li2TiO3).

[0081] As with the positive electrode, the binder may be a fluoropolymer or a rubber polymer, and is preferably a rubbery polymer such as styrene-butadiene copolymer (SBR). The binder may be used in combination with a thickener.

[0082] Separator The separator is preferably present between the positive electrode and the negative electrode. The separator has insulating properties. The separator may include a porous film having ion permeability. Examples of porous films include microporous thin films, woven fabrics, and nonwoven fabrics. Suitable materials for the separator include polyolefins such as polyethylene and polypropylene.

[0083] case The battery components are preferably disposed within a protective case.

[0084] The case may comprise any suitable resilient material to provide support to the battery and electrical contact to the device being powered.

[0085] In one embodiment, the case comprises a metal material, preferably in sheet form, formed into the battery shape. The metal material preferably comprises multiple pieces that are adaptable to be attached together (e.g., by pressing) during assembly of the battery. Preferably, the case comprises an iron / steel-based material.

[0086] In another embodiment, the case comprises a plastic material molded to the shape of the battery. The plastic material preferably comprises multiple parts that are adaptable to be joined together (e.g., by press-fitting / adhesion) during battery assembly. Preferably, the case comprises a polymer such as polystyrene, polyethylene, polyvinyl chloride, polyvinylidene chloride, or polymonochlorofluoroethylene. The case may also include other additives for the plastic material, such as fillers or plasticizers. In this embodiment in which the battery case primarily comprises a plastic material, a portion of the casing may further comprise a conductive / metallic material for establishing electrical contact with a device powered by the battery.

[0087] arrangement The positive and negative electrodes may be wound or stacked with a separator between them, and together with a non-aqueous electrolyte, they are contained in an external case, to which the positive and negative electrodes are electrically connected at their respective portions.

[0088] The invention will now be described with reference to the following non-limiting examples. [Example]

[0089] Preparation of 2,2,5,5-tetrafluoro-1,4-dioxane 2,2,5,5-Tetrafluoro-1,4-dioxane was prepared by the reaction of 1,4-dioxane-2,5-dione with sulfur tetrafluoride using a method based on that taught by Muratov et al., except that a reduced excess of SF was used (1.4 vs. 4 equivalents). The crude product was purified by distillation and characterized by mass spectrometry and NMR spectroscopy. Mass spectrum: (m / z) 160, 141, 113, 99, 83, 64, 51. NMR: 1 Hδ(ppm) 4.22(triplet); 19 F(ppm)-81.5(triplet)

[0090] Compositions of the Invention All values ​​below are in % w / w. [Table 1] [Table 2]

[0091] Flammability and Safety Tests flash point Flash points were determined according to the ASTM D6450 standard method using a Grabner Instruments Miniflash FLP / H device. [Table 3]

[0092] These measurements show that the addition of an additive called MEXI-15 increased the flash point of the standard electrolyte.

[0093] Self-extinguishing time The self-extinguishing time was measured with a custom-made device that included an automatically controlled stopwatch connected to an ultraviolet detector. The electrolyte solution to be tested (500 μL) was applied to a Whatman GF / D (diameter = 24 mm) glass microfiber filter. The ignition source was moved under the sample and held in this position for a preset time (1, 5 or 10 seconds) to ignite the sample. Ignition and combustion of the sample was detected using a UV photodetector. The rating is calculated as burn time / electrolyte weight [sg -1 ] over ignition time [s] and extrapolating to ignition time = 0 s by a linear regression line. ·Self-extinguishing time (sg -1 ) is the time it takes for the sample to stop burning once ignited. [Table 4]

[0094] These measurements indicate that compound MEXI-15 has flame retardant properties.

[0095] Electrochemical Testing Drying Prior to testing, MEXI-15 was dried by pre-treatment with activated type 4A molecular sieves. The water levels of the pre-treated and post-treated samples were determined by the Karl Fischer method. [Table 5]

[0096] Electrolyte supplements Electrolyte preparation and storage were carried out in an argon-filled glove box (less than 0.1 ppm HO and O). The base electrolyte was 1 M LiPF in ethylene carbonate:ethyl methyl carbonate (3:7 wt%) with MEXI-15 additive at concentrations of 2, 5, 10, and 30 wt%.

[0097] Cell chemistry and construction The performance of each electrolyte formulation was tested in multi-layer pouch cells (two cells per electrolyte) for 50 cycles. Chemical 1: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and artificial graphite (specific capacity: 350 mAhg -1 ) anode. The areal capacity of NMC622 and graphite is 3.5 mAh cm, respectively. -2 and 4.0mAhcm -2 The N / P ratio was 115%. Chemistry 2: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and SiO x / Graphite (specific capacity: 550mAhg -1 ) Negative electrode: NMC622 and SiO x / graphite areal capacity is 3.5mAh / cm -2 and 4.0mAhcm -2 The N / P ratio reached 115%.

[0098] The test pouch cell has the following characteristics: ·Nominal capacity 240mAh+ / -2% Standard deviation: Capacity: ±0.6mAh Coulombic efficiency (CE) 1st cycle: ±0.13% Coulombic efficiency (CE) subsequent cycles: ±0.1% Positive electrode: NMC-622 ·Active material content: 96.4% ·Mass load: 16.7mgcm -2 Negative electrode: artificial graphite ·Active material content: 94.8% ·Mass load: 10mgcm -2 Separator: PE (16 μm) + 4 μm Al2O3 Balanced with a cutoff voltage of 4.2V Negative electrode: Artificial graphite + SiO ·Active material content: 94.6% ·Mass load: 6.28mgcm -2 Separator: PE (16 μm) + 4 μm Al2O3 Balanced with a cutoff voltage of 4.2V After assembly, the following fabrication protocol was used. 1. Step charge to 1.5V followed by a 5-hour rest step (wet step at 40°C) 2. CCCV(C / 10, 3.7V(I limit : 1 hour) (pre-formation step) 3. Rest step (6 hours) 4. CCCV(C / 10, 4.2V(I limit :0.05C)) Rest step (20 min) 5. CC discharge (C / 10, 3.8V), (cell degassing) 6.CC discharge (C / 10, 2.8V) Following this formation step, the cells were tested as follows. Rest step (1.5V, 5 hours), CCCV (C / 10, 3.7V (1 hour)) Rest step (6 hours), CCCV(C / 10, 4.2V(I limit :0.05C)) Rest step (20 min), CC discharge (C / 10, 3.8 V) Degassing step Discharge (C / 10, 2.8V), rest step (5 hours) CCCV(C / 3, 4.2V(I limit :0.05C), rest step (20 min) ·CC discharge (C / 3, 2.8V) 50 cycles or until 50% SOH is reached at 40°C: CCCV(C / 3, 4.2V(I limit :0.02C), rest step (20 min) CC discharge (C / 3, 3.0V), rest step (20 min)

[0099] Test results The test results for the additive MEXI-15 in each cell chemistry are summarized in Tables 1-2 and Figures 1-2. From this data, it can be seen that the additive in both cell chemistries positively impacted cell performance, improving both coulombic efficiency and cycling stability. These results, combined with safety-related studies, demonstrate that the compounds of the present invention simultaneously improved both the safety and performance of energy storage devices containing them. [Brief explanation of the drawings]

[0100] [Figure 1] 1 shows the 19F NMR spectra of compositions 1a, 1b and 1c. [Figure 2] 19F NMR spectra of compositions 2a, 2b and 2c are shown. [Figure 3] 19F NMR spectra of compositions 3a, 3b and 3c are shown. [Figure 4] 19F NMR spectra of compositions 4a, 4b and 4c are shown. [Figure 5] 1 shows the 19F NMR spectra of compositions 5a, 5b and 5c. [Figure 6] 19F NMR spectra of compositions 6a, 6b and 6c are shown.

[0101] The present invention includes the following aspects. [Aspect 1] Use of compounds of formula 1 in non-aqueous battery electrolyte formulations: [ka] where R is H, F, CF3, alkyl or fluoroalkyl. [Aspect 2] The use according to aspect 1, wherein the alkyl group has a chain length of C1 to C6. [Aspect 3] 3. The use of any one of claims 1 to 2, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. %, based on the total weight of the non-aqueous electrolyte formulation. [Aspect 4] 4. The use according to aspect 3, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc or nickel. [Aspect 5] 5. The use of embodiment 4, wherein the metal salt is a salt of lithium selected from the group comprising lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 6] 6. The use according to any one of aspects 1 to 5, wherein the formulation comprises additional solvent in an amount of 0.1% to 99.9% by weight of the liquid components of the formulation. [Aspect 7] 7. The use according to embodiment 6, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) or ethylene carbonate. [Aspect 8] A battery electrolyte formulation comprising a compound of Formula 1. [Aspect 9] A formulation comprising a metal ion and a compound of formula 1, optionally in combination with a solvent: [ka] where R is H, F, CF3, alkyl or fluoroalkyl. [Aspect 10] A battery comprising a battery electrolyte formulation comprising a compound of Formula 1: [ka] where R is H, F, CF3, alkyl or fluoroalkyl. [Aspect 11] 11. The formulation of any one of aspects 8 to 10, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt % based on the total mass of the non-aqueous electrolyte formulation. [Aspect 12] 12. The formulation of aspect 11, wherein the metal salt is a lithium, sodium, magnesium, calcium, lead, zinc, or nickel salt. [Aspect 13] 13. The formulation of embodiment 12, wherein the metal salt is a salt of a lithium salt selected from the group comprising lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 14] A formulation according to any one of aspects 8 to 13, wherein the formulation comprises additional solvent in an amount between 0.1% and 99.9% by weight of the liquid components of the formulation. [Aspect 15] Aspect 15. The formulation of aspect 14, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC). [Aspect 16] 1. A method for reducing the flammability of a battery and / or a battery electrolyte, comprising: Compounds of Formula 1: [ka] wherein R is H, F, CF3, alkyl, or fluoroalkyl. [Aspect 17] 1. A method of powering an article, comprising using a battery comprising a battery electrolyte formulation comprising a compound of Formula 1: [ka] where R is H, F, CF3, alkyl or fluoroalkyl. [Aspect 18] 1. A method of improving a battery electrolyte formulation, comprising: (a) at least partially replacing a battery electrolyte with a battery electrolyte formulation comprising a compound of Formula 1; and / or (b) incorporating into said battery electrolyte a compound of Formula 1: [ka] wherein R is H, F, CF3, alkyl, or fluoroalkyl. [Aspect 19] 1. A method of preparing a battery electrolyte formulation comprising combining a compound of Formula 1 with ethylene, propylene or fluoroethylene carbonate and lithium hexafluorophosphate. [Aspect 20] A method for improving battery capacity / charge transfer within a battery / battery life, etc., by using a compound of Formula 1. [Aspect 21] 21. The method of any one of aspects 16 to 20, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt %, based on the total mass of the non-aqueous electrolyte formulation. [Aspect 22] 22. The method of embodiment 21, wherein the metal salt is a lithium, sodium, magnesium, calcium, lead, zinc, or nickel salt. [Aspect 23] 23. The method of claim 22, wherein the metal salt is a salt of lithium selected from the group including lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 24] 24. The method of any one of aspects 16-23, wherein the formulation comprises additional solvent in an amount between 0.1% and 99.9% by weight of the liquid components of the formulation. [Aspect 25] 25. The method of embodiment 24, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC).

Claims

1. Use of compounds of formula 1 in non-aqueous battery electrolyte formulations: 【Chemistry 1】 (Wherein, R is H, F, CF ３ , alkyl or fluoroalkyl).

2. The alkyl group has a chain length C １ ~C ６ 2. The use according to claim 1, wherein

3. 3. The use according to claim 1 or claim 2, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20% by weight, based on the total mass of the non-aqueous electrolyte formulation.

4. 4. The use according to claim 3, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc or nickel.

5. The metal salt is lithium hexafluorophosphate (LiPF ６ ), lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium triflate (LiSO ３ CF3), lithium bis(fluorosulfonyl)imide (Li(FSO ２ ) ２ N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO ２ ) ２ 5. The use according to claim 4, wherein the lithium salt is selected from the group comprising:

6. 6. The use according to any one of claims 1 to 5, wherein the formulation comprises additional solvent in an amount of from 0.1% to 99.9% by weight of the liquid component of the formulation.

7. 7. The use according to claim 6, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) or ethylene carbonate.

8. A battery electrolyte formulation comprising a compound of Formula 1.

9. A formulation comprising a metal ion and a compound of Formula 1, optionally in combination with a solvent: 【Chemistry 2】 (Wherein, R is H, F, CF ３ , alkyl or fluoroalkyl).

10. A battery comprising a battery electrolyte formulation comprising a compound of Formula 1: 【Transformation 3】 (Wherein, R is H, F, CF ３ , alkyl or fluoroalkyl).

11. 11. The formulation of any one of claims 8 to 10, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. % based on the total mass of the non-aqueous electrolyte formulation.

12. 12. The formulation of claim 11, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

13. The metal salt is lithium hexafluorophosphate (LiPF ６ ), lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium triflate (LiSO ３ CF3), lithium bis(fluorosulfonyl)imide (Li(FSO ２ ) ２ N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO ２ ) ２ 13. The formulation of claim 12, wherein the salt is a salt of lithium selected from the group comprising:

14. A formulation according to any one of claims 8 to 13, wherein the formulation comprises additional solvent in an amount of from 0.1% to 99.9% by weight of the liquid component of the formulation.

15. 15. The formulation of claim 14, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) and ethylene carbonate (EC).

16. 1. A method for reducing the flammability of a battery and / or a battery electrolyte, comprising: Compound of Formula 1: 【Chemistry 4】 (Wherein, R is H, F, CF ３ , alkyl or fluoroalkyl).

17. 1. A method of powering an article, comprising using a battery comprising a battery electrolyte formulation comprising a compound of Formula 1: 【Transformation 5】 (Wherein, R is H, F, CF ３ , alkyl or fluoroalkyl).

18. 1. A method of improving a battery electrolyte formulation, comprising: (a) at least partially replacing a battery electrolyte with a battery electrolyte formulation comprising a compound of Formula 1; and / or (b) adding to said battery electrolyte a compound of Formula 1: 【Transformation 6】 (Wherein, R is H, F, CF ３ and replenishing the battery electrolyte formulation with a hydroxybenzoate, wherein the hydroxybenzoate is hydroxybenzoate, alkyl, or fluoroalkyl.

19. 1. A method of preparing a battery electrolyte formulation comprising mixing a compound of Formula 1 with ethylene, propylene or fluoroethylene carbonate and lithium hexafluorophosphate.

20. A method for improving battery capacity / charge transfer within a battery / battery life, etc. by using the compound of formula 1.

21. 21. The method of any one of claims 16 to 20, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. % based on the total mass of the non-aqueous electrolyte formulation.

22. 22. The method of claim 21, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

23. The metal salt is lithium hexafluorophosphate (LiPF ６ ), lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium triflate (LiSO ３ CF3), lithium bis(fluorosulfonyl)imide (Li(FSO ２ ) ２ N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO ２ ) ２ 23. The method of claim 22, wherein the lithium salt is selected from the group comprising:

24. 24. The method of any one of claims 16 to 23, wherein the formulation comprises additional solvent in an amount of from 0.1% to 99.9% by weight of the liquid component of the formulation.

25. 25. The method of claim 24, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) and ethylene carbonate (EC).

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