Composition

Abstract

1. Use of a compound of formula I in a non-aqueous battery electrolyte formulation, comprising: [Formula 1] TIFF2022552872000027.tif31166 formula, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, Use where p is an integer from 0 to 9.

Description

Technical Field

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

Background Art

[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 rechargeable battery is the lithium-ion battery. Lithium-ion batteries have a high energy density, no memory effect, and low self-discharge.

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

[0004] Typically, the electrolyte includes 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, common examples including lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide "LiFSI", and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

[0005] The electrolyte must perform several individual roles within the battery.

[0006] The main role of the electrolyte is to facilitate the flow of charge carriers between the cathode and the anode. This occurs by the transport of metal ions within the battery from one or both of the anode and cathode and to or from them, and by chemical reduction or oxidation, where charge is released / acquired.

[0007] Therefore, the electrolyte needs to provide a medium that can solvate and / or support metal ions.

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

[0009] Additionally, the electrolyte must have rheological properties suitable for enabling / enhancing the flow of ions therein at typical operating temperatures at which the battery is expected to be exposed and function.

[0010] Furthermore, the electrolyte should be chemically inert as much as possible. This is particularly relevant in the context of the expected battery life with regard to internal corrosion (e.g., of the electrodes and casing) within the battery and the problem of battery leakage. Also important in considering chemical stability is flammability. Unfortunately, typical electrolyte solvents often contain flammable substances, which can be a safety issue.

[0011] This can be a problem because the battery may accumulate heat during operation when it is discharging or has been discharged. This is particularly true for high-density batteries such as lithium-ion batteries. Therefore, it is desirable for the electrolyte to exhibit low flammability along with other relevant properties such as a high flash point.

[0012] Also, it is desirable for the electrolyte not to cause environmental problems regarding its disposability after use or other environmental problems such as the global warming potential. DISCLOSURE OF THE INVENTION

[0013] An object of the present invention is to provide a non-aqueous electrolyte solution having improved properties compared to the non-aqueous electrolyte solutions of the prior art.

[0014] A list or discussion of documents that are clearly disclosed earlier in this specification should not necessarily be construed as an admission that such documents are part of the prior art or common general knowledge.

[0015] Mode of use According to a first aspect of the present invention, there is provided the use of a compound of formula I 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 I in a battery.

[0017] Composition / device aspect According to a third aspect of the present invention, there is provided a battery electrolyte formulation comprising a compound of formula I.

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

[0020] Method aspect According to a sixth aspect of the present invention, there is provided a method for reducing the flash point of a battery and / or a battery electrolyte formulation, comprising adding a formulation comprising a compound of formula I.

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

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

[0023] According to a ninth aspect of the present invention, there is provided a method for preparing a battery electrolyte formulation comprising mixing a compound of formula I with a lithium-containing salt and another solvent or co-solvent.

[0024] According to a tenth aspect of the present invention, there is provided a method for preparing a battery electrolyte formulation comprising mixing a composition comprising a compound of formula I 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 within the battery / battery life / etc. by using a compound of formula I.

[0026] A compound of formula I,

Chemical formula

[0027] Within general formula I, in a preferred embodiment, the compound can be one of formula (Ia), (Ib), or (Ic), or a combination thereof. Compound of formula (Ia)

Chemical formula

Chemical formula

[0028] In each case, W is independently selected from the group consisting of H, F, Cl, Br, and I, Y is independently selected from the group consisting of F, Cl, Br, and I, Z is H, O(CW2) p CW3, (CW2) p CW3, OCY3, OCW3, polyalkylene glycol, and polyol ester, n is an integer from 1 to 1000, a and b are each an integer from 1 to 1000, m is an integer from 0 to 3, p is an integer from 0 to 9.

[0029] In the compound of formula (Ic), the sub-units of the compound (mimicking the sub-units of formula (Ia) and formula (Ib)) can be present in any order in the compound.

[0030] In a preferred embodiment, the compound of formula (Ib) can alternatively be represented by: [Chemical formula] wherein n is an integer from 1 to 1000.

[0031] The compounds of formula (I), (Ia), (Ib), (Ic), and (Id) can have an M W of 100000 or less, preferably 50000 or less, more preferably 25000 or less.

[0032] The compounds of formula (I), (Ia), (Ib), (Ic), and (Id) can have a polydispersity index of about 1.45, preferably about 1.35, more preferably about 1.30, and even more preferably about 1.25.

[0033] In each case of the compounds of formula (I), (Ia), (Ib), (Ic) and (Id), Y is preferably F or Cl, more preferably, Y is F.

[0034] W is preferably H, F or Cl. More preferably, W is H.

[0035] Advantageously, m is an integer from 0 to 3, preferably 0.

[0036] n is preferably an integer from 2 to 1000, for example, an integer from 5 to 500, preferably, n is an integer from 6 to 100.

[0037] It will be understood that, unless the context otherwise indicates, reference to formula (I) includes reference to formula (Ia), formula (Ib), formula (Ic) and / or formula (Id).

[0038] In some of the referenced compounds of formula (I) (including formula (Ia)-(Id)), at least one Z derivative may contain a polyalkylene glycol. Alternatively, both Z derivatives may contain a polyalkylene glycol (PAG). In both cases, the polyalkylene glycol may be selected from the group consisting of poly(ethylene) oxide, poly(propylene) oxide, and mixtures thereof. In such embodiments, the PAG group may be conjugated to the compound of formula (I) through the formation of an ether or ester bond between the alcohol or carboxylic acid end-capped PAG of the hydroxyl terminal capping group of formula (I) (i.e., Z = OH).

[0039] In some compounds of formula (I), at least one Z derivative may contain a fluorinated PAG (F-PAG). The F-PAG may be selected from the group consisting of F3C-terminated PAG and hydroxyl-terminated PAG.

[0040] The hydroxyl end groups of the F-PAG can provide further scope for derivatization and can be converted, for example, into ether or ester groups. These groups can be aliphatic, aromatic, straight-chain, branched, fluorine-containing, or otherwise functionalized in order to allow for further adjustment of the properties of the product.

[0041] In some compounds of formula (I), the Z derivatives can independently be alkyl or alkoxy groups containing 1 to 10 carbon atoms.

[0042] Both Z derivatives can be the same. Alternatively, the two Z derivatives may be different.

[0043] The compounds of formula (Ia) can advantageously be compounds of formula (IIa).

Chemical formula

[0044] Those skilled in the art will understand that the above formulas are merely representative and that structural defects may exist in the polymer chain.

[0045] The composition can include, for example, at least two different compounds of formula (I). In such cases, the value of n can be the same for at least two compounds of formula (I). Alternatively, the value of n may be different for at least two compounds of formula (I).

[0046] In some preferred embodiments, the compounds of formula (I) are compounds of formula (Ib).

[0047] The compounds of formula (I) can be a mixture of compounds of formula (Ia) and (Ib). In this situation, it is preferred that the majority of the mixture is a compound of formula (Ib), for example, more than 50% by weight of the mixture is a compound of formula (Ib), preferably more than 75%, more preferably more than 90% or 95%.

[0048] The compound of formula (I) can be prepared by a method involving the polymerization of an epoxide precursor.

[0049] The epoxide precursor has the formula (IV),

Chemical formula

[0050] Examples of epoxide precursors that can be used are the epoxide according to formula (IV) (where R1 is CF3, R2 is H, R3 is H, R4 is H) (epoxide of 3,3,3-trifluoropropene (1243zf)), the epoxide according to formula (IV) (wherein R1 is CF3, R2 is F, R3 is H, R4 is H) (epoxide of 2,3,3,3-tetrafluoropropene (1234yf)), the epoxide according to formula (IV) (wherein R1 is CF3, R2 is H, R3 is F, R4 is H) (epoxide of 1,3,3,3-tetrafluoropropene (1234ze)), and the epoxide according to formula (IV) (wherein R1 is CF3, R2 is H, R3 is CF3, R4 is H) (epoxide of 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz)). Preferably, the epoxide is the epoxide of 1243zf (1,1,1-trifluoro-2,3-epoxypropane).

[0051] The method can include the polymerization of an epoxide using an initiator formed from a base and an alcohol, and the selected alcohol determines the nature of the Z group in formulation I.

[0052] Preferably, the base is a Group I or Group II metal hydroxide, more preferably a Group I metal hydroxide, even more preferably sodium hydroxide or potassium hydroxide, and even more preferably potassium hydroxide.

[0053] Preferably, the alcohol is a primary alcohol. The primary alcohol can be, for example, a C1-C 10 glycol, preferably ethylene glycol. The primary alcohol can be, for example, a C1-C 10 branched or straight-chain alcohol. The primary alcohol can be, for example, a fluorinated alcohol, for example, a C1-C 10 fluorinated alcohol, preferably trifluoroethanol.

[0054] The polymerization of the epoxide can be carried out in the absence of a solvent.

[0055] The polymerization reaction can be carried out at a temperature of about 0 to about 130 °C, preferably about 40 to about 100 °C, more preferably about 50 to about 90 °C.

[0056] The polymerization reaction can be carried out at a pressure of about 100 to about 1000.3 kPa, preferably about 101 kPa.

[0057] It should be noted that the ninth aspect of the present invention should be construed as applicable to all embodiments of formula I.

[0058] Advantages In aspects of the present invention, electrolyte formulations have been found to be surprisingly advantageous.

[0059] The advantages of using the compounds of formula I in electrolyte solvent compositions become apparent in several ways. Their presence can reduce the flammability of the electrolyte composition (e.g., as measured by flash point). Their oxidation stability makes them useful for batteries that have to operate under harsh conditions, and they are compatible with common electrochemistry and can even enhance the performance of these electrodes through their interactions with them.

[0060] Additionally, electrolyte compositions containing the compounds of formula I can have excellent physical properties including low viscosity and low melting point, and can have high boiling points with the associated advantage of little or no gas generation during use. The electrolyte formulations wet and spread very well on surfaces, especially fluorine-containing surfaces, which is presumably due to a beneficial relationship between its adhesive and cohesive forces resulting in a low contact angle.

[0061] Furthermore, electrolyte compositions containing the compounds of formula I can have excellent electrochemical properties. These include improved capacity retention, improved cyclability and capacity, and improved compatibility with other battery components such as separators and current collectors, and with all types of cathode and anode chemistries (including systems operating at a range of voltages, especially high voltages, and including systems containing additives such as silicon). Additionally, the electrode formulations exhibit good solvation of metal (e.g., lithium) salts and interaction with any other electrolyte solvents present.

[0062] Preferred features associated with aspects of the present invention are as follows.

[0063] Preferred compounds Preferred compounds of the present invention where n = 1 to 50 are shown below.

Chemical formula

[0064] Metal salts The non-aqueous electrolyte further contains 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.

[0065] Metal salts generally include salts of lithium, sodium, magnesium, calcium, lead, zinc or nickel.

[0066] Preferably, the metal salt includes a lithium salt such as those selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflate (LiSO3CF3), lithium bis(fluorosulfonyl)imide (Li(FSO2)2N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N).

[0067] Most preferably, the metal salt includes LiPF6. Thus, in the most preferred variant of the fourth aspect of the present invention, a formulation is provided that optionally includes LiPF6 and a compound of Formula I in combination with a solvent.

[0068] Other solvents The non-aqueous electrolyte may include an additional solvent. Preferred examples of the solvent include fluoroethylene carbonate (FEC) and / or propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or ethylene carbonate (EC).

[0069] When present, the solvent constitutes 0.1% to 99.9% by weight of the liquid component of the electrolyte.

[0070] Additives The non-aqueous electrolyte may include additives.

[0071] Suitable additives may serve as surface film-forming agents that form an ion-permeable film on the surface of the positive or negative electrode. This can anticipate the decomposition reaction between the non-aqueous electrolyte and the electrolyte salt occurring on the surface of the electrode, thereby preventing the decomposition reaction of the non-aqueous electrolyte on the surface of the electrode.

[0072] Examples of film-forming agent additives include vinylene carbonate (VC), ethylene sulfite (ES), lithium bis(oxalato)borate (LiBOB), cyclohexylbenzene (CHB), and ortho-terphenyl (OTP). The additives may be used alone or in combination of two or more.

[0073] When present, the additive is present in an amount of 0.1 to 3% by weight based on the total weight of the non-aqueous electrolyte composition.

[0074] Battery The battery may include a primary (non-rechargeable) or secondary (rechargeable) battery. Most preferably, the battery includes a secondary battery.

[0075] A battery containing a non-aqueous electrolyte will generally include several elements. The elements constituting a preferred non-aqueous electrolyte secondary battery cell will be described below. It is understood that other battery elements may be present (such as a temperature sensor, etc.), and the following list of battery components is not intended to be exhaustive.

[0076] Electrode A battery generally includes a positive electrode and a negative electrode. Usually, the electrodes are porous and allow metal ions (lithium ions) to enter and exit their structures by a process called intercalation or deintercalation.

[0077] For a rechargeable battery (secondary battery), the term cathode refers to the electrode at which reduction occurs during the discharge cycle. For a lithium-ion battery, the positive electrode (the "cathode") is a lithium-based electrode.

[0078] Positive electrode (cathode) The positive electrode is generally composed of a positive electrode current collector such as a metal foil, and optionally, a positive electrode active material layer is disposed on the positive electrode current collector.

[0079] The positive electrode current collector can be a foil of a metal that is stable within the range of the potential applied to the positive electrode, or a film having a skin layer of a metal that is stable within the range of the potential applied to the positive electrode. As the metal that is stable within the range of the potential applied to the positive electrode, aluminum (Al) is desirable.

[0080] The positive electrode active material layer generally contains a positive electrode active material and other components such as a conductive agent and a binder. This is generally obtained by mixing the components in a solvent, applying the mixture to the positive electrode current collector, and then drying and rolling.

[0081] The positive electrode active material can be lithium (Li) or a lithium-containing 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.

[0082] Furthermore, in certain embodiments, transition metal fluorides may be preferred.

[0083] Some of the transition metal atoms in the transition metal oxide can be replaced by atoms of non-transition metal elements. The non-transition element 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.

[0084] Preferred examples of the positive electrode active material include lithium-containing transition metal oxides such as 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. LiNi containing nickel at a ratio of 50 mol% or more for all transition metals 1-y-z Co y Mn z O2(0 < y + z < 0.5) and LiNi 1-y-z Co y Al zO2 (0 < y + z < 0.5) is desirable from the viewpoints of cost and specific capacity. These cathode active materials contain a large amount of alkaline components and thus accelerate the decomposition of the non-aqueous electrolyte, causing a decrease in durability. However, the non-aqueous electrolyte of the present disclosure is resistant to decomposition even when used in combination with these cathode active materials.

[0085] The cathode active material can be a lithium (Li)-containing transition metal fluoride. 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.

[0086] The conductive agent can be used to increase the electron conductivity of the cathode 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. The binder can be used to ensure good contact between the cathode active material and the conductive agent and increase the adhesion of components such as the cathode active material to the surface of the cathode current collector. Preferred examples of the binder include fluoropolymers and rubber polymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-isoprene copolymer, and ethylene-propylene-butadiene copolymer. The binder can be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).

[0087] Negative electrode (anode) The negative electrode is generally composed of a negative electrode current collector such as a metal foil, and optionally, a negative electrode active material layer is disposed on the negative electrode current collector.

[0088] The negative electrode current collector can be a metal foil. Copper (lithium-free) is suitable as the metal. Copper can be processed easily at low cost and has good electronic conductivity.

[0089] Generally, the negative electrode contains carbon such as graphite or graphene.

[0090] Silicon-based materials can also be used for the negative electrode. A preferred form of silicon is in the form of nanowires, which preferably exist on a support material. The support material can include a metal (such as steel) or a non-metal such as carbon.

[0091] The negative electrode may include an active material layer. When present, the active material layer includes a negative electrode active material and other components such as a binder. This is generally obtained by mixing the components in a solvent, applying the mixture to the positive electrode current collector, and then drying and rolling.

[0092] The negative electrode active material is not particularly limited as long as the material can store and release lithium ions. Examples of suitable negative electrode active materials include carbon materials, metals, alloys, metal oxides, metal nitrides, and carbon and silicon intercalated with lithium. Examples of carbon materials include natural / artificial graphite and pitch-based carbon fibers. Preferred examples of metals include lithium (Li), silicon (Si), tin (Sn), germanium (Ge), indium (In), gallium (Ga), titanium (Ti), lithium alloys, silicon alloys, and tin alloys. Examples of lithium-based materials include lithium titanate (Li2Ti03).

[0093] Similar to the positive electrode, the binder can be a fluoropolymer or a rubber polymer, and preferably a rubbery polymer such as styrene-butadiene copolymer (SBR). The binder can be used in combination with a thickener.

[0094] 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 membrane having ion permeability. Examples of the porous membrane include microporous thin films, woven fabrics, and non-woven fabrics. Suitable materials for the separator are polyolefins such as polyethylene and polypropylene.

[0095] Case The battery components are preferably disposed within a protective case.

[0096] The case may include any suitable elastic material to provide support to the battery and electrical contact to the device being powered.

[0097] In one embodiment, the case includes a metallic material shaped to the battery form, preferably in sheet form. The metallic material preferably includes several parts that can be adapted to be attached together (e.g., by press fitting) in the assembly of the battery. Preferably, the case includes an iron / steel-based material.

[0098] In another embodiment, the case includes a plastic material shaped to the battery form. The plastic material preferably includes several parts that can be adapted to be joined together (e.g., by press fitting / adhesion) in the assembly of the battery. Preferably, the case includes a polymer such as polystyrene, polyethylene, polyvinyl chloride, polyvinylidene chloride, or polychlorotrifluoroethylene. The case may also include other additives for the plastic material, such as fillers or plasticizers. In this embodiment where the case for the battery mainly includes a plastic material, a part of the casing may additionally include a conductive / metallic material for establishing electrical contact with the device powered by the battery.

[0099] Arrangement The positive and negative electrodes can be wound together or stacked through a separator. Together with the non-aqueous electrolyte, they are housed in an external case. The positive and negative electrodes are electrically connected to the external case at their separated parts.

[0100] Module / Pack Some / plural battery cells can be configured into a battery module. In a battery module, the battery cells can be wired in series and / or in parallel. Typically, these are housed in a mechanical structure.

[0101] A battery pack can be assembled by connecting multiple modules together in series or in parallel. Typically, a battery pack includes additional functions such as sensors and controllers including a battery management system and a thermal management system. A battery pack generally includes a housing structure for constituting the final battery pack product.

[0102] End Use The batteries of the present invention are intended to be used in one or more of various final products in the form of individual batteries / cells, modules and / or packs (and the electrolyte formulations therefor).

[0103] Preferred examples of final products include portable electronic devices such as GPS navigation devices, cameras, laptops, tablets, and mobile phones. Other preferred examples of final products include vehicle devices such as electric bicycles and bikes, and automotive applications (including hybrid vehicles and pure electric vehicles) (as a power supply for a propulsion system and / or any other electrical system or device present therein).

[0104] The priorities and options of a given aspect, feature, or parameter of the present invention should be considered to be as disclosed in combination with any and all priorities and options regarding all other aspects, features, and parameters of the present invention, unless the context indicates otherwise.

[0105] Next, the present invention will be described with reference to the following non-limiting examples.

Example

[0106] The present invention will be described by the following non-limiting examples.

[0107] The compounds according to the present invention were synthesized by the following method.

[0108] General method An initiator mixture was prepared by adding an amount of base (e.g., 85 - 86% KOH) together with 2 - 3 drops of Aliquat 336 to the alcohol (e.g., ethylene glycol or trifluoroethanol) in a Pyrex round-bottom flask while stirring and cooling. When the base was dissolved in the alcohol, a dropping funnel and a condenser were attached to the reaction flask before adding the epoxide monomer (e.g., 3,3,3-trifluoro-1,2-epoxypropane). Next, the mixture was heated with stirring. At the end of the reaction, the product was cooled and dissolved in a minimum amount of chloroform (e.g., 250 ml). This chloroform solution was washed with acidic water (e.g., 4 g of 36% HCl in 100 ml of water), and then washed three times with water only (e.g., 100 ml). The washed chloroform solution of the polymer product was dried over anhydrous sodium sulfate, and after filtration, the solvent was removed by distillation under reduced pressure.

[0109] The resulting polymer product was analyzed and characterized by gel permeation chromatography (GPC).

[0110] GPC was performed on a Shimadzu Prominence LC system equipped with an RI detector having 300 mm × 75 mm, 5 μm PLgel 100 A and 300 mm × 7.5 mm, 5 μm PLgel 500 A columns in series, at 40 °C with a THF eluent at 1.0 ml / min. This method was calibrated with poly(styrene) standards having MWs of 1000 - 10000.

[0111] Viscosity measurement: Viscosity measurement was performed using a TA Instruments Discovery Hybrid Rheometer at -20 to 70 °C at 10 rad / s using a 40 mm 2.008° cone-plate geometry.

[0112] Using this general method, a series of polymer products were produced. The details of each preparation and the main properties of each product are outlined in Table 1.

Table 1

[0113] The preparation procedure used in Example 2 was scaled up to obtain 1440 g of the F(F) product, which was dissolved in tetrahydrofuran (THF, 1000 ml) and cooled to 5 °C. Potassium t-butoxide (220 g) was added to the THF solution little by little so that the temperature did not exceed 10 °C.

[0114] After the resulting solution was stirred for 30 minutes, methyl iodide (142 g) was added. The reaction mixture was warmed to room temperature and stirred overnight. Next, the reaction mixture was quenched with water (2000 ml), and after phase separation, the organic layer was washed 5 more times with water (1000 ml). After drying the organic layer with anhydrous MgSO4, the THF solvent and other volatile substances were removed by vacuum distillation at 90 °C and 1 mmHg for 1 - 2 hours. The final product was treated with activated carbon and filtered to remove haze, and 1100 g of the product of formula I was obtained.

Chemical formula

Table 2

[0115] Composition A composition containing the product of formula I (as in the above preparation example) was prepared as shown in Table 2 below.

Table 3

[0116] Flammability and safety tests Flash point The flash point was determined using a Miniflash FLP / H device from Grabner Instruments according to the ASTM D6450 standard method. [Table 4]

[0117] These measurements indicate that the addition of an additive called F-PAGF(F) methyl end cap increased the flash point of the standard electrolyte.

[0118] Self-extinguishing time The self-extinguishing time was measured with a custom device that included an automatically controlled stopwatch connected to an ultraviolet detector. · The electrolyte to be tested (500 μL) was applied to a Whatman GF / D (Φ = 24 mm) glass microfiber filter. · The ignition source was moved under the sample and held at that position for a preset time (1, 5, or 10 seconds) to ignite the sample. The ignition and combustion of the sample were detected using a UV light detector. · The evaluation was performed by plotting the combustion time / weight [s g -1 of the electrolyte over the ignition time [s] and extrapolating with a linear regression line to ignition time = 0 s. · The self-extinguishing time (s.g -1 ) is the time required for the sample to stop burning once it has flared up. [Table 5]

[0119] Electrochemical tests Drying Before the test, the F-PAGF(F) methyl-terminal cap was dried by treatment with pre-activated type 4A molecular sieves. The water levels of the pretreated and post-treated samples were determined by the Karl Fischer method.

Table 6

[0120] Electrolyte formulation The preparation and storage of the electrolytes were carried out in an argon-filled glove box (H2O and O2 < 0.1 ppm). The base electrolyte was 1 M LiPF6 in ethylene carbonate:ethyl methyl carbonate (3:7 wt%) with F-PAGF(F) methyl-terminal cap additives at concentrations of 2, 5, 10, and 30 wt%.

[0121] Cell chemistry and structure The performance of each electrolyte formulation was tested in a multilayer pouch cell over 50 cycles (2 cells per electrolyte). Chemistry 1: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and artificial graphite (specific capacity: 350 mAh g -1 ) anode. The areal capacities of NMC622 and graphite reached 3.5 mAh cm -2 and 4.0 mAh cm -2 , respectively. The N / P ratio reached 115%. Chemistry 2: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and SiO x / graphite (specific capacity: 550 mAh g -1 ) anode. The areal capacities of NMC622 and SiO x / graphite reached 3.5 mAh / cm -2 and 4.0 mAh cm -2 , respectively. The N / P ratio reached 115%. The test pouch cells had the following characteristics. · Nominal capacity 240 mAh + / - 2% · Standard deviation: Capacity: ±0.6 mAh Coulombic efficiency (CE) first cycle: ±0.13% Coulombic efficiency (CE) subsequent cycles: ±0.1% Positive electrode: NMC-622 · Active material content: 96.4% · Mass loading: 16.7 mg cm -2 Negative electrode: artificial graphite · Active material content: 94.8% · Mass loading: 10 mg cm -2 · Separator: PE (16 μm) + 4 μm Al2O3 · Balanced at a cut-off voltage of 4.2 V Negative electrode: artificial graphite + SiO · Active material content: 94.6% · Mass loading: 6.28 mg cm -2 · Separator: PE (16 μm) + 4 μm Al2O3 · Balanced at a cut-off voltage of 4.2 V After assembly, the following formation protocol was used. 1. Charged stepwise to 1.5 V, followed by a 5-hour rest step (wet step at 40 °C) 2. CCCV (C / 10, 3.7 V (I 限界 : 1 hour)) (pre-formation step) 3. Rest step (6 hours) 4. CCCV (C / 10, 4.2 V (I 限界 : 0.05C)) rest step (20 minutes) 5. CC discharge (C / 10, 3.8 V), (degassing of the cell) 6. CC discharge (C / 10, 2.8 V) Following this formation step, the cells were tested as follows. · Rest step (1.5 V, 5 hours), CCCV (C / 10, 3.7 V (1 hour)) · Rest step (6 hours), CCCV (C / 10, 4.2 V (I 限界 : 0.05C)) · Rest step (20 minutes), CC discharge (C / 10, 3.8 V) · Degassing step · Discharge (C / 10, 2.8 V), Rest step (5 hours) · CCCV (C / 3, 4.2 V (I 限界 : 0.05C)), Rest step (20 minutes) · CC discharge (C / 3, 2.8 V) · 50 cycles, or until reaching 50% SOH at 40 °C CCCV (C / 3, 4.2 V (I 限界 : 0.02C)), Rest step (20 minutes) CC discharge (C / 3, 3.0 V), Rest step (20 minutes)

[0122] Test results The test results for the additive F-PAGF(F) methyl end cap in each cell chemistry are summarized in Tables 3 and 4 and Figures 3 and 4. From this data, it can be confirmed that the additives in both cell chemistries had a positive effect on cell performance. These results, combined with safety-related research, demonstrate that the compounds of the present invention simultaneously improved both the safety and performance of the energy storage devices containing them.

Table 7

Table 8

Brief Description of the Drawings

[0123]

Figure 1

Figure 2

Figure 3

Figure 4

Claims

1. Use of a compound of Formula I in a non-aqueous battery electrolyte composition: 【Chemical 1】 (wherein n is an integer from 1 to 50).

2. Use of a compound of Formula I in a battery: [Chemical Formula 2] in a non-aqueous battery electrolyte composition comprising a compound of Formula I:

3. The use according to claim 1 or 2, wherein the non-aqueous battery electrolyte composition 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 battery electrolyte composition.

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

5. The metal electrolyte salt is lithium hexafluorophosphate (LiPF ６ ), lithium hexafluoroarsenate monohydrate (LiAsF ６ ), lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium triflate (lithium triflate) (LiSO ３ CF3), lithium bis(fluorosulfonyl)imide (Li(FSO ２ )) ２ N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CF ３ SO ２ )) ２ N), and the use according to claim 4, which is a salt of lithium selected from the group consisting of

6. The use according to any one of claims 1 to 5, wherein the non-aqueous battery electrolyte composition comprises an additional solvent in an amount of 0.1% to 99.9% by weight of the liquid component of the non-aqueous battery electrolyte composition.

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

8. A non-aqueous battery electrolyte composition comprising a compound of Formula I: 【Chemical Formula 3】 (wherein n is an integer from 1 to 50).

9. A battery comprising a non-aqueous battery electrolyte composition comprising a compound of Formula I: 【Chemical Formula 4】 (wherein n is an integer from 1 to 50).

10. The non-aqueous battery electrolyte composition according to claim 8, wherein the non-aqueous battery electrolyte composition 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 battery electrolyte composition.

11. The non-aqueous battery electrolyte composition according to claim 10, wherein the metal electrolyte salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc or nickel.

12. The metal electrolyte salt is lithium hexafluorophosphate (LiPF ６ ), lithium hexafluoroarsenate monohydrate (LiAsF 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(CF ３ SO ２ )) ２ N), and the non-aqueous battery electrolyte composition according to claim 11, which is a lithium salt selected from the group consisting of these substances.

13. The non-aqueous battery electrolyte composition according to any one of claims 8 and 10 to 12, wherein the non-aqueous battery electrolyte composition comprises an additional solvent in an amount of 0.1% to 99.9% by weight of the liquid component of the non-aqueous battery electrolyte composition.

14. The non-aqueous battery electrolyte composition according to claim 13, wherein the additional solvent is selected from the group consisting of fluoroethylene carbonate (FEC), propylene carbonate (PC) and ethylene carbonate (EC).

15. A method for reducing the flammability of a battery and / or a battery electrolyte, comprising adding a non-aqueous battery electrolyte composition comprising a compound of Formula I: 【Chemical Formula 5】 (wherein n is an integer from 1 to 50).

16. Compound of formula I: [Chemical Formula 6] A method of powering an article, including use of a battery comprising a non-aqueous battery electrolyte composition containing a compound of formula I (wherein n is an integer from 1 to 50).

17. A method of improving a non-aqueous battery electrolyte composition, comprising (a) at least partial substitution of a non-aqueous battery electrolyte composition with a compound of formula I: [Chemical Formula 7] A method comprising either (a) at least partial substitution of a non-aqueous battery electrolyte composition with a non-aqueous battery electrolyte composition containing a compound of formula I (wherein n is an integer from 1 to 50), and / or (b) replenishment of a non-aqueous battery electrolyte composition with a non-aqueous battery electrolyte composition containing a compound of formula I.

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