CN114573616A - Ternary electrolyte containing bicyclic salt and preparation method and application thereof - Google Patents

Abstract

The invention relates to a ternary electrolyte containing a bicyclic salt, a preparation method and application thereof, wherein the electrolyte comprises a boron trifluoride salt represented by the following general formula I: in the general formula I, R and R₁Represents a ring comprising a monocyclic ring and a polycyclic ring consisting of at least two monocyclic rings; e₈Is a chain containing no, at least one atom or a structure containing a ring; m is a metal cation; e₄Is a chain without or containing at least one atom; -E₃‑OBF₃M is connected to E₄、E₈R or R₁On any one atom of; e₁、E₂、E₃Independently a chain structure or a structure containing a ring, which is free of, contains at least one atom; r' and R₁' is independently a substituent. Boron trifluoride salts in the present applicationthree-OBF in the structure₃M group, and preferably-OBF₃M is bonded to the carbon atom C. The boron trifluoride salt can be used as an additive in a battery, and the electrolyte can be applied to a liquid battery, a mixed solid-liquid battery, a semi-solid battery, a gel battery, a quasi-solid battery and an all-solid battery, and has a good effect.

Description

Ternary electrolyte containing bicyclic salt and preparation method and application thereof

Technical Field

The invention relates to the technical field of batteries, in particular to a ternary electrolyte containing a bicyclic salt, and a preparation method and application thereof.

Background

The electrolyte is the important and necessary constitution of battery, and the battery has advantages such as high energy density, high voltage, the number of cycles is many, storage time is long, since commercialization, by the wide application in each aspect such as electric automobile, energy storage power station, unmanned aerial vehicle, portable equipment, no matter which kind of direction of application, all urgent needs improve the energy density and the circulation performance of battery under the prerequisite of guaranteeing battery security.

The currently developed liquid battery mainly comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, and the improvement of the energy density of the battery is to improve the working voltage and the discharge capacity of the battery, namely, a high-voltage high-capacity positive electrode material and a low-voltage high-capacity negative electrode material are matched for use; the improvement of the cycle performance of the battery is mainly to improve the stability of an interface layer formed between an electrolyte and a positive electrode and a negative electrode.

Taking a liquid lithium battery as an example, commonly used cathode materials include high voltage Lithium Cobaltate (LCO), high nickel ternary (NCM811, NCM622, NCM532, and NCA), Lithium Nickel Manganese Oxide (LNMO), lithium rich (Li-rich), and the like; common negative electrode materials include metallic lithium, graphite, silicon carbon, silicon oxycarbide, and the like; the commonly used diaphragm is mainly a polyethylene porous membrane or a polypropylene porous membrane; the liquid electrolyte is a mixture of a non-aqueous solvent and a lithium salt, and is classified into a carbonate liquid electrolyte and an ether liquid electrolyte according to the type of the solvent, and the salt mainly comprises lithium hexafluorophosphate, lithium perchlorate, lithium bis (trifluoromethyl) sulfonimide, lithium difluorooxalate phosphate and the like. The carbonate and ether solvents have narrow electrochemical windows and are easily oxidized and decomposed by high-voltage anode materials, so that the gas generation is serious, the liquid electrolyte is gradually consumed, and the battery rapidly loses efficacy. At present, two solutions are mainly provided, namely, a method for adding a functional additive into a liquid electrolyte and a method for partially or completely replacing the liquid electrolyte with a solid electrolyte.

According to the first method, some functional additives such as fluoroethylene carbonate and vinylene carbonate are added into the liquid electrolyte, a passivation layer is formed on the surface of the electrode in the first-cycle charging and discharging process, the decomposition of the electrode on the liquid electrolyte is inhibited, the discharge specific capacity of the battery is improved, and the cycle life of the battery is prolonged. However, the conventional liquid electrolyte additive does not contain dissociable ions, and only ions of the positive electrode can be consumed to form a surface passivation layer which only conducts ions and does not conduct ions, and if the formed passivation layer is unstable, the passivation layer is continuously destroyed and formed along with the increase of the cycle number, so that active lithium ions in the battery are continuously consumed, the first-cycle discharge capacity of the battery is low, the capacity attenuation is serious, and the battery still loses efficacy quickly. If the functional groups are combined with the groups capable of providing ions, the added salt/additive can form a passivation layer which conducts ions and has good stability on the surface of the electrode, and the liquid electrolyte with a narrow electrochemical window can be applied to a high-voltage battery system due to less consumption of ions from the positive electrode.

For method two, the liquid electrolyte is partially or fully replaced with a solid electrolyte. The solid electrolyte mainly comprises a polymer electrolyte, an inorganic oxide electrolyte and a sulfide electrolyte. The sulfide electrolyte is extremely sensitive to air and is easy to generate hydrogen sulfide, the electrochemical window is narrow, and the sulfide electrolyte is unstable to the anode material of an oxide; the oxide electrolyte has too high hardness and high brittleness; the electrochemical window of the polymer electrolyte is not wide, the conductivity is low, and the ion transference number is low. Therefore, the currently used electrolyte is still mostly a liquid electrolyte or a semi-solid electrolyte, and the secondary battery is mostly a liquid battery or a semi-solid battery. Sodium ion batteries also suffer from similar problems. It is also very important to develop single ion conductor polymer electrolyte with higher conductivity, wide electrochemical window and high ion migration number.

One of the groups of the Applicant has been working on compositions containing-OBF obtained by substitution of a hydroxyl group-OH₃Compounds of the M group were studied. Due to [ -OBF [ ]₃]^-Is a strongly polar group capable of forming a salt structure with a cation, thus, -OBF₃M has a strong sense of presence in one molecular structure, which may change the properties of the entire molecular structure. In the prior art, BF-containing samples were also only investigated by very individual researchers₃Combination of radicalsThe substances were studied sporadically and all contained only one BF₃The group is researched, at present, no great results are obtained, and no results of industrial application are found; the prior art is directed to-O-BF₃Investigation of the M group, let alone three-OBF₃Studies of the M group are published. This is also because-OBF₃M is strongly present, if-OBF is added to the molecule₃The number of M may vary unpredictably in the overall properties of the overall molecular structure, and thus research teams may be able to conduct procedures involving two or more-OBFs₃M research, resistance is greatly increased, time cost and economic cost are extremely high, and results are not well predicted, so that the research team only always contains one-OBF₃M was studied. Even if the pair contains one-OBF₃M is used for research, and the prior art is very few, so that the reference value is very small, and the research on three groups has no reference source. The group also discovered unexpectedly in occasional studies-OBF containing trihydroxy substitutions₃The M organic matter has a good effect of improving the cycle performance of the battery, so that a special research team is organized to research the application of the ternary structure in the liquid battery or the solid battery, and a good research result is obtained.

More importantly, the present application is directed to-OBF₃M Structure attached to the link rings, i.e. three-OBF₃M is either directly or indirectly attached to a ring, and the two rings are connected by a single bond, a chain, or a cyclic group. This is because such structures are particularly and the electrical and other chemical properties of the ring itself are also more specific and self-contained, three-OBF₃M, when attached to a ring, affects the chemical and physical properties of the entire ring, where it is substantially different from a single ring, chain structure, etc., and therefore the relationship or deductibility between them is uncertain. Thus, connecting-OBF to the link₃M, it is possible to produce effects different from those of other structures, in particular the connection of three-OBFs₃M, it may have a more unexpected superior effect. Therefore, the subject of this application is identified as having the direct or indirect attachment of-O-BF to the linking ring₃M, i.e.The main body of the ring is distinguished from aromatic ring, heterocyclic ring, carbocycle and unsaturated ring, and the like to carry out independent research, so that the-O-BF can be more specifically and definitely determined₃M is the specific case when linking rings.

Disclosure of Invention

The invention provides a ternary electrolyte containing a bicyclic salt, and preparation and application thereof, aiming at overcoming the defects in the prior art.

The purpose of the invention is realized by the following technical scheme:

one aspect of the present invention is to provide a ternary electrolyte containing a bicyclic salt, which is characterized in that: the electrolyte comprises a bicycloheteroboron trifluoride salt represented by the following general formula I:

in the above general formula I, R and R₁Represents a ring comprising a monocyclic ring and a polycyclic ring consisting of at least two monocyclic rings; e₈Is a chain of no, at least one atom or a structure containing a ring, E₈When cyclic, it also includes monocyclic or polycyclic rings; when E is₈When not present, R and R₁By single or double bond (e.g. R-R)₁Or R ═ R₁) (ii) a M is a metal cation; e₄Is a chain without or containing at least one atom; in the general formula I there is also one-E₃-OBF₃M, the-E₃-OBF₃M is connected to E₄、E₈R or R₁On any one atom of; e₁、E₂、E₃Independently a chain structure or a structure containing a ring, which is free of, contains at least one atom; r' and R₁' is independently a substituent, any one H on the representative ring may be substituted by a substituent, and the substituent may be substituted for one H or two or more H, and if two or more H are substituted, the substituents may be the same or different, i.e., each H may be substituted by a substituent defined as any one of R.

Further, in the tubeIn the formula I, E₈The linkage to R and R1 is by a single or double bond, rather than a common/atomic connection as bridged spirocyclic rings and the like.

Further, the monocyclic ring is a three-to twenty-membered ring, and the monocyclic ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring; saturated, unsaturated heterocycles are rings containing at least one heteroatom selected from O, N, P, Si, Se, B, S, Se or Al.

Further, the polycyclic ring composed of a single ring includes a parallel ring, a bridged ring, a spiro ring, a ring containing at least two of the aforementioned three polycyclic rings at the same time; the ring combination is formed by combining more than 2 monocyclic rings together, and in the two combined rings, two adjacent atoms on one ring share with two adjacent atoms on the other ring; the bridge ring is a polycyclic structure sharing more than two atoms; the spiro ring shares one atom with two adjacent monocyclic rings.

Further, in the formula I, with-OBF₃The atoms to which M is directly connected include C, S, N, Si, P, B or O; preferably with said-OBF₃The atom to which M is attached is a carbon atom C, and it may be preferred that at least one of the carbon atoms is attached to a carbon atom other than a carbonyl carbon, including-C ═ O or-C ═ S.

Further, H on any one C in the general formula I can be independently substituted by halogen, that is, H on any C in I such as a ring, a substituent, E, etc., can be substituted, and therefore, in the following definition, some technical features do not particularly describe the case where H on any one C is substituted by halogen.

Further, the substituents R' and R₁' independently include H, halogen atoms, ether oxygen bonds/groups, ether sulfur bonds/groups, nitro groups, cyano groups, C ═ O containing substituents, O ═ S ═ O containing substituents, N containing substituents, alkyl groups, heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl groups, heteroalkynyl groups, alkenylalkynyl groups, heteroalkynyls, ═ O, ═ S, and,

A salt substituent, a cyclic substituent, and a group in which H on any one of C of these groups is substituted with a halogen atom.

Preferably, the cyclic substituent includes a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring and a polycyclic substituent having two or more ring structures at the same time; r₅、R₆Independently H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, and heteroalkynyl; such salt substituents include, but are not limited to, sulfate (e.g., lithium sulfate, sodium sulfate, potassium sulfate), sulfonate (e.g., lithium sulfonate), sulfonimide salt (e.g., lithium sulfonimide), carbonate, carboxylate (e.g., COOLi), ether salt (e.g., -OLi, -SLi), nitrogen salt (e.g., COOLi), and the like

＝N^-Na⁺Etc.), silicates, phosphates, hydrochlorides, nitrates, azides; any of the structures in the heteroalkane/alkene/alkyne/alkenynyl group contains at least one non-carbon atom selected from halogen, S, N, O, P, Se, Ca, Al, B, or Si.

Each of the above substituents being capable of optionally being bonded to a first substituent on an atom, which first substituent may be bonded to substituent R' or R₁The species defined are consistent.

Further, E₁、E₂Or E₃Independently selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, a group containing a cyclic structure, a substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, or a substituted or unsubstituted alkyl, heterocycloalkyl, or substituted cycloalkyl group,

Or ═ N-R₇’-。E₄Is of a chain structure without or with 3 free connecting bonds, and the 3 free connecting bonds are respectively connected with the ring R, E₁And E₃Is connected, if E₁And/or E₂If not, then E₄Free connecting key of and-OBF₃And M is connected. E₈Is nothing, ether oxygen group, ether sulfur group, carbonyl group, ester group, phosphate group, alkyl group, heteroalkyl group, alkenyl group, heteroalkenyl group or cyclic group, and the cyclic group comprises

and-R₅₂-R₅₁-R₅₃-，R₅₁Is a first monocyclic ring, a first fused ring or a first linked ring, wherein the first linked ring contains at least two monocyclic rings, adjacent monocyclic rings are linked by a single bond or by a chain containing at least one atom, R is₅₂And R₅₃Independently a chain containing no or at least one atom;

represents a second monocyclic ring or a second fused ring, R₅₀Represents an atom in a second monocyclic ring or a second fused ring, the atom containing two atoms which are respectively associated with R and R₁A linked key. Wherein the double bond in the heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-nitrogen double bond C ═ N, and R is₅’、R₆' and R₇' independently of R in the preceding paragraph₅、R₆The species defined in (1) are identical.

E₈Optionally attached to a second substituent, which may be substituted with substituent R' or R₁The species defined are consistent.

Further, the monocyclic ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, and the monocyclic ring is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a nine-membered ring, a ten-membered ring, a twelve-membered ring, a fourteen-membered ring, a sixteen-membered ring or an eighteen-membered ring. Wherein the tri-unsaturated carbocyclic ring comprises a1 double-bonded carbocyclic ring; a ternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the ternary unsaturated heterocycle comprises 1 double bond and simultaneously contains 1 or 2 heteroatoms; the quaternary unsaturated carbocycle includes carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not adjacently disposed; a quaternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the quaternary unsaturated heterocycle is a four-membered ring which contains 1 or 2 double bonds and simultaneously contains 1 or 2 heteroatoms; five-membered unsaturated carbocycles include carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not disposed adjacently; a five-membered saturated heterocycle includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the five-membered unsaturated heterocyclic ring containing 1 or 2 bisA bond and contains simultaneously 1,2, 3 or 4 heteroatoms; the six-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; six membered saturated heterocyclic rings include saturated rings containing 1,2, 3 or 4 heteroatoms; the six-membered unsaturated heterocycle is a six-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3, 4, 5 or 6 heteroatoms; the seven-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; a seven membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the seven-membered unsaturated heterocycle is a seven-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms; the eight-membered unsaturated carbocyclic ring includes carbocyclic rings containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, they are not adjacent to each other; an eight membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; an eight-membered unsaturated heterocycle is an eight-membered ring containing 1,2, 3 or 4 double bonds and simultaneously 1,2, 3 or 4 heteroatoms; the nine-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; a nine membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the nine-membered unsaturated heterocycle is a nine-membered ring which contains 1,2, 3 or 4 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms; the ten-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two are arranged non-adjacently; a ten-membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the ten-membered unsaturated heterocycle is a ten-membered ring containing 1,2, 3 or 4 double bonds and simultaneously containing 1,2, 3 or 4 heteroatoms; the twelve-membered ring, the fourteen-membered ring, the sixteen-membered ring and the eighteen-membered ring respectively and independently comprise a saturated carbon ring, a saturated heterocyclic ring containing 1,2, 3, 4, 5 or 6 heteroatoms and an unsaturated heterocyclic ring containing 1,2, 3, 4, 5 or 6 heteroatomsAnd rings containing 1,2, 3, 4, 5 or 6 unsaturated bonds. The polycyclic ring is formed by combining more than 2-5 single rings; any one of the monocyclic ring or polycyclic ring is connected with the substituent R' or R₁'. Any one heteroatom of the heterocyclic ring is independently selected from O, N, P, Si or S.

Further, the monocyclic ring is selected from the following rings: cyclopropane, cyclopropene, ethylene oxide, cyclobutane,

Cyclobutene, cyclopentane, cyclopentene (containing one double bond), cyclopentadiene, pyrrole, dihydropyrrole

Tetrahydropyrrole, furan, dihydrofuran

Tetrahydrofuran, thiophene, dihydrothiophene

Tetrahydrothiophene, imidazole, pyrazole, thiazole

Dihydrothiazoles and oxazoles

Dihydrooxazole and isoxazole

Dihydroisoxazole, triazole

Dihydrotriazoles, tetrazoles, benzene rings, pyridines, dihydropyridines, tetrahydropyridines, pyrimidines, pyrazines, pyridazines, p-diazabenzenes, triazines

Cyclohexane, bisOxanes of the formula

Cyclohexene (containing a double bond), 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, dihydrothiopyran

Tetrahydrothiopyrans, dithianes

1, 2-dithianes

[1,3]Oxazolidines

Morpholine, piperazine, pyrone, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, cycloheptane, cyclohexene oxide, cycloheptene, 1, 3-cycloheptene, 1,3, 5-cycloheptene, cyclooctane, cyclononane triene, cyclododecane, 1,5, 9-triazacyclododecane, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, cycloheptane, epoxyhexane, cycloheptene, 1, 3-cycloheptene, cyclooctane, cyclononane, cyclododecane, 1,5, 9-triazacyclododecane, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, cycloheptane, cyclododecane, and mixtures thereof,

Or 18-crown-6; the polycyclic ring is composed of the above-mentioned monocyclic ring.

Further, the general formula I includes, but is not limited to, the following compounds:

in the above structure, Q₁、Q₂、Q₃All indicate-OBF₃M; e in each ring structure₁、E₂、E₃Independently in accordance with any of the above definitions; e in each ring structure₈Are each independently of E as defined in any of the preceding paragraphs₈The consistency is achieved; any one H on each ring can be independently selected from A₁、A₂、A₃Or A₄Any one substituent of (A), A₁、A₂、A₃Or A₄Are all independently selected from the substituents R' or R as described in any of the above paragraphs₁' any one substituent defined in (1).

Further, the substituents R', R₁’、A₁、A₂、A₃Or A₄Independently selected from H, halogen atom, carbonyl, ester group, aldehyde group, ether oxygen group, ether sulfur group, ═ O, ═ S,

Nitro, cyano, amino, amide, sulfonamide, sulfoalkane, hydrazino, diazo, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenylalkynyl, heteroalkynyl, cyclic substituents and substituents of said salts; ester groups include, among others, carbonates, carboxylates, sulfonates, and phosphates.

Preferably, in the substituent, the halogen atom comprises F, Cl, Br, I, and the carbonyl group is-R₁₀COR₁₁The ester group is-R₁₂COOR₁₃、-R₁₂OCOR₁₇、-R₁₂SO₃R₁₃、R₁₂O-CO-OR₁₃Or

The ether oxygen radical is-R₁₄OR₁₅The etherthio radical is-R₁₄SR₁₅Amino is ═ N-R₂₀、

or-CH ═ N-R₂₄Amide is

Sulfonamide group of

The sulfoalkane is-R₁₈SO₂R₁₉The diazo group is-N ═ N-R₃₈Salt substituents include, but are not limited to, sulfate, sulfonate, sulfonimide, carbonate, carboxylate, nitrate; wherein R is₅、R₆、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₇、R₁₈、R₁₉、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₈、R₂₉、R₃₀、R₃₁、R₃₂、R₃₃、R₃₄、R₃₅、R₃₈Independently is C_1-10Alkyl radical, C_1-10Heteroalkyl group, C_1-10Alkenyl radical, C_1-10Heteroalkenyl radical, C_1-10Alkynyl, C_1-10Heteroalkynyl, heteroalkenyl/alkynyl being a heteroalkenyl/alkenyl/alkynyl group bearing at least one of the non-carbon atoms; the group directly attached to N or O can also be a metal ion, such as R₁₃、R₁₅、R₁₆、R₂₀、R₂₂、R₂₄、R₂₆、R₃₀、R₃₁、R₃₅Etc. R₅、R₆、R₁₀、R₁₂、R₁₄、R₁₈、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₉、R₃₀、R₃₃、R₃₅、R₃₈Can independently be H or。

Further, R₅、R₆、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₇、R₁₈、R₁₉、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₈、R₂₉、R₃₀、R₃₁、R₃₂、R₃₃、R₃₄、R₃₅Independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, trifluoromethyl, hexyl, heptyl, or alkenyl; r₃₈Is phenyl or phenyl with methyl, halogen atom or nitro connected; wherein R is₅、R₆、R₁₀、R₁₂、R₁₄、R₁₈、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₉、R₃₀、R₃₃、R₃₅、R₃₈May independently be H or none; the group directly attached to N or O can also be a metal ion, such as R₁₃、R₁₅、R₁₆、R₂₀、R₂₂、R₂₄、R₂₆、R₃₀、R₃₁、R₃₅Etc., the ester group can also be selected from-OCH₂COOEt、COOCH₂COOEt、COOCH₂OCOCH(CH₃)₃、CH＝CHCOOCH₂CH₃or-CH₂(CH₂)₆COOEt; the amide can also be selected from

R₁₈Can also be-O-; r₂₀Can also be NO₂、CH₂COOCH₃Cyclopentane, cyclohexane, cyclohexadiene or phenyl, the amino group can also be

Cyano radicals selected from-CN, -CH₂CN、-SCH₂CH₂CN、-N(CH₃)CH₂CH₂CN or-CH₂CH₂CN。

The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl; heteroalkyl is an alkyl group containing at least one of the heteroatoms; preferably, the heteroalkyl group comprises-CH₂CH₂-O-NO₂、-CH₂S-S-CH₃、-CO-CH₂-Cl、-CO-CH₂-Br、-CH₂NO₂、-Z₁CF₃、-CH(CH₃)₂、-CH₂Z₁、-CH₂Z₁CH₃、-CH₂CH₂Z₁、-Z₁(CH₂CH₃)₂、-CH₂N(CH₃)₂、-CH₂Z₁CH(CH₃)₂、-C(CH₃)₂CH₂C(CH₃)₃、-C(CH₃)₂CH₂CH₃、-COCH₂CH(CH₃)₂、-CH(Z₁CH₂CH₃)₂、-CH₂CH(SCH₂CH₃)₂、-CH₂Z₁CH(CH₃)₂、-OCH₂(CH₂)₆CH₃、-CH₂(CH₃)Z₁CH₃、-CH₂(CH₃)Z₁CH₂CH₃、-CH₂CH₂Z₁CH₃、-CH₂CH(CH₃)Z₁CH₃-、-CH(CH₃)CH₂Z₁CH₃、-CH₂CH₂Z₁CH₂CH₃、-CH₂CH(CH₃)Z₁CH₂CH₃、-CH(CH₃)CH₂Z₁CH₂CH₃、-CH₂CH₂CH₂Z₁CH₃、-CH₂CH₂CH₂Z₁CH₂CH₃、-CH₂CH(CH₃)CH₂Z₁CH₃、-CH₂CH₂CH(CH₃)Z₁CH₃、-Z₁CH₂CH₂Si(CH₃)₃、

The alkenyl group includes vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1, 3-hexadienyl, -C (CH)₃)＝CH₂、-CH₂CH＝CH(CH₃)₂、-CH₂CH＝C(CH₃)CH₂CH₂CH＝C(CH₃)₂、-C(CH₃)＝CH₂、-CH₂CH＝CH-CH₂CH₃、

And the like belong to the alkenyl category; heteroalkenyl is alkenyl containing at least one of the heteroatoms; preferably, the heteroalkenyl group comprises-N ═ CHCH₃、-CH₂CH＝CH-(CH₂)₃COOCH₃、-OCH₂CH＝CH₂、-CH₂-CH＝CH-Z₁CH₃、-CH₂CH＝CH-(CH₂)₃COOCH(CH₃)₂、-CH₂-CH＝CH-Z₁CH₃、-C(CH₃)＝CHCH₃、-CH₂CH＝C(CH₃)₂、-C(CH₃)＝CHCOCH₃、-COCH＝CHCH₂CH₃、-C(CH₃)＝CH₂、-CH₂CH₂CO-(CH₂)₆-CH₃、-CH＝CHCH₂-CH₂Z₁CH₃、

The alkynyl group comprises ethynyl, propynyl, butynyl, pentynyl, hexynyl or heptynyl; heteroalkynyl is an alkynyl group containing at least one of the heteroatoms; preferably said heteroalkynyl radical comprises-C ≡ CCH₂CH₂CH₂Z₁CH₂CH₃、-C≡CCH₂Z₁CH₂CH₃or-C.ident.C-Si (CH)₃)₃(ii) a The alkenylalkynyl group is a structure containing at least one double bond and at least one triple bond; preferably, said alkenynyl is selected from: -C ≡ CCH ═ CHCH₃or-C ≡ CCH₂CH₂CH＝CHCH₃(ii) a Said heteroalkynyl is an alkynyl containing at least one of said heteroatoms; preferably, said heteroalkynyls are selected from: -CH ═ c (cn)₂、-C≡CCH₂CH＝CHCH₂Z₁CH₃。

The cyclic substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and polycyclic rings, preferably selected from the group consisting of cyclopropylalkyl, cyclopropene, oxirane, cyclobutylalkyl, cyclobutylheteroalkyl (e.g., cyclobutylheteroalkyl)

Etc.), cyclobutenyl, cyclobutynyl, phenyl, pyridine, pyrimidine, cyclopentyl, cyclopentenyl, cyclopentadienyl, pyrrolyl, dihydropyrrolyl, tetrahydropyrrolyl, furyl, dihydrofuran, tetrahydrofuran, thiophene, dihydrothiophene, tetrahydrothiophene, imidazolyl, thiazolyl, dihydrothiazolyl, isothiazolyl, dihydroisothiazolyl, pyrazolyl, oxazolyl, and the like

Dihydrooxazolyl, tetrahydrooxazolyl, isoxazolyl, dihydroisoxazolyl, thiopyran, dihydrothiopyran

Tetrahydrothiopyrans, dithianes

1, 2-dithianes

1, 4-dithiane, [1,3 ]]Oxazolidines

Dioxane (dioxane)

1, 3-dioxolane, triazolyl, cyclohexane, cyclohexenyl, cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, morpholine, piperazine, pyrone, pyridazine, pyrazine, triazine, dihydropyridine, tetrahydropyridine, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, biphenyl, naphthyl, anthryl, phenanthryl, quinonyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, alkanyl, benzoxazole, p-diazepine, pyrenyl, acenaphthenyl, phenanthrenyl, and phenanthrenyl,

Wherein, Z₁is-O-, -S-S,

-COO-、-N＝N-、

R₃₆、R₃₇、R₃₈、R₄₃、R₉₀、R₉₁、R₉₂Independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, fluoromethyl, fluoroethyl, methoxy, ethenyl, propenyl, or a metal ion; r mentioned above or below₃₆、R₃₇Consistent with the definition herein, it is not repeated.

Any one ring of the ring substituents is independently linked to the substituted bicyclic ring through any one of the following linking groups: -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH(CH₃) -, butyl, ethylene, propylene, butene, acetylene, propyne, -COO-, -CO-, -SO₂-、-N＝N-、-O-、-OCH₂-、-OCH₂CH₂-、-CH₂OCH₂-、-COCH₂-、-CH₂OCH₂CH₂-、-OCH₂CH₂O-、-COOCH₂CH₂-、-S-、-S-S-、-CH₂OOC-、-CH＝CH-CO-、-COOCH₂OCOCH₂-、

Or a single bond, i.e. a direct ring-to-ring connection; r₄₂Selected from H, methyl, ethyl or propyl; r₈₃Selected from alkyl or cyclic.

R₂₀Independently selected from said linking groups, preferably R₂₀Is none (i.e. singly bonded), -CH₂-or-CO-, R₂₁Is H, hydrocarbyl, heterohydrocarbyl or cyclic;

and

independently a monocyclic ring or a polycyclic ring consisting of at least two monocyclic rings, preferably, the monocyclic ring can be a 3-8 membered ring, which can be a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, and the polycyclic ring can be a fused ring, a bridged ring or a spiro ringAnd, more preferably,

and

independently phenyl, cyclopropyl, oxirane, cyclobutyl, cyclopentyl, cyclopentenyl, furan, dihydro/tetrahydrofuran, thiophene, dihydro/tetrahydrothiophene, pyrrole, dihydro/tetrahydrothiophene, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrimidine, piperidine, 1, 3-dioxacycloalkane, imidazole, pyrazine, pyridazine, p-diazabenzene, triazine, cyclohexane, cyclohexenyl, cycloheptyl.

Any atom with H on any ring of the above ring substituents can be selectively connected with the first substituent; the first substituent is selected from H, halogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, fluoromethyl, fluoroethyl, methoxy, ethoxy, nitro, alkenyl, alkynyl, ester group, sulfonate, sulfoalkane, amido, cyano, aldehyde group, -SCH₃、-COOCH₃、COOCH₂CH₃、-OCF₃、＝O、＝S、-N(CH₃)₂、-CON(CH₃)₂、-SO₂CH₃、-SO₂CH₂CH₃Or a substituent wherein H on any one C of these groups is substituted with a halogen.

Further, E₁、E₂Or E₃Independently selected from the group consisting of none, carbonyl, keto, ester, -CH₂-、-CH₂CO-, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, N-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, cyclohexyl, cyclopentyl, 1, 3-hexadienyl, -C ═ N-, -C (CH)₃)₂-、-CH(CH₃)-、-CH(CF₃)-、-C(CF₃)₂-、-CH₂CH₂CH(CH₃)-、-Z'₁CH₂CH₂-、-CH＝CH-CO-、-OCH₂CH₂CH₂CO-、＝N-CH₂-CO-、-Z'₁CH₂CO-、-Z'₁CH₂CH₂CO-、-Z'₁CH₂CH₂CH₂CO-、-COOCH₂CH₂-、-O-CH₂(CH₂)₄CH₂-、-CH₂CH₂CO-、-CH₂CH(CH₃)-、-OCH₂-、-CH(CH₃)CO-、-CH(CH₂Cl)-、-CH(OCH₃)-、-CH(CHO)-、-CH₂COCO-、-C(CH₃)₂CH₂CH₂-、-CH₂(CH₂)₅CO-、-CH₂(CH₂)₆CO-、-N＝C(CH₃)-、-O-(CH₂)₆-、-CH₂Z'₁CH₂-、-CH₂(CH₃)Z'₁CH₂-、-CH₂CH₂Z'₁CH₂-、

-O-CH₂-CH₂-O-CH₂-CH₂-、

-(CH₃)CHCH₂CH₂Z’₁CH₂-、-O-CH(CH₃)-(CH₂)₄CH₂-、

E₈Is selected from-CH, -CH₂-、-CH₂CH₂-、-C(CH₃)₂-、-CH(CH₃)-、-CH(CH₃)CH(CH₃)-、-CH(Et)CH(Et)-、＝CH-CH＝、-CH₂CH(CH₃)-、-CO-、-O-、COO-、-OCH₂O-、-CH＝CH-、-COCH＝CH-、-CH＝N-N＝CH-、-CH＝CHCOCH₂COCH＝CH-、-S-、-S-S-、

At the E₈In which the number of free links includes 2, 3 or 4, in the above-enumerated structures, if E₈To which only two rings are attached, then E₈The number of free bonds in (1) is 2, e.g.

If E₈In addition to two rings, there is a third ring or a structure of-E-Q, E₈The number of free bonds in (1) is 3, if

And the like. If E₈In addition to the two rings, there are also other two radicals, then E₈The number of free connecting bonds in (1) is 4, e.g.

And the like.

Wherein, Z 'is'₁is-O-, -S-S-),

-COO-、

Sulfonyl, sulfonylimino or sulfonyloxy, wherein R₄₁Is H, methyl, ethyl, propyl, isopropyl, butyl, ethoxy, methoxy or a metal ion; r₄₄、R₄₅Independently an alkyl group or a ring; r₃₉、R₅₀Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, nitro, hexyl, thiazole, -CH (CH)₃)₂、-CH₂CH(CH₃)₂、-CH₂CH₂NO₃、

Wherein R is₈、R₄₀、R₄₆、R₄₇、R₄₈、R₄₉Independently is halogen-free, methyl, nitro or trifluoromethyl, R₉Is nothing, methylene, -CH (CH)₃)-Ph；R₃₈Selected from among nothing, methyl, ethyl, halogen atoms, fluoromethyl, fluoroethyl or-CH₂-N(CH₃)₂；R₃₇Selected from halogen atom, alkyl, fluoroalkyl, methoxyl, nitryl, aldehyde group, ketone group or ester group.

Further, the general formula I is lithium salt, potassium salt, sodium salt, calcium salt or magnesium salt, namely M in the general formula I comprises Na⁺、K⁺、Li⁺、Mg²⁺Or Ca²⁺Preferably a lithium, potassium or sodium salt.

Further, the general formula I is: a compound of formula i as described in any of the preceding paragraphs wherein H on any one of the C groups is substituted, either fully or partially, with halogen, preferably F.

It is another object of the present invention to provide a method for preparing the electrolyte according to any one of the above paragraphs, wherein the method comprises a three-OH-containing bicyclic ternary structure, a three-OH-containing bicyclic ternary structureReacting boron fluoride compound with M source to obtain product containing three-OBF₃And (3) a bicyclic boron trifluoride salt of M.

Another aspect of the present invention is to provide an application of the ternary electrolyte containing a bicyclic salt described in any one of the above paragraphs in a secondary battery, where the application is: the general formula I can be used as an additive.

It is a further aspect of the present invention to provide an additive for use in a battery, the additive comprising the general formula I as described in any of the above paragraphs, i.e. comprising a bicyclic boron trifluoride salt as described in any of the above paragraphs.

The invention also provides an electrolyte, which comprises a liquid electrolyte, a gel electrolyte, a mixed solid-liquid electrolyte, a quasi-solid electrolyte and an all-solid electrolyte, wherein the liquid electrolyte, the gel electrolyte, the mixed solid-liquid electrolyte, the quasi-solid electrolyte and the all-solid electrolyte respectively and independently comprise the bicyclic boron trifluoride salt described in any section above, namely the electrolyte comprises the general formula I described in any section above.

The invention also provides a battery, which comprises the ternary electrolyte containing the bicyclic salt, a positive electrode, a negative electrode, a diaphragm and a packaging shell, wherein the ternary electrolyte comprises the bicyclic salt; the battery comprises any one of a liquid battery, a mixed solid-liquid battery, a semi-solid battery, a gel battery, a quasi-solid battery and an all-solid battery.

A final aspect of the present invention is to provide a battery pack including the battery.

The invention has the following main beneficial effects:

the electrolyte in the present application creatively combines three-OBF₃M is complexed in a compound, and is preferably-OBF₃M is connected with carbon atom C, and the structural effect protected by the invention is more prominent.

Specifically, the boron organic compound can be used as an additive in a battery, can form a stable and compact passivation film on the surface of an electrode of the battery, prevents direct contact between an electrolyte and an electrode active substance, inhibits decomposition of each component of the electrolyte, widens the electrochemical window of the whole electrolyte system, and can remarkably improve the discharge specific capacity, the coulombic efficiency and the cycle performance of the battery; in addition, the boron organic compound is an ionic conductor and is used as an additive, the active ions coming out of the positive electrode are less consumed while a passivation layer is formed on the surface of the electrode, and the first coulombic efficiency and the first cycle discharge specific capacity of the battery can be obviously improved. And when the electrolyte containing the boron organic compound, the existing high-voltage high-specific-volume anode material and the low-voltage high-specific-volume cathode material are compounded into a battery, the electrochemical performance of the battery is improved. In addition, the structure of the application can be mixed with conventional additives for use, namely, a double additive or a multi-additive, and the battery using the double additive or the multi-additive shows more excellent electrochemical performance.

In addition, the structure in the application can be used in the electrolyte, and the structure can also act synergistically as an additive property and a salt property, so that the electrolyte has excellent effect superior to that of the traditional additive, for example, when the structure is used as the additive, a stable passivation layer can be formed on the surface of an electrode in the battery cycling process, PEO or other components are prevented from being further decomposed, and the structure also has good ion transmission performance, so that the battery shows more excellent long-cycle stability and comprehensive effect.

In addition, the boron organic compound has the advantages of rich raw material sources, wide raw material selectivity, low cost, very simple preparation process, simple reaction and mild conditions, and has excellent industrial application prospect, and only a compound containing three-OH groups is required to react with a boron trifluoride organic substance and an M source (M is a metal cation).

In addition, the lithium-ion battery can also adopt metals except traditional lithium such as sodium and potassium to form salts, so that more possibilities are provided for later application, cost control or raw material selection, and the like, and the lithium-ion battery has a great significance.

Drawings

FIGS. 1-10 are nuclear magnetic hydrogen spectra of products of some embodiments of the invention;

fig. 11 to 14 are graphs showing the effect of the circulation of boron trifluoride salt as a liquid electrolyte additive according to the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the present invention, unless the position of the substituent to the substituted structure is explicitly indicated, it means that any atom in the substituent may be bonded to the substituted atom or structure, for example: if the substituent is

R₉₁、R₉₂Respectively is a substituent on two benzene rings, then any carbon atom and R on any benzene₉₁、R₉₂Or R₉₃(if R is₉₁、R₉₂、R₉₃Not absent) may be attached to a substituted bicyclic structure. Furthermore, where two linkages are present in a substituent, the linked structure may be linked to either linkage, e.g. if R₉₃is-OCH₂CH₂The linkage on O can be either to the left or to the right phenyl ring, likewise the linkage on methylene is also possible.

In the present invention, if a group is desired to be attached to a two-part structure, it has two linkages or radicals to be attached, and if it is not explicitly indicated which two atoms are attached to the attached part, any one atom containing H may be attached. E if in the claims of this application₁Is n-butyl due to E₁Having 2 linkages to be linked (one with-OBF)₃One to the main structure) and n-butyl has only one bond at the end, then the other bond may be locatedOn any of the 4 carbon atoms in the n-butyl group.

In the context of the present invention, a chemical bond is drawn not on an atom, but on a position where it intersects the bond, e.g. on a line

Represents any one H on the ring and may be independently substituted by a substituent A₁Substituted, and can replace one H and also can replace two or more H, and the substituents can be the same or different; for example, if a1 is a substituent such as O, methyl, F, etc., then any one or more H may be independently substituted with methyl, F, etc., and any one C containing two H may be linked to O, e.g., it may be

And the like.

The "Et" is ethyl. "Ph" is phenyl.

In the title and description of the invention, -OBF₃M in M may be a monovalent, divalent, trivalent or polyvalent metal cation, if it is not a monovalent ion, -OBF₃The number of (c) is increased correspondingly so that it exactly matches the valence of M.

In the structural formulae of the present invention, when a group in the parentheses "()" is contained after a certain atom, it means that the group in the parentheses is connected to the atom before it. Such as-C (CH)₃)₂-is of

-CH(CH₃) -is of

In this application, the xx group may have a bond to the substituted structure, or may have two or three, depending on the actual requirement. If it is a general substituent, then it has only one bond, if it is E₁、E₂Or some R in the first substituent, etc., which has 2 or 3 linkages.

The "boron trifluoride-based compound" refers to boron trifluoride, a compound containing boron trifluoride, a boron trifluoride complex or the like.

The invention provides a ternary organic boron trifluoride salt serving as an electrolyte additive, namely the ternary organic boron trifluoride salt contains three-OBF₃M is a group of Li⁺Or Na⁺And the like. The ternary boron trifluoride salt can be applied to liquid batteries, and can also be excellently applied to gel batteries and solid batteries. The preparation method of the compound is simple and ingenious, and the yield is high. Namely, the boron trifluoride compound is obtained by reacting a raw material, a boron trifluoride compound and an M source, specifically, -OH in the raw material participates in the reaction, and other structures do not participate in the reaction. The specific preparation method mainly comprises two methods:

adding an M source and a raw material into a solvent in a nitrogen/argon atmosphere, mixing, reacting at 5-50 ℃ for 5-24 hours, and drying the obtained mixed solution at 20-80 ℃ under the vacuum degree of about-0.1 MPa under reduced pressure to remove the solvent to obtain an intermediate; adding boron trifluoride compounds, stirring and reacting at 5-50 ℃ for 6-24 hours, drying the obtained mixed solution under reduced pressure at 30-80 ℃ and under the vacuum degree of about-0.1 MPa to obtain a crude product, and washing, filtering and drying the crude product to obtain the final product, namely the ternary organic boron trifluoride salt, wherein the yield is 74-95%.

Secondly, under the atmosphere of nitrogen/argon, adding the raw materials and boron trifluoride compounds into a solvent, uniformly mixing, reacting for 6-24 hours at the temperature of 5-50 ℃, decompressing and drying the obtained mixed solution at the temperature of 20-80 ℃ and the vacuum degree of about-0.1 MPa to remove the solvent, and reacting to obtain an intermediate; adding an M source into a solvent, then adding the solvent containing the M source into the intermediate, stirring and reacting for 5-24 hours at 5-50 ℃ to obtain a crude product, directly washing the crude product or washing the crude product after drying under reduced pressure, and then filtering and drying to obtain a final product, namely the ternary organic boron trifluoride salt, wherein the yield is 74-95%.

In the above two specific preparation methods, the boron trifluoride compounds may include boron trifluoride diethyl etherate complex, boron trifluoride tetrahydrofuran complex, boron trifluoride dibutyl etherate complex, boron trifluoride acetic acid complex, boron trifluoride monoethyl amine complex, boron trifluoride phosphoric acid complex, and the like. M sources include, but are not limited to, metallic lithium/sodium platelets, lithium/sodium methoxide, lithium/sodium hydroxide, lithium/sodium ethoxide, butyl lithium/sodium, lithium/sodium acetate, and the like. The solvent is independently alcohol (some liquid raw materials can be simultaneously used as the solvent), ethyl acetate, DMF, acetone, hexane, dichloromethane, tetrahydrofuran, ethylene glycol dimethyl ether and the like. The washing can be carried out with a small polar solvent such as diethyl ether, n-butyl ether, n-hexane, cyclohexane, diphenyl ether, etc.

Example 1: raw materials

The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride tetrahydrofuran complex (4.19g, 0.03mol) were mixed uniformly in 15ml of ethylene glycol dimethyl ether in a nitrogen atmosphere, and reacted at room temperature for 12 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Dissolving lithium ethoxide (1.56g, 0.03mol) in 10ml ethanol, slowly adding into the intermediate, stirring at 45 deg.C for reaction for 8 hr, drying the obtained mixed solution at 45 deg.C under reduced pressure of about-0.1 MPa to obtain solid, washing with n-butyl ether for three times, filtering, and drying to obtain product M1, wherein Q is OBF₃And Li. The yield was 85%, and the nuclear magnetization is shown in FIG. 1.

Example 2: raw materials

The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride diethyl etherate (4.26g,0.03mol) were mixed uniformly in 15ml of ethylene glycol dimethyl ether under an argon atmosphere, and reacted at room temperature for 12 hours. The obtained mixed solution is decompressed and dried at 30 ℃ and the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Adding 18.90ml of butyl lithium hexane solution (c is 1.6mol/L) into the intermediate, stirring at room temperature for 6 hours, washing the obtained mixed solution with xylene for 3 times, drying under reduced pressure at 40 deg.C and a vacuum degree of about-0.1 MPa, washing the obtained crude product with cyclohexane for 3 times, filtering, and dryingObtaining a product M2, wherein Q is OBF₃And Li. The yield was 87%.

Example 3: raw materials

The preparation method comprises the following steps: 0.01mol of the starting material and lithium methoxide (1.14g,0.03mol) were mixed uniformly with 20ml of methanol under a nitrogen atmosphere, and reacted at room temperature for 8 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Adding boron trifluoride tetrahydrofuran complex (4.19g, 0.03mol) into the intermediate, stirring at room temperature for reaction for 6 hours, drying the obtained mixed solution under reduced pressure at 40 ℃ and under the vacuum degree of-0.1 MPa, washing the obtained solid with isopropyl ether for three times, filtering and drying to obtain a product M3, wherein Q is OBF₃And Li. Yield 88%, nuclear magnetization is shown in figure 2.

Example 4: raw materials

The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride tetrahydrofuran complex (4.19g, 0.03mol) were mixed uniformly in 15ml of ethylene glycol dimethyl ether under an argon atmosphere, and reacted at room temperature for 12 hours. The resulting mixed solution was dried under reduced pressure at 30 ℃ and a vacuum of about-0.1 MPa to remove the solvent, and an intermediate was obtained. Adding 18.90ml of butyl lithium hexane solution (c is 1.6mol/L) into the intermediate, stirring and reacting for 6 hours at room temperature, washing the obtained mixed solution for 3 times by using dimethylbenzene, drying under reduced pressure at 40 ℃ and the vacuum degree of about-0.1 MPa, washing the obtained crude product for 3 times by using cyclohexane, filtering and drying to obtain a product M4, wherein Q is OBF₃And Li. The yield was 84%, and the nuclear magnetization is shown in FIG. 3.

Example 5: raw materials

The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride-acetic acid complex (5.63g, 0.03mol) were placed in 15ml of ethylene glycol under an argon atmosphereUniformly mixing the dimethyl ether, reacting for 12 hours at 40 ℃, and drying the obtained mixed solution under reduced pressure at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent to obtain an intermediate. Dissolving sodium acetate (2.46g, 0.03mol) in 10ml of N, N-dimethylformamide, adding into the intermediate, stirring at 50 deg.C for 8 hr, drying the obtained mixture under reduced pressure at 80 deg.C and vacuum degree of-0.1 MPa to obtain solid, washing with diphenyl ether three times, filtering, and drying to obtain product M5, wherein Q is OBF₃And (4) Na. The yield was 85%, and the nuclear magnetization is shown in FIG. 4.

Example 6: raw materials

Preparation: the product M6 was prepared from the starting material by the method of example 2, wherein Q is OBF₃And Li. The yield was 89%.

Example 7: raw materials

Preparation: the product M7 was prepared from the starting material by the method of example 1, wherein Q was OBF₃And Li. Yield 82%, nuclear magnetization is shown in fig. 5.

Example 8: raw materials

Preparation: the product M8 was prepared from the starting material by the method of example 4, wherein Q is OBF₃And Li. The yield was 80%.

Example 9: raw materials

Preparation: the product M9 was prepared from the starting material by the method of example 1, wherein Q is OBF₃And Li. Yield 79% and nuclear magnetization are shown in fig. 6.

Example 10: raw materials

Preparation: the product M10 was prepared from the starting material by the method of example 3, wherein Q is OBF₃And Li. Yield 81%, nuclear magnetization is shown in fig. 7.

Example 11: starting materials

Preparation: the product M11 was prepared from the starting material by the method of example 2, wherein Q is OBF₃And Li. Yield 86%, nuclear magnetization is shown in fig. 8.

Example 12: raw materials

Preparation: the product M12 was prepared from the starting material by the method of example 3, wherein Q is OBF₃And Li. The yield was 90%.

Example 13: raw materials

Preparation: the product M13 was prepared from the starting material by the method of example 2, wherein Q is OBF₃And Li. Yield 88%, nmr is shown in figure 9.

Example 14: raw materials

Preparation: the product M14 was prepared from the starting material by the method of example 1, wherein Q is OBF₃And Li. Yield 84%, nmr is shown in figure 10.

Example 15: raw materials

Preparation: the product M15 was prepared from the starting material by the method of example 1, wherein Q is OBF₃And Li. The yield was 84%.

Example 16

The protected bicyclic boron trifluoride salt is mainly used as an additive, mainly plays a role in generating a stable passivation layer, and has ions capable of being dissociated, so that the ions provided by an electrode are less consumed in the process of forming the passivation layer, and the first effect and the cycle performance of the battery are obviously improved. The performance of the invention is illustrated in experimental manner below.

(1) Positive pole piece

Adding the active substance of the main anode material, the electronic conductive additive and the binder into a solvent according to the mass ratio of 95:2:3, wherein the solvent accounts for 65% of the total slurry by mass percent, and uniformly mixing and stirring to obtain anode slurry with certain fluidity; and coating the anode slurry on an aluminum foil, drying, compacting and cutting to obtain the usable anode piece. Lithium cobaltate (LiCoO) is selected as the active material₂LCO for short), lithium nickel cobalt manganese oxide (NCM811 for selection), lithium nickel cobalt aluminate (LiNi)_0.8Co_0.15Al_0.05O₂Abbreviated NCA) and lithium nickel manganese oxide (LiNi)_0.5Mn_1.5O₄Abbreviated LNMO), Na_0.9[Cu_0.22Fe_0.3Mn_0.48]O₂(NCFMO for short), Carbon Nanotubes (CNT) and Super P are selected as the electron conductive additive, polyvinylidene fluoride (PVDF) is used as the binder, and N-methylpyrrolidone (NMP) is used as the solvent.

(2) Negative pole piece

Adding a main negative material active substance (except metal Li), an electronic conductive additive and a binder into solvent deionized water according to a ratio of 95:2.5:2.5, wherein the solvent accounts for 42% of the total slurry, and uniformly mixing and stirring to obtain negative slurry with certain fluidity; and coating the negative electrode slurry on copper foil, drying and compacting to obtain the usable negative electrode piece. Graphite (C), silicon carbon (SiOC450), metallic lithium (Li) and Soft Carbon (SC) are selected as the active materials, CNT and Super P are used as the conductive agents, and carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) are used as the binders.

The anode and cathode systems selected by the invention are shown in table 1:

TABLE 1 Positive and negative electrode system

Positive and negative electrode system of battery	Positive electrode main material	Negative electrode main material
			A1	LCO	SiOC450
A2	NCM811	SiOC450
			A3	NCM811	Li
A4	NCA	C
			A5	LNMO	C
A6	LCO	Li
			A7	NCFMO	SC

(3) Preparing liquid electrolyte

M1-M15, an organic solvent, a conventional salt and a conventional additive are uniformly mixed to obtain series electrolytes E1-E15, wherein the used solvents are Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethylene Carbonate (EC) and Propylene Carbonate (PC). Conventional additives are fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), trimethyl phosphate (TMP), ethoxypentafluorocyclotriphosphazene (PFPN), vinyl sulfate (DTD); conventional salts are lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium bis (fluorosulfonylimide) (LiFSI), lithium hexafluorophosphate (LiPF)₆) Lithium bis (trifluoromethyl) sulfonimide (LiTFSI), sodium hexafluorophosphate (NaPF)₆). The specific components and ratios are shown in table 2.

Table 2 electrolytes formulated as additives in the present application

Note: 1M means 1 mol/L.

Comparison sample: and replacing M1-M15 with blanks according to the proportion of E1-E15 (namely, not adding M1-M15), thus obtaining corresponding conventional electrolyte comparison samples L1-L15.

(4) Button cell assembly

Electrolyte series E1-E15 containing the structure of the embodiment as an additive and conventional electrolytes L1-L15 are assembled into a button cell in a comparative way, and the details are as follows: negative electrode shell, negative electrode pole piece, PE/Al₂O₃A button cell is assembled by a diaphragm, an electrolyte, a positive pole piece, a stainless steel sheet, a spring piece and a positive shell, and a long circulation test is carried out at room temperature, wherein the circulation modes are 0.1C/0.1C 1 week, 0.2C/0.2C 5 week and 1C/1C 44 week (C represents multiplying power), the positive pole piece is a circular sheet with the diameter of 12mm, the negative pole piece is a circular sheet with the diameter of 14mm, and the diaphragm is a circular sheet with the diameter of 16.2mmWafer of commercial Al₂O₃a/PE porous separator.

The battery systems prepared from E1 to E15 were batteries 1 to 15, respectively, and the battery systems prepared from L1 to L15 were comparative batteries 1 to 15, respectively. The specific configuration and voltage range of the cell are shown in table 3. The results of the first cycle specific discharge capacity, the first cycle efficiency, and the capacity retention rate at 50 cycles of the batteries 1 to 15 and the comparative batteries 1 to 15 at room temperature are shown in table 4.

Table 3 arrangement and test mode of example and comparative example cells

Table 4 comparison of test results for example cells and comparative example cells

From the test results of the battery and the comparative battery, in the button battery, when the positive and negative electrode systems are the same, the first cycle efficiency, the discharge specific capacity and the capacity retention rate of the lithium/sodium battery using the structures M1-M15 as the liquid electrolyte additive are much better than those of the lithium/sodium battery without the additive, and the performance of the lithium/sodium battery is superior to that of the conventional additive at present. Furthermore, cells using the boron trifluoride salt additives herein exhibit superior electrochemical performance in the presence of conventional additives.

In addition, the application also shows the effect graph of some examples as additives. Fig. 11-14 are graphs comparing the performance of battery 1/2/5/15 made as a liquid electrolyte additive in accordance with example 1/2/5/15 with a corresponding comparative battery 1/2/5/15 that did not include an example of the present invention. The figures also show that the structure of the application has excellent effect. In addition, in the circulation diagram, there are small squares on the upper sideBlock

The lines of (A) represent the cells of the examples, with small circles

The lines representing the comparative example cells indicate that the example cells are all above the lines representing the comparative example cells, and the example cells are more excellent.

The first cycle efficiency, specific discharge capacity, capacity retention rate and other properties have direct and significant influence on the overall performance of the battery, and directly determine whether the battery can be applied or not. Therefore, it is the goal or direction of many researchers in this field to improve these properties, but in this field, the improvement of these properties is very difficult, and generally about 3-5% improvement is a great progress. In the early experimental data, the data are surprisingly found to be greatly improved compared with the conventional data, particularly when the additive is used as an electrolyte additive, the performance is improved by about 5-30%, and the additive and the conventional additive are combined to be used for showing better effect. More importantly, the structural type of the application is greatly different from the conventional structure, so that a new direction and thought are provided for the research and development in the field, a large space is brought for further research, and the application can also have multiple purposes; has great significance.

Example 17:

for further study and understanding of the structural properties in the present application, the applicant evaluated the effect of the following 2 structures as liquid electrolyte additives on the long cycle performance of the battery at room temperature. The structure of the present application was selected from the structure in example 1 (i.e., M1), and the following 2 comparative example structures were structure W1 and structure W2, respectively.

The effects of W1-W2 and M1 on the long-cycle performance of the cell at room temperature were evaluated by using them as liquid electrolyte additives, respectively.

(1) Liquid electrolyte configuration

TABLE 5 electrolytes S1 to S3 with W1 to W2 and M1 as additives

Wherein S0 is a control group.

(2) Button cell assembly

The obtained liquid electrolytes S0 to S3 were assembled into button cells, and the sizes of the positive and negative electrodes, the separator, the assembly method, and the battery cycle were the same as those of the button cell shown in "one" of example 16, i.e., batteries Y0 to Y3, respectively. The specific configuration, cycling profile and voltage range of the cell are shown in table 6 and the test results are shown in table 7.

TABLE 6 Battery Assembly and test mode

TABLE 7 test results of the batteries

The test results of the batteries Y0-Y3 show that the first efficiency, the 1-50-week discharge specific capacity and the capacity retention rate of the batteries can be improved by using the batteries W1-W2 and M1 as liquid electrolyte additives. However, compared with W1-W2, M1 has more obvious improvement on the first efficiency and first cycle specific discharge capacity of the battery, probably because W1 contains 1-OBF₃M, W2 is a complex, no bond, chemically unstable and free of lithium, and contains three-OBF₃M1 of the lithium ion battery contains a lithium source, and lithium ions removed from the positive electrode are less consumed in the process of forming a good passivation layer, so that the first-effect, first-cycle discharge specific capacity and capacity retention rate of the battery are excellent. The applicant is still in further research with a clearer and more clear mechanism. But no matter whetherIn any case, it is certain that the OBF₃The presence and amount of M has a substantial effect on battery performance.

In the present invention, the structures in examples 1 to 15 were selected as representative to explain the production method and effects of the present application. Other structures not shown are all very effective and similar to examples 1-15, and other structures not shown can be prepared by the method described in any of examples 1-5. The preparation method is that the raw material, boron trifluoride compounds and M source react to obtain the product boron trifluoride organic salt, namely-OH in the raw material is changed into-OBF₃M, M may be Li⁺、Na⁺Etc., and the other structures are not changed. In addition, many research teams of the applicant have already made serial effect tests, which are similar to the effect in the above embodiments, such as: from raw materials

Etc., the boron trifluoride salt of the present application is excellent in effect, but only partial structure and data are given due to space relation.

In the present invention, it is also noted that (i) -OBF₃-BF of M₃It must be bonded to the oxygen atom O, which is in turn bonded by a single bond to the carbon atom C, so that O cannot be a ring-located oxygen. If O is bonded to N, S or another atom, or if O is located on a ring (or if O is bonded to another two groups), the structure is greatly different from the present application, and therefore, it cannot be predicted whether such a structure can be applied to the electrolyte of the present application, what effects and application scenarios are expected, and therefore, the inventors of the present invention will conduct independent studies on these structures, and will not conduct much discussion here; ② the structure does not contain sulfydryl. ③ the bicyclic boron trifluoride salts are preferably in a non-polymeric stateThe organic, polymeric state has its unique characteristics and features, and the applicant may later develop specific studies on the polymeric state, which is referred to herein as the non-polymeric state.

In the present application, the above three cases are all required to be satisfied, and if not, the properties of the present application are greatly different, so that the application scene or effect after change is not well predicted, and may be greatly changed, and if valuable, the present inventors will perform special research separately later.

It should be noted that, the applicant has performed a great number of tests on the series of structures, and sometimes, for better comparison with the existing system, there are cases where the same structure and system are tested more than once, and therefore, there may be some error in the tests performed at different times.

In addition, the raw materials of the present invention can be obtained by purchase or simple preparation, which is extremely fundamental in the field of organic chemistry, and there is no difficulty, so that the structure of the raw materials or the synthesis of the raw materials is conventional and not described much, which is out of the scope of the present invention.

Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (13)

1. A ternary electrolyte comprising a bicyclic salt, wherein: the electrolyte comprises a bicycloheteroboron trifluoride salt represented by the following general formula I:

in the above general formula IR and R₁Represents a ring comprising a single ring and a multiple ring composed of at least two single rings; e₈Is a chain containing no, at least one atom or a structure containing a ring; when E is₈When not present, R and R₁By a single or double bond;

m is a metal cation;

E₄is a chain without or containing at least one atom;

-E₃-OBF₃m is connected to E₄、E₈R or R₁On any one atom of;

E₁、E₂、E₃independently a chain structure or a structure containing a ring, which is free of, contains at least one atom;

r' and R₁' independently is a substituent, any one H on the representative ring may be substituted by a substituent, and the substituent may be substituted for one H or two or more H, and if two or more H are substituted, the substituents may be the same or different.

2. The ternary electrolyte comprising a bicyclic salt according to claim 1, wherein: in the general formula I, E₈By single or double bonds with R and R₁Connecting;

the monocyclic ring is a three-to twenty-membered ring and comprises a saturated carbocycle, a saturated heterocycle, an unsaturated carbocycle and an unsaturated heterocycle; saturated, unsaturated heterocyclic rings are rings containing at least one heteroatom selected from O, N, P, Si, Se, B, S, Se or Al;

the polycyclic ring composed of a single ring includes a parallel ring, a bridged ring, a spiro ring, and a ring containing at least two of the three polycyclic rings; the fused ring is formed by combining more than 2 single rings together, and two adjacent atoms on one ring share with two adjacent atoms on the other ring in the two fused rings; the bridge ring is a polycyclic structure sharing more than two atoms; the spiro ring shares one atom with two adjacent monocyclic rings.

3. The birch-containing compound of claim 2A salt-like ternary electrolyte characterized by: in the general formula I, with-OBF₃The atoms to which M is directly connected include C, S, N, Si, P, B or O; preferably with said-OBF₃The atom to which M is attached is a carbon atom C;

preferably, H on any one C in said formula i may be independently substituted by halogen.

4. The ternary electrolyte comprising a bicyclic salt according to claim 3, wherein: the substituents R' and R₁' independently include H, a halogen atom, an etheroxy group, an etherthio group, a nitro group, a cyano group, a C ═ O containing substituent, an O ═ S ═ O containing substituent, an N containing substituent, an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, a heteroalkynyl group, an alkenylalkynyl group, a heteroalkynyl group, an O ═ S, a nitro group, a cyano group, a C ═ O containing substituent, a O ═ S ═ O substituent, a N containing substituent, an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, an alkenylalkynyl group, a heteroalkynyl group, a hetero alkenylalkynyl group, a hetero alkynyl group, a,

A salt substituent, a cyclic substituent, and a group in which H on any one of C of these groups is substituted with a halogen atom;

preferably, the cyclic substituent includes a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring and a polycyclic substituent having two or more ring structures at the same time; r₅、R₆Independently H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, and heteroalkynyl; such salt substituents include, but are not limited to, sulfate, sulfonate, sulfonimide, carbonate, carboxylate, ether, nitrogen, silicate, phosphate, hydrochloride, nitrate, azide; any one of the structures of heteroalkane/alkene/alkyne/alkenynyl contains at least one non-carbon atom selected from halogen, S, N, O, P, Se, Ca, Al, B, or Si;

the first substituent can be optionally bonded to an atom of each of the above substituents.

5. The tricyclic salt-containing ternary electrolyte of claim 4, wherein: e₁、E₂Or E₃Independently selected from the group consisting of none, carbonyl, ester, alkaneA group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, a group containing a cyclic structure,

Or ═ N-R₇’-；

E₄Is a chain structure without or containing 3 free connecting bonds, and the 3 free connecting bonds are respectively connected with a ring and E₁And E₃Connecting;

E₈is nothing, ether oxygen group, ether sulfur group, carbonyl group, ester group, phosphate group, alkyl group, heteroalkyl group, alkenyl group, heteroalkenyl group or cyclic group, and the cyclic group comprises

and-R₅₂-R₅₁-R₅₃-，R₅₁Is a first monocyclic ring, a first fused ring or a first linked ring, wherein the first linked ring contains at least two monocyclic rings, adjacent monocyclic rings are linked by a single bond or by a chain containing at least one atom, R is₅₂And R₅₃Independently a chain containing no or at least one atom;

represents a second monocyclic ring or a second fused ring, R₅₀Represents an atom in a second monocyclic ring or a second fused ring, the atom containing two atoms which are respectively associated with R and R₁A linked key;

wherein the double bond in the heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-nitrogen double bond C ═ N, and R is₅’、R₆' and R₇' independently of R in claim 4₅、R₆The species defined in (1) are identical.

6. The tricyclic salt-containing ternary electrolyte of claim 5, wherein:

the monocyclic ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, and the monocyclic ring is a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a nine-membered ring, a ten-membered ring, a twelve-membered ring, a fourteen-membered ring, a sixteen-membered ring or an eighteen-membered ring;

wherein the tri-unsaturated carbocyclic ring comprises a1 double-bonded carbocyclic ring; a ternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the ternary unsaturated heterocycle comprises 1 double bond and simultaneously contains 1 or 2 heteroatoms;

the quaternary unsaturated carbocycle includes carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not adjacently disposed; a quaternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the quaternary unsaturated heterocycle is a four-membered ring which contains 1 or 2 double bonds and simultaneously contains 1 or 2 heteroatoms;

five-membered unsaturated carbocycles include carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not disposed adjacent; a five-membered saturated heterocycle includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the five-membered unsaturated heterocycle is a five-membered ring which contains 1 or 2 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;

six-membered unsaturated carbocycles include carbocycles containing 1,2 or 3 double bonds, and if 2 or 3 double bonds, are non-adjacent to each other; six membered saturated heterocyclic rings include saturated rings containing 1,2, 3 or 4 heteroatoms; the six-membered unsaturated heterocycle is a six-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3, 4, 5 or 6 heteroatoms;

the seven-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; a seven membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the seven-membered unsaturated heterocycle is a seven-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;

the eight-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; an eight membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; an eight-membered unsaturated heterocycle is an eight-membered ring containing 1,2, 3 or 4 double bonds and simultaneously 1,2, 3 or 4 heteroatoms;

the nine-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; a nine membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the nine-membered unsaturated heterocycle is a nine-membered ring which contains 1,2, 3 or 4 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;

the ten-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two are arranged non-adjacently; a ten-membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the ten-membered unsaturated heterocycle is a ten-membered ring containing 1,2, 3 or 4 double bonds and simultaneously containing 1,2, 3 or 4 heteroatoms;

the twelve-membered ring, the fourteen-membered ring, the sixteen-membered ring and the eighteenth-membered ring respectively and independently comprise a saturated carbon ring, a saturated heterocyclic ring containing 1,2, 3, 4, 5 or 6 heteroatoms and an unsaturated heterocyclic ring, wherein the unsaturated heterocyclic ring is a ring containing 1,2, 3, 4, 5 or 6 heteroatoms and simultaneously containing 1,2, 3, 4, 5 or 6 unsaturated bonds;

the polycyclic ring is formed by combining more than 2-5 single rings; any one of the monocyclic ring or polycyclic ring is connected with the substituent R' or R₁’；

Any one heteroatom on the above heterocyclic ring is independently selected from O, N, P, Si or S.

7. The tricyclic salt-containing ternary electrolyte of claim 6, wherein: the monocyclic ring is selected from the following rings: cyclopropane, cyclopropene, ethylene oxide, cyclobutane,

Cyclobutene, cyclopentane, cyclopentene, cyclopentadiene, pyrrole, dihydropyrrole, tetrahydropyrrole, furan, dihydrofuran, tetrahydrofuran, thiophene, dihydrothiopheneTetrahydrothiophene, imidazole, pyrazole, thiazole, dihydrothiazole, oxazole, dihydrooxazole, isoxazole, dihydroisoxazole, triazole, dihydrotriazole, tetrazole, benzene ring, pyridine, dihydropyridine, tetrahydropyridine, pyrimidine, pyrazine, pyridazine, p-diazabenzene, triazine, cyclohexane, dioxane, cyclohexene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, dihydrothiopyran, tetrahydrothiopyran, dithiane, 1, 2-dithiane, [1, 3-dithiane]Oxazolidines, morpholines, piperazines, pyrones, dihydropyrimidines, tetrahydropyrimidines, hexahydropyrimidines, cycloheptanes, epoxyhexanes, cycloheptenes, 1, 3-cycloheptenes, 1,3, 5-cycloheptenes, cyclooctanes, cyclononanes, cyclononanatrienes, cyclododecanes, 1,5, 9-triazacyclododecanes, pentazocines, and combinations thereof,

Or 18-crown-6;

the polycyclic ring is composed of the above-mentioned monocyclic ring.

8. The tricyclic salt-containing ternary electrolyte of claim 7, wherein: included for said formula I are, but not limited to, the following compounds:

in the above structure, Q₁、Q₂、Q₃homo-OBF₃M; e in each ring structure₁、E₂、E₃Independently of each other, as defined in any one of claims 1 to 7; e in each ring structure₈Are each independently as defined in any one of claims 1 to 6E₈The consistency is achieved; any one H on each ring can be independently selected from A₁、A₂、A₃Or A₄Any one substituent of (A), A₁、A₂、A₃Or A₄Are each independently selected from the substituents R' or R as defined in any one of claims 1 to 7₁' any one substituent defined in (1).

9. The ternary electrolyte comprising a bicyclic salt according to any one of claims 4 to 8, wherein: the substituents R' and R₁’、A₁、A₂、A₃Or A₄Independently selected from H, halogen atom, carbonyl, ester group, aldehyde group, ether oxygen group, ether sulfur group, ═ O, ═ S,

Nitro, cyano, amino, amide, sulfonamide, sulfoalkane, hydrazino, diazo, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenylalkynyl, heteroalkynyl, cyclic substituents and substituents of said salts; wherein ester groups include carbonates, carboxylates, sulfonates, and phosphates;

preferably, in the substituent, the halogen atom comprises F, Cl, Br, I, and the carbonyl group is-R₁₀COR₁₁The ester group is-R₁₂COOR₁₃、-R₁₂OCOR₁₇、-R₁₂SO₃R₁₃、R₁₂O-CO-OR₁₃Or

The ether oxygen radical is-R₁₄OR₁₅The etherthio radical is-R₁₄SR₁₅Amino is ═ N-R₂₀、

or-CH ═ N-R₂₄Amide is

Or

Sulfonamide group of

The sulfoalkane is-R₁₈SO₂R₁₉The diazo group is-N ═ N-R₃₈Salt substituents include, but are not limited to, sulfate, sulfonate, sulfonimide, carbonate, carboxylate, nitrate;

wherein R is₅、R₆、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅、R₁₆、R₁₇、R₁₈、R₁₉、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₈、R₂₉、R₃₀、R₃₁、R₃₂、R₃₃、R₃₄、R₃₅、R₃₈Independently is C_1-10Alkyl radical, C_1-10Heteroalkyl group, C_1-10Alkenyl radical, C_1-10Heteroalkenyl, C_1-10Alkynyl, C_1-10Heteroalkynyl, heteroalkenyl/alkynyl being a heteroalkenyl/alkenyl/alkynyl group bearing at least one of the non-carbon atoms; the group directly bound to N or O can also be a metal ion, R₅、R₆、R₁₀、R₁₂、R₁₄、R₁₈、R₂₀、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇、R₂₉、R₃₀、R₃₃、R₃₅、R₃₈May independently be H or none;

cyano radicals selected from-CN, -CH₂CN、-SCH₂CH₂CN、-N(CH₃)CH₂CH₂CN or-CH₂CH₂CN。

The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl; heteroalkyl is an alkyl group containing at least one of the heteroatoms;

the alkenyl group includes vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl; heteroalkenyl is alkenyl containing at least one of the heteroatoms; the alkynyl group comprises ethynyl, propynyl, butynyl, pentynyl, hexynyl or heptynyl; heteroalkynyl is an alkynyl group containing at least one of the heteroatoms; the alkenylalkynyl group is a structure containing at least one double bond and at least one triple bond; said heteroalkynyl is an alkynyl containing at least one of said heteroatoms;

the cyclic substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and polycyclic rings;

preferably, any one ring of the ring substituents is independently linked to the substituted bicyclic ring by any one of the following linking groups: -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH(CH₃) -, butyl, ethylene, propylene, butene, acetylene, propyne, -COO-, -CO-, -SO₂-、-N＝N-、-O-、-OCH₂-、-OCH₂CH₂-、-CH₂OCH₂-、-COCH₂-、-CH₂OCH₂CH₂-、-OCH₂CH₂O-、-COOCH₂CH₂-、-S-、-S-S-、-CH₂OOC-、-CH＝CH-CO-、-COOCH₂OCOCH₂-、

Or a single bond; r₄₂Independently selected from H, methyl, ethyl or propyl; r₃₆、R₃₇、R₄₂Independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, fluoromethyl, fluoroethyl, methoxy, ethenyl, propenyl, or a metal ion; r₈₃Selected from alkyl or cyclic;

any atom with H on any ring of the above ring substituents can be selectively connected with the first substituent; the first substituent is selected from H, halogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, fluoromethyl, fluoroethyl, methoxy, ethoxy, nitro, alkenyl, alkynyl, ester group, sulfonate, sulfoalkane, amido, cyano, aldehyde group, -SCH₃、-COOCH₃、COOCH₂CH₃、-OCF₃、＝O、＝S、-N(CH₃)₂、-CON(CH₃)₂、-SO₂CH₃、-SO₂CH₂CH₃Or a substituent wherein H on any one C of these groups is substituted with a halogen.

10. The tricyclic salt-containing ternary electrolyte of claim 8, wherein: e₁、E₂Or E₃Independently selected from the group consisting of none, carbonyl, keto, ester, -CH₂-、-CH₂CO-, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, N-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, cyclohexyl, cyclopentyl, 1, 3-hexadienyl, -C ═ N-, -C (CH)₃)₂-、-CH(CH₃)-、-CH(CF₃)-、-C(CF₃)₂-、-CH₂CH₂CH(CH₃)-、-Z'₁CH₂CH₂-、-CH＝CH-CO-、-OCH₂CH₂CH₂CO-、＝N-CH₂-CO-、-Z'₁CH₂CO-、-Z'₁CH₂CH₂CO-、-Z'₁CH₂CH₂CH₂CO-、-COOCH₂CH₂-、-O-CH₂(CH₂)₄CH₂-、-CH₂CH₂CO-、-CH₂CH(CH₃)-、-OCH₂-、-CH(CH₃)CO-、-CH(CH₂Cl)-、-CH(OCH₃)-、-CH(CHO)-、-CH₂COCO-、-C(CH₃)₂CH₂CH₂-、-CH₂(CH₂)₅CO-、-CH₂(CH₂)₆CO-、-N＝C(CH₃)-、-O-(CH₂)₆-、-CH₂Z'₁CH₂-、-CH₂(CH₃)Z'₁CH₂-、-CH₂CH₂Z'₁CH₂-、

-(CH₃)CHCH₂CH₂Z’₁CH₂-、-O-CH(CH₃)-(CH₂)₄CH₂-、

E₈Is selected from-CH, -CH₂-、-CH₂CH₂-、-C(CH₃)₂-、-CH(CH₃)-、-CH(CH₃)CH(CH₃)-、-CH(Et)CH(Et)-、＝CH-CH＝、-CH₂CH(CH₃)-、-CO-、-O-、COO-、-OCH₂O-、-CH＝CH-、-COCH＝CH-、-CH＝N-N＝CH-、-CH＝CHCOCH₂COCH＝CH-、-S-、-S-S-、

Wherein Z 'of claim'₁is-O-, -S-S-),

-COO-、

Sulfonyl, sulfonylimino or sulfonyloxy, wherein R₄₁Is H, methyl, ethyl, propyl, isopropyl, butyl, ethoxy, methoxy or a metal ion; r is₄₄、R₄₅Independently an alkyl group or a ring;

R₃₉、R₅₀independently selected from H, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, nitro, hexyl, thiazole, -CH (CH)₃)₂、-CH₂CH(CH₃)₂、-CH₂CH₂NO₃、

Wherein R is₈、R₄₀、R₄₆、R₄₇、R₄₈、R₄₉Independently is halogen-free, methyl, nitro or trifluoromethyl, R₉Is nothing, methylene, -CH (CH)₃)-Ph；R₃₈Selected from among nothing, methyl, ethyl, halogen atoms, fluoromethyl, fluoroethyl or-CH₂-N(CH₃)₂；R₃₇Selected from halogen atom, alkyl, fluoroalkyl, methoxyl, nitryl, aldehyde group, ketone group or ester group.

11. The ternary electrolyte comprising a bicyclic salt according to any one of claims 1 to 10, wherein: the general formula I is lithium salt, potassium salt, sodium salt, calcium salt or magnesium salt, preferably lithium salt, potassium salt or sodium salt;

the general formula I is as follows: a compound of formula i according to any one of claims 1-10 wherein H on any one C is substituted, wholly or partially, with halogen, preferably F.

12. A method for producing an electrolyte according to any one of claims 1 to 11, characterized in that: the method comprises the step of reacting a three-OH-contained catenated ring ternary structure, a boron trifluoride compound and an M source to obtain a product, namely the product contains three-OBF₃And (3) a bicyclic boron trifluoride salt of M.

13. Use of the ternary electrolyte containing a bicyclic salt according to any one of claims 1 to 11 in a secondary battery, characterized in that: the application is as follows: the bicyclic boron trifluoride salt shown in the general formula I can be used as an additive;

preferably, the application comprises application in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes, which each independently comprise a bicyclic boron trifluoride salt according to any one of claims 1 to 11.

Preferably, the application further comprises the application as a battery or a battery pack, wherein the battery comprises the ternary electrolyte containing the bicyclic salt and a positive electrode, a negative electrode, a separator and a packaging shell; the battery comprises any one of a liquid battery, a mixed solid-liquid battery, a semi-solid battery, a gel battery, a quasi-solid battery and an all-solid battery;

the battery pack includes the battery.

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