CN114573617A

CN114573617A - Ternary electrolyte containing saturated heterocycles, and preparation and application thereof

Info

Publication number: CN114573617A
Application number: CN202011380889.2A
Authority: CN
Inventors: 俞会根; 杨萌
Original assignee: Beijing WeLion New Energy Technology Co ltd
Current assignee: Beijing WeLion New Energy Technology Co ltd
Priority date: 2020-11-30
Filing date: 2020-11-30
Publication date: 2022-06-03

Abstract

The invention relates to a saturated heterocyclic ternary electrolyte, and a preparation method and an application thereof, wherein the electrolyte comprises boron trifluoride salt represented by the following general formula I: in the general formula I, the compound has the following structure,

represents a saturated heterocyclic ring containing at least one heteroatom in the ring; the heteroatom is selected from S, N, O, P, Se, Ca, Al, B or Si; m is a metal cation; e₄Is a chain without or containing at least one atom; -E₂‑OBF₃M is connected to E₄Or saturated heterocyclic rings

On 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 is a substituent, and any H on the representative ring can be substituted by the substituent. The boron trifluoride salt can be used as an additive in a battery, 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 saturated heterocycles, and preparation and application thereof

Technical Field

The invention relates to the technical field of batteries, in particular to a saturated heterocyclic ternary electrolyte and preparation 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 functional additive is added into the liquid electrolyte, and the liquid electrolyte is partially or completely replaced by 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 an 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.

One of the groups of the Applicant has been working on compositions containing-OBF obtained by substitution of one 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 researchers₃Compounds of the group 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 researched, and the prior art is few, so that the reference value is small, and the research on three groups does not have any reference source. The present research team also discovered unexpectedly in occasional studies-OBF containing trihydroxy substitutions₃M organic matter is applied to batteries in liquid electrolyte and solid electrolyte, and the prepared batteries have excellent performance and surprising effect after being tested, so that a specially established team carries out special research on trisubstituted-OBF₃M, and obtains better research results.

More importantly, the present application is directed to-OBF₃The structure of M attached to a heterocycle, especially a saturated heterocycle, was independently studied. This is because the chemical properties such as electrical properties of the hetero atoms themselves are also quite specific, and their presence on the ring affects the chemical and physical properties of the entire ring, including the structure of the carbocyclic ring, aromatic ring, and chainAnd so on, are substantially different from each other, so that the association or deductibility between each other is uncertain. Thus, the-OBF is attached to a saturated heterocyclic ring₃M, 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. The subject of the present application is therefore identified as having the-O-BF attached directly or indirectly to the saturated heterocycle₃M, i.e. the main body of the ring is independently studied by distinguishing it from aromatic, carbocyclic and unsaturated rings, etc., so as to more specifically and definitely determine-O-BF₃Specific case when M is linked to a saturated heterocycle.

Disclosure of Invention

The invention provides a saturated heterocyclic ternary electrolyte 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 saturated heterocycles, the electrolyte comprising a saturated heterocyclic boron trifluoride salt represented by the following general formula I:

in the general formula I above, the compound of formula I,

represents a saturated heterocyclic ring containing at least one heteroatom in the ring; the heteroatom is selected from S, N, O, P, Se, Ca, Al, B or Si; m is a metal cation; e₄Is a chain without or containing at least one atom; in the general formula I there is also one-E₂-OBF₃M, the-E₂-OBF₃M is connected to E₄Or saturated heterocyclic rings

On any one atom of; e₁、 E₂、E₃Independently is absent, at least oneA chain structure of atoms or a structure containing a ring; r is a substituent, any one H on the representative ring can be substituted by the substituent, and the substituent can be substituted by one H and can also be substituted by two or more H, if two or more H are substituted, the substituents can be the same or different, that is, each H can be substituted by the substituent defined in any one of R.

Further, in the general formula I, the saturated heterocyclic ring is a three-to twenty-membered ring.

Further, in the formula I, with-OBF₃M is bonded to an atom comprising C, S, N, Si, P, B or O; preferably with-OBF₃The atom to which M is directly attached is a carbon atom C.

Further, the heteroatom is selected from S, N, O, P, B or Si.

Further, H on any one C in the general formula I may be independently substituted by halogen, i.e. ring, substituent, E₁、 E₂Etc., and therefore, in the definitions described below, there are some technical features that do not specifically describe the substitution of any one C H by a halogen.

Further, in three-OBF of the formula I₃In M, at least one is attached to a carbon atom other than the carbonyl carbon, which includes-C ═ O or-C ═ S.

Further, the substituent R is selected from H, halogen atoms (including F, Cl, Br, I), carbonyl, ester groups, aldehyde groups, ether oxy groups, ether thio groups, ═ O, ═ S, and,

Nitro, cyano, amino, amide, sulfonamide, sulfoalkane, hydrazino, diazo, alkyl, heteroalkyl, cyclic substituents, salt substituents, and those wherein any hydrogen H is substituted with a halogen atom. Wherein the ester group includes carboxylic acid esters, carbonic acid esters, sulfonic acid esters, and phosphoric acid esters; hydrocarbyl groups include alkyl, alkenyl, alkynyl, and alkenylalkynyl groups; heterohydrocarbyl is hydrocarbyl containing at least one non-carbon atom, including heteroalkyl, heteroalkenyl, heteroalkynyl, and heteroalkynynyl; the non-carbon atoms being selected from halogen, N, P, S, O,Se, Al, B and Si; the ring substituent comprises a ternary-eight-membered ring and a polycyclic ring formed by at least two monocyclic rings; the salt substituents include but are not limited to sulfate, sulfonate, sulfonimide, carbonate, thioether, oxoether, nitrogen, hydrochloride, nitrate, azide, silicate, phosphate.

Further, the carbonyl group is

The ester group is-R₅₅COOR₅₆、-R₅₅OCOR₅₄、-R₅₅SO₂OR₅₆Or R₅₅O-CO-OR₅₆Or

Amino is ═ N-R₂₁、

or-CH ═ N-R₈₁Amide is

Sulfonamide group of

The sulfoalkane is

Diazo is-N ═ N-R₁₆With an ether oxygen radical of-R₃₁OR₃₂The etherthio radical is-R₃₁SR₃₂(ii) a Wherein R is₂、R₃、R₁₆、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₃₁、R₃₂、R₄₀、R₄₁、R₄₂、R₄₃、R₄₄、R₄₅、 R₄₆、R₅₀、R₅₁、R₅₂、R₅₄、R₅₅、R₅₆、R₅₇、R₇₉、R₈₀、R₈₁Independently an alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, ring, or a group in which H on any one of these groups, C, is substituted with a halogen, a heteroalkane/alkene/alkynyl being an alkane/alkene/alkynyl containing at least one of the non-carbon atoms; and R is₂、R₃、R₁₆、R₂₁、R₂₃、R₂₅、R₄₀、R₄₁、R₄₂、R₇₉、R₈₀、R₈₁Can also be H, R₂₂、R₂₄、R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent; the group directly attached to N or O can also be a metal ion, such as R₂₅、R₃₂、R₄₀、R₄₂、R₅₆、R₅₇、R₇₉Etc. may be metal ions, such as Li⁺、Na⁺、K⁺、Ca²⁺And the like.

Further, E₁、E₂Or E₃Selected from the group consisting of a carbonyl group, a carbonyl-containing group, an ester-containing group, an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, a group containing a cyclic structure, a substituted aryl group, a substituted heteroaryl,

or-N-R₆-, said heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-carbon double bond C ═ N, R₄、R₅And R₆Independently of R in the preceding paragraph₂、R₃The species defined in (1) are identical. E₄Is a chain structure without or containing 3 free connecting bonds and at least one atom, the 3 free connecting bonds are respectively connected with a saturated heterocyclic ring and E₁And E₂Is connected, if E₁And/or E₂If not, then E₄Free bond of (A) and-OBF₃And M is connected.

Further, in the general formula i, the saturated heterocyclic 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 and an eighteen-membered ring; preferably, the saturated heterocycle is three-membered, four-membered, five-membered, six-membered, seven-membered, eight-membered, sixteen-membered and eighteenth-membered. Preferably, the three-membered ring: contains a heteroatom; a four-membered ring: containing 1 or 2 heteroatoms; five-membered ring: containing 1,2, 3 or 4 heteroatoms; a six-membered ring: containing 1,2, 3, 4, 5 or 6 heteroatoms; seven-, eight-, nine-membered rings: containing 1,2, 3 or 4 heteroatoms; ten-, twelve-, fourteen-membered rings: containing 1,2, 3, 4 or 5 heteroatoms; sixteen and eighteen membered rings: containing 1,2, 3, 4, 5 or 6 heteroatoms; any one of the heteroatoms in each heterocycle is independently selected from S, N, O, P, Se, B, or Si.

Further, in the general formula I, the saturated heterocyclic ring is selected from a ternary heterocyclic ring containing 1O, 1N or 1S, a quaternary heterocyclic ring containing 1O, 1S, 1N, 2O, 2N or both 1N and 1O, a five-to eight-membered heterocyclic ring containing 1S, 1N, 1O, 1 Si, 1P, 2S, 2N, 2O, 3O, simultaneously containing 1O and 1S, simultaneously containing 1O and 1N, simultaneously containing 1N and 1S, simultaneously containing 1 Si and 1N, simultaneously containing 1O and 1P, simultaneously containing 1N and 1P, simultaneously containing 2N and 1P, simultaneously containing 3N and 3P, simultaneously containing 2O and 1P or simultaneously containing 2O and 1 Si; a ten-to sixteen-membered heterocycle containing 1O, 1S, 1N, 3N, 4O, 4S, 4N, 5O or 5S, or an eighteen-membered heterocycle containing 5O, 5S, 6O, 6S or both 5O and 1N, in each of which there are two-OBFs₃M is directly or indirectly attached to any one or two of the heterocyclic ring atoms. More preferably, the saturated heterocyclic ring includes, but is not limited to:

h on any one C in the saturated heterocyclic ring can be independently substituted by the substituent R.

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、E₃And E₄Independently in accordance with any one of the preceding paragraphs; any one H on each saturated heterocycle may be independently selected from A₁Or A₂Any one substituent of (A), A₁、A₂Are each independently selected from any one of the substituents defined in said substituent R in any of the above paragraphs.

Further, in the substituent A₁、A₂Or in R, the halogen atom comprises F, Cl, Br and I. R₂、R₃Independently H, methyl or ethyl; r₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₃₁、R₃₂、R₄₀、R₄₁、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆、 R₅₀、R₅₁、R₅₂、R₅₄、R₅₅、R₅₆、R₅₇、R₇₉、R₈₀、R₈₁Independently an alkyl group containing 1-20 atoms, a heteroalkyl group containing 1-15 atoms, an alkenyl group containing 1-20 atoms, a heteroalkenyl group containing 1-15 atoms, or a CN containing group, and R₂₂、R₂₄、 R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent, R₂₁、R₂₃、R₂₅、R₄₀、R₄₁、R₄₂、R₇₉、R₈₀、R₈₁Can also be H, R₂₂、R₂₄、R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent; the group directly attached to N or O can also be a metal ion; wherein the ester group can also be selected from-OCH₂COOEt or-CH₂(CH₂)₆COOEt; the amide can also be selected from

R₄₆Can also be N (CH)₂CH₂CH₂CH₃)₂；R₂₁Can also be NO₂2-methylphenyl, 2, 4-dimethylphenyl, 2-methyl-3-chloro-phenyl, 3-trifluoromethylphenyl, CH₂COOCH₃Cyclohexane, 1, 3-cyclohexadiene, thiazole,

Or a fluorotolyl group; r₃₅Can also be selected from the group consisting of octyl, decyl, octadecyl, and-O- (CH)₂)₂CH(CH₃)₂(ii) a The carbonyl group can also be selected from the group consisting of-CO-CH (CH)₃)CH₂CH(CH₃)CH₂CH₃or-CO-CH (CH)₃)CH₂CH(CH₃)CCl₂CH₂Cl。

Diazo is-N ═ N-R₁₆，R₁₆Is phenyl or phenyl with methyl, halogen atom or nitro connected.

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, tetradecylAlkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, -CH (CH)₃)₂、-C(CH₃)₂CH₂C(CH₃)₃、-C(CH₃)₂CH₂CH₃Etc. fall within the scope defined by the alkyl group.

Heteroalkyl is an alkyl group containing at least one of the heteroatoms, preferably the heteroalkyl group comprises-CH₂NO₂、-Z₁CF₃、 -CH₂Z₁、-CH₂Z₁CH₃、-CH₂CH₂Z₁、-Z₁(CH₂CH₃)₂、-CH₂N(CH₃)₂、-CH₂CH₂-O-NO₂、-CH₂S-S-CH₃、 -CO-CH₂Cl、-CO-CH₂Br、-CH₂Z₁CH(CH₃)₂、-CH(Z₁CH₂CH₃)₂、-CH₂CH(SCH₂CH₃)₂、 -CH₂Z₁CH(CH₃)₂、-COCH₂CH(CH₃)₂、-OCH₂(CH₂)₆CH₃、-CH₂(CH₃)Z₁CH₃、 -CH₂(CH₃)Z₁CH₂CH₃、-CH₂CH₂Z₁CH₃、-CH₂CH(CH₃)Z₁CH₃、-CH(CH₃)CH₂Z₁CH₃、 -CH₂CH₂Z₁CH₂CH₃、-CH₂CH₂CH₂Z₁CH₃、-CH₂CH₂CH₂Z₁CH₂CH₃、-CH₂CH(CH₃)CH₂Z₁CH₃、 -Z₁CH₂CH₂Si(CH₃)₃、

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

And the like belong to the alkenyl category.

Heteroalkenyl is alkenyl containing at least one of the heteroatoms, preferably selected from the group consisting of-N ═ CHCH₃、 -OCH₂CH＝CH₂、-CH₂-CH＝CH-Z₁CH₃、-C(CH₃)＝CHCH₃、-CH₂CH＝C(CH₃)₂、 -C(CH₃)＝CHCOCH₃、-COCH＝CHCH₂CH₃、-C(CH₃)＝CH₂、-CH＝CHCH₂-CH₂Z₁CH₃、 -CH₂-CH＝CH-Z₁CH₃。

Alkynyl includes ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl.

Heteroalkynyl is alkynyl containing at least one of said heteroatoms, preferably heteroalkynyl includes-C ≡ CCH₂CH₂CH₂Z₁CH₂CH₃、 -C≡CCH₂Z₁CH₂CH₃、-C≡C-Si(CH₃)₃。

Alkenynyl is a structure containing at least one double bond and at least one triple bond, preferably alkenynyl includes-C ≡ CCH ═ CHCH₃、 -C≡CCH₂CH＝CHCH₂Z₁CH₃、-C≡CCH₂CH₂CH＝CHCH₃。

Heteroalkynyls are alkynyls containing at least one of the heteroatoms mentioned, preferably heteroalkynyls selected from the group consisting of-CH ═ C (CN)₂、 -C≡CCH₂CH＝CHCH₂Z₁CH₃。

The ring substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and polycyclic; wherein: the cyclopropyl group is selected from a cyclopropyl group, an oxirane group, a thiirane group, a cycloazethane group or a cyclopropene group; the cyclobutyl group is selected from the group consisting of cyclobutyl and cyclobutylheteroalkyl (e.g.

Etc.), cyclobutenyl; the cyclopentyl group is selected from cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, pyrrolyl group, dihydropyrrolyl group, tetrahydropyrrolyl group, furyl group, dihydrofuryl group, tetrahydrofuryl group, thienyl group, dihydrothienyl group, tetrahydrothienyl group, imidazolyl group, thiazolyl group

Dihydrothiazolyl, tetrahydrothiazolyl, isothiazolyl, dihydroisothiazolyl, pyrazolyl, oxazolyl

Dihydrooxazolyl, tetrahydrooxazolyl, isoxazolyl

Dihydroisoxazolyl, tetrahydroisooxazolyl, triazolyl, tetrazolyl, triazolyl, tetrazolyl, and tetrazolyl,

The cyclohexyl is selected from: phenyl, pyridine, dihydropyridine, tetrahydropyridine, pyrimidine, p-diazepine, cyclohexane, cyclohexenyl, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, morpholine, piperazine, pyrone, pyridazinePyrazine, triazine, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, thiopyran, dihydrothiopyran

Tetrahydrothiopyrans, dithianes

1, 2-dithianes

1, 4-dithianes, oxazolidines (e.g. [1,3 ]]Oxazolidines

)、

The polycyclic ring is selected from: biphenyl, naphthyl, anthryl, phenanthryl, quinonyl, pyrenyl, acenaphthenyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, alkanyl, benzoxazole,

Wherein, Z is as defined above₁is-O-, -S-S-),

Wherein R is₁₅、R₉₀、R₉₁、R₉₂Independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, fluoromethyl, fluoroethyl, methoxy, ethenyl, propenyl, or metal ions. On any one of the above-mentioned ring substituentsEach of the H-bearing atoms of (a) may independently be attached to a first substituent of the same type as that defined for substituent R; more preferably, the first substituent is selected from the group consisting of H, halogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, fluoromethyl, fluoroethyl, methoxy, ethoxy, nitro, alkenyl, alkynyl, ester, sulfonate, sulfoalkane, amide, cyano, aldehyde, -SCH₃、-COOCH₃、COOCH₂CH₃、-OCF₃、＝O、-CO-N(CH₃)₂、

Or a substituent in which H on any one C of these groups is substituted with halogen; r₁₀Selected from methyl, ethyl or propyl.

Any atom with H in any ring structure of the ring substituents of the ring may be independently linked to the saturated heterocycle via the following linking groups: single bond (direct bond, i.e., ring to ring direct bond), methyl (-CH)₂-), ethyl (-CH)₂CH₂-), propyl, butyl, ethylene, propylene, butylene, acetylene, propyne, -COO-, -COCH₂-、 COOCH₂CH₂-、-CH₂OCH₂-、-CH₂OCH₂CH₂-、-OCH₂CH₂O-、-OCH₂-、-OCH₂CH₂-、-N＝N-、 -S-、-S-S-、-O-、-CH＝CH-COO-CH₂CH₂-、-CH₂OOC-、-CH＝CH-CO-、-CH₂N(CH₃)CH₂-、

Connecting; r₁₄Selected from H, methyl, ethyl or propyl, R₈₃Selected from alkyl or cyclic; r is₄₇、R₉₃、R₉₇Is independently selected from the group consisting ofA linking group.

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, the polycyclic ring can be a fused ring, a bridged ring or a spiro ring; more preferably, the amount of the organic solvent is,

and

independently phenyl, cyclopropane, oxirane, cyclobutane, cyclopentane, 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, cycloheptane.

Further, E₁、E₂And E₃Independently selected from the group consisting of none, carbonyl, keto, ester, -CH₂-, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, N-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octenyl, nonenyl, decenyl, cyclohexyl, cyclopentyl, 1, 3-hexadienyl, -C ═ N-, -C (CH)₃)₂-、-CH(CH₃)-、-CH(CF₃)-、-C(CF₃)₂-、-CH₂CH₂CH(CH₃)-、-Z'₁CH₂CH₂-、-CH₂CH(CH₃)-、 -OCH₂-、-CH＝CH-CO-、-OCH₂CH₂CH₂CO-、＝N-CH₂-CO-、-Z'₁CH₂CO-、-Z'₁CH₂CH₂CO-、 -Z'₁CH₂CH₂CH₂CO-、-COOCH₂CH₂-、-CH(CH₃)CO-、-CH(CH₂Cl)-、-CH(OCH₃)-、-CH(CHO)-、 -CH₂COCO-、-C(CH₃)₂CH₂CH₂-、-O-CH₂(CH₂)₄CH₂-、-CH₂CH₂CO-、-CH₂(CH₂)₅CO-、 -N＝C(CH₃)-、-O-(CH₂)₆-、-CH₂Z'₁CH₂-、-CH₂(CH₃)Z'₁CH₂-、-CH₂CH₂Z'₁CH₂-、 -CH₂CH(CH₃)Z'₁CH₂-、

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

E₄Selected from among,

Wherein, Z 'is'₁is-O-, -S-S-, -COO-,

wherein R is₁₁Is H, methyl, ethyl, propyl, isopropyl, butyl, ethoxy or methoxy, and the R is₁₁Any one of hydrogen and H in (1) can be replaced by F or Cl; r₅₉、R₆₀Independently an alkyl group or a ring. R₁₃、R₉₆Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, nitro, hexyl, thiazolyl, pyrrolyl, -CH (CH)₃)₂、 -CH₂CH(CH₃)₂、-CH₂CH₂NO₃、-CH₂CH₂CH(CH₃)₂、

Wherein R is₉Is nothing, methylene, -CH (CH)₃)-Ph；R₈、R₁₂、R₁₇、R₁₈、R₃₅、R₈₅、R₉₄、R₉₅Independently selected from halogen atom, alkyl, fluoroalkyl, methoxyl, nitryl, aldehyde group, ketone group, ester group or-CH₂-N(CH₃)₂Optionally R being attached to thiazolyl, pyrrolyl or phenyl Ph₁₇Such as trifluoromethyl.

Further preferably, E₁、E₂Or E₃Independently selected from the group consisting of none, -CH₂-、-CH₂CH₂-、-CO-、-CH₂CO-、-CH₂CH₂CO-、 -OCH₂-、-OCH₂CH₂-、-CH₂OCH₂-、-CH₂(CH₂)₁₂CO-、

R₁₃Independently selected from methyl, ethyl, propyl, -CH (CH)₃)₂Cyclopropane, cyclopentane, cyclohexane, benzene ring and nitro; r₁₇And R₁₈Selected from among none, methyl, ethyl, halogen atoms, fluoromethyl, fluoroethyl, methoxy, nitro; e₄Selected from among,

Further, M of the general formula I includes Na⁺、K⁺、Li⁺、Mg²⁺Or Ca²⁺Preferably Na⁺、K⁺Or Li⁺。

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.

Another aspect of the present invention is to provide a method for preparing an electrolyte according to any one of the above, wherein the method comprises reacting a saturated heterocyclic-containing ternary structure containing three-OH groups, a boron trifluoride compound and an M source to obtain a product containing three-OBF groups₃M is a saturated heterocyclic boron trifluoride salt.

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 saturated heterocyclic 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 ternary electrolyte containing saturated heterocycles in any section, namely the ternary electrolyte comprises the general formula I in any section.

The invention also provides a battery, which comprises the saturated heterocyclic ternary electrolyte, a positive electrode, a negative electrode, a diaphragm and a packaging shell, wherein the saturated heterocyclic ternary electrolyte comprises a saturated heterocyclic ternary electrolyte; 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 one compound, and is preferably-OBF₃M is connected with carbon atom C, and the structural effect protected by the invention is more prominent.

1. 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 an electrolyte from being in direct contact with an electrode active substance, inhibits the 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, is used as an additive, and consumes less active ions coming out of the positive electrode while forming a passivation layer on the surface of the electrode, so that the first coulombic efficiency and the first peripheral 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 positive electrode material and the low-voltage high-specific-volume negative electrode 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, when the structure in the application is used in an electrolyte, the structure can act synergistically as an additive property and a salt property, so that the electrolyte has an excellent effect superior to that of a traditional additive, for example, when the structure is used as an 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.

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

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

Drawings

FIGS. 1-12 are nuclear magnetic hydrogen spectra of products of some embodiments of the invention;

fig. 13 to 16 are graphs showing the effect of the circulation of boron trifluoride salt as an 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 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, -OBF₃Is increased correspondingly to the valence of MAnd (4) mixing.

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 saturated heterocyclic 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)₃To which one is attached to the main structure) and n-butyl has only one bond at the terminus, then the other bond can be located on any of the 4 carbon atoms in n-butyl.

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

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, when a1 is a substituent such as ═ O, methyl, F or the like, the five-membered ringWherein any one or more H may be independently substituted with methyl, F, etc., and any one of 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 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, 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 in which M is Li⁺Or Na⁺And so on. 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 under the atmosphere of nitrogen/argon, mixing, reacting at 5-50 ℃ for 5-24 hours, and drying the obtained mixed solution under reduced pressure at 20-80 ℃ and the vacuum degree of about-0.1 MPa 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 20-80 ℃ 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 the solution into the intermediate, stirring and reacting for 8 hours at 45 ℃, drying the obtained mixed solution under reduced pressure at 40 ℃ and a vacuum degree of about-0.1 MPa, washing the obtained solid with n-butyl ether for three times, and filtering and drying to obtain a product M1. The yield was 88%, 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 and reacting for 6 hours at room temperature, drying the obtained mixed solution under reduced pressure at 40 ℃ and the vacuum degree of about-0.1 MPa, washing the obtained crude product with cyclohexane for 3 times, filtering and drying to obtain a product M2, wherein Q is OBF₃And Li. The yield was 89%.

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. Boron trifluoride tetrahydrofuran complex (4.19g, 0.03mol) and 10ml THF are added into the intermediate, the mixture is stirred and reacted for 6 hours at room temperature, the obtained mixed solution is decompressed and dried at 40 ℃ and the vacuum degree of about-0.1 MPa, the obtained solid is washed three times by isopropyl ether, and the product M3 is obtained after filtration and drying. Yield 79% and nuclear magnetization are shown in fig. 2.

Example 4: original sourceMaterial

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 THF (tetrahydrofuran) 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 and reacting for 6 hours at room temperature, drying the obtained mixed solution under reduced pressure at 40 ℃ and the vacuum degree of about-0.1 MPa, washing the obtained crude product with cyclohexane for 3 times, filtering and drying to obtain a product M4, wherein Q is OBF₃And Li. The yield was 90%.

Example 5: starting materials

The preparation method comprises the following steps: 0.01mol of the starting material and sodium hydroxide (1.20g, 0.03mol) were mixed uniformly with 10ml of a methanol solution under a nitrogen atmosphere, and reacted at 10 ℃ 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. Boron trifluoride diethyl etherate (4.26g,0.03mol) is added into the intermediate, 10ml of ethylene glycol dimethyl ether solvent is added, the mixture is stirred for 24 hours at room temperature, the obtained mixed solution is decompressed and dried at 40 ℃ and the vacuum degree of about-0.1 MPa, the obtained solid is washed three times by dichloromethane, and the product M5 is obtained after filtration and drying. The yield is 72%, wherein Q is OBF₃Na。

Example 6: raw materials

Preparation: the product M6 was prepared from the starting material by the method of example 1. Yield 76% and nuclear magnetization are shown in figure 3.

Example 7: starting materials

Preparation: the product M7 was prepared from the starting material by the method of example 1. Yield 79% and nuclear magnetization are shown in fig. 4.

Example 8: raw materials

Preparation: the product M8 was prepared from the starting material by the method of example 3, 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 2, wherein Q is OBF₃And Li. The yield was 88%.

Example 10: starting materials

Preparation: the product M10 was prepared from the starting material by the method of example 4. Yield 86%, nuclear magnetization is shown in fig. 5.

Example 11: raw materials

Preparation: the product M11 was prepared from the starting material by the method of example 4, wherein Q is OBF₃And Li. The yield was 87%.

Example 12: raw materials

Preparation: the product M12 was prepared from the starting material by the method of example 1. Yield 79% and nuclear magnetization are shown in fig. 6.

Example 13: raw materials

Preparation: the product M13 was prepared from the starting material by the method of example 3, wherein Q is OBF₃And Li. The yield was 78%.

Example 14: starting materials

Preparation: the product M14 was prepared from the starting material by the method of example 2, wherein Q is OBF₃And Li. The yield was 87%.

Example 15: raw materials

Preparation: the product M15 was prepared from the starting material by the method of example 1. Yield 88%, nuclear magnetization is shown in fig. 7.

Example 16: starting materials

Preparation: the product M16 was prepared from the starting material by the method of example 3, wherein Q is OBF₃And Li. The yield was 82%.

Example 17: raw materials

Preparation: the product M17 was prepared from the starting material by the method of example 4. Yield 86%, nuclear magnetization is shown in fig. 8.

Example 18: raw materials

Preparation: the product M18 was prepared from the starting material by the method of example 1. The yield was 89%.

Example 19: raw materials

Preparation: the product M19 was prepared from the starting material by the method of example 2. Yield 83%, nuclear magnetization is shown in fig. 9.

Example 20: raw materials

Preparation: the procedure of example 3 was followed to produce M20 wherein Q is OBF₃And Li. The yield was 82%.

Example 21: raw materials

Preparation: the product M21 was prepared from the starting material by the method of example 1. Yield 77%, nuclear magnetization is shown in fig. 10.

Example 22: starting materials

Preparation: the product M22 was prepared from the starting material by the method of example 3. Yield 86%, nuclear magnetization is shown in fig. 11.

Example 23: raw materials

Preparation: the product M22 was prepared from the starting material by the method of example 3. Yield 76% and nuclear magnetization are shown in figure 12.

Example 24

The saturated heterocyclic boron trifluoride salt provided by the invention is mainly used as an additive in an electrolyte (including liquid and solid), 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 efficiency and the cycle performance of a battery are obviously improved. The performance of the present application is described below by way of tests.

(1) Positive pole piece

Adding the active substance of the main material of the positive electrode, the electronic conductive additive and the binder into a solvent according to the mass ratio of 95:2:3, wherein the solvent accounts for the mass of the total slurryThe amount fraction is 65%, and the positive electrode slurry with certain fluidity is obtained after uniform mixing and stirring; 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 is selected), lithium nickel cobalt aluminate (LiNi)_0.8Co_0.15Al_0.05O₂NCA for short), 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 systems

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) Preparation of electrolyte

M1-M23, organic solvent, conventional salt and conventional additives are mixed uniformly to obtain series electrolytes E1-E23, wherein the organic solvent is Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethylene Carbonate (EC) and Propylene Carbonate (PC). Namely, the conventional additives are fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), trimethyl phosphate (TMP), ethoxypentafluorocyclotriphosphazene (PFPN), and vinyl sulfate (DTD); the conventional salts are lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), bis (oxalato) borateLithium fluorosulfonylimide (LiFSI) and 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-M23 with blanks according to the proportion of E1-E23 (namely, not adding M1-M23), thus obtaining corresponding conventional electrolyte comparison samples L1-L23.

(4) Button cell assembly

Electrolyte series E1-E23 containing the structure of the embodiment as an additive and conventional electrolytes L1-L23 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, the diaphragm is a circular sheet with the diameter of 16.2mm, and is a commercial Al circular sheet₂O₃a/PE porous separator.

The battery systems prepared from E1 to E23 were batteries 1 to 23, respectively, and the battery systems prepared from L1 to L23 were comparative batteries 1 to 23, 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 23 and the comparative batteries 1 to 23 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 of example cell and comparative example cell

From the test results of the batteries in the above examples and comparative batteries, in the button battery, when the positive and negative electrode systems are the same, the first cycle efficiency, specific discharge capacity and capacity retention rate of the battery using the structure M1-M23 of the invention as an electrolyte additive are much better than those of the battery without the electrolyte additive, and the performance of the battery is superior to that of the conventional additive at present. In addition, the battery shows more excellent cycle performance using the boron trifluoride salt additive of the present application in the presence of conventional additives, showing a synergistic effect.

In addition, the application also shows the effect graph of some examples as additives. FIGS. 13-16 are graphs comparing the performance of battery 8/14/20/22 made with example 8/14/20/22 as an electrolyte additive to a corresponding comparative battery 8/14/20/22 that did not contain example 8/14/20/22 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 surface

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

The lines representing the cells of the comparative examples represent the cells of the comparative examples, and it can be seen that the lines representing the cells of the examples are all above the lines representing the cells of the comparative examples, and the cells of the examples have better effects.

In summary, the first cycle efficiency, specific discharge capacity, capacity retention rate, and other properties have a direct and significant impact on the overall performance of the battery, which directly determines whether the battery can be used. 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 25

For further study and understanding of the structural properties in the present application, the applicant evaluated the effect of the following 4 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 22 (i.e., M22), and the following 4 comparative example structures were structure W1, structure W2, structure W3, and structure W4, respectively.

The effects of W1-W4 and M22 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

Tables 5W 1 to W4, and liquid electrolytes S1 to S5 in which M22 was added as an additive

Wherein S0 is a control group.

(2) Button cell assembly

The obtained liquid electrolytes S0 to S5 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 embodiment 24, i.e., batteries Y0 to Y5, 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.

Watch 6 button cell assembling and testing mode

TABLE 7 test results of the batteries

The test results of the batteries Y0-Y5 show that the first efficiency, the 1-50-cycle discharge specific capacity and the capacity retention rate of the batteries can be improved by using the batteries W1-W4 and M22 as liquid electrolyte additives. However, compared with W1-W4, M22 has more obvious improvement on the first efficiency and first cycle specific discharge capacity of the battery, probably because W1 contains 1-OBF₃M, W2, W4 contain-BF₃And without lithium, -OLi in W3 compared to-OBF₃Li having a low degree of dissociation and containing three-OBF₃M22 of M contains a lithium source, and lithium ions extracted from the positive electrode are less consumed in the process of forming a good passivation layer, so that the first-effect and first-cycle discharge specific capacity and capacity retention rate of the battery are improved. The applicant is still in further research with a clearer and more clear mechanism. However, in 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 23 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 1-23, and other structures not shown can be prepared by the method described in any of examples 1-5. The manufacture thereofThe 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

The boron trifluoride salt prepared by the method has good effect, but only partial structural data are recorded 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.

In the present application, both of the above cases need to be satisfied, and if not, the properties of the present application are greatly different from those of the present application, so that the application scene or effect after the change is not well predicted, and may be greatly changed, and if valuable, the present inventors will make a special study 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 invention can be obtained by purchase or simple preparation, are extremely basic in the field of organic chemistry, have no difficulty, and therefore the raw material structure is conventional and is not within the protection scope of the 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 should 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

1. A ternary electrolyte comprising saturated heterocycles, characterized in that: the electrolyte comprises saturated heterocyclic boron trifluoride salt represented by the following general formula I:

in the general formula I above, the compound of formula I,

represents a saturated heterocyclic ring containing at least one heteroatom in the ring; the heteroatom is selected from S, N, O, P, Se, Ca, Al, B or Si; m is a metal cation;

E₄is a chain without or containing at least one atom;

-E₂-OBF₃m is connected to E₄Or a saturated heterocyclic ring

On 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 is a substituent, any one H on the substituent can be substituted by the substituent, and the substituent can be substituted by one H and can also be substituted by two or more H, if two or more H are substituted, the substituents can be the same or different.

2. The electrolyte of claim 1, wherein: in the general formula I, the saturated heterocyclic ring is a three-to twenty-membered ring;

preferably, in the formula I, with-OBF₃The atom to which M is directly bonded is a carbon atom C;

more preferably, the heteroatom is selected from S, N, O, P, B or Si;

h on any C in the general formula I can be independently substituted by halogen.

3. The electrolyte of claim 2, wherein: the substituent R is 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, cyclic substituents, salt substituents, and any of these groups wherein hydrogen H is substituted with a halogen atom; r₂And R₃Independently is H, hydrocarbyl or a ring;

wherein the ester group includes carboxylic acid esters, carbonic acid esters, sulfonic acid esters, and phosphoric acid esters; hydrocarbyl groups include alkyl, alkenyl, alkynyl, and alkenylalkynyl groups; heterohydrocarbyl is hydrocarbyl containing at least one non-carbon atom, including heteroalkyl, heteroalkenyl, heteroalkynyl, and heteroalkynynyl; the non-carbon atoms are selected from halogen, N, P, S, O, Se, Al, B and Si; the ring substituent comprises a ternary-eight-membered ring and a polycyclic ring formed by at least two monocyclic rings; such salt substituents include, but are not limited to, sulfate, sulfonate, sulfonimide salts, carbonate, thioether, oxoether, nitrogen, hydrochloride, nitrate, azide, silicate, phosphate;

preferably, the carbonyl group is

Amino is ═ N-R₂₁、

or-CH ═ N-R₈₁Amide is

Sulfonamide group of

The sulfoalkane is

Diazo is-N ═ N-R₁₆With an ether oxygen radical of-R₃₁OR₃₂The etherthio radical is-R₃₁SR₃₂(ii) a Wherein R is₂、R₃、R₁₆、R₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₃₁、R₃₂、R₄₀、R₄₁、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆、R₅₀、R₅₁、R₅₂、R₅₄、R₅₅、R₅₆、R₅₇、R₇₉、R₈₀、R₈₁Independently an alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, ring, or a group in which H on any one of these groups, C, is substituted with a halogen, a heteroalkane/alkene/alkynyl being an alkane/alkene/alkynyl containing at least one of the non-carbon atoms; and R is₂、R₃、R₁₆、R₂₁、R₂₃、R₂₅、R₄₀、R₄₁、R₄₂、R₇₉、R₈₀、R₈₁Can also be H, R₂₂、R₂₄、R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent; the group directly attached to N or O can also be a metal ion.

4. The electrolyte of claim 3, wherein: e₁、E₂Or E₃Selected from the group consisting of a carbonyl group, a carbonyl-containing group, an ester-containing group, an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, a group containing a cyclic structure, a substituted aryl group, a substituted heteroaryl,

Or ═ N-R₆-, said heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-carbon double bond C ═ N, R₄、R₅And R₆Independently of R in claim 3₂、R₃The species defined in (1) are identical;

E₄is a chain structure without or containing 3 free connecting bonds and at least one atom, the 3 free connecting bonds are respectively connected with a saturated heterocyclic ring and E₁And E₂And (4) connecting.

5. The electrolyte of claim 4, wherein: in the general formula I, the saturated heterocycle 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 and an eighteen-membered ring; preferably, the saturated heterocyclic 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 sixteen-membered ring and an eighteen-membered ring;

preferably, the three-membered ring: contains a heteroatom; a four-membered ring: containing 1 or 2 heteroatoms; five-membered ring: containing 1,2, 3 or 4 heteroatoms; a six-membered ring: containing 1,2, 3, 4, 5 or 6 heteroatoms; seven-, eight-, nine-membered rings: containing 1,2, 3 or 4 heteroatoms; ten-, twelve-, fourteen-membered rings: containing 1,2, 3, 4 or 5 heteroatoms; sixteen and eighteen membered rings: containing 1,2, 3, 4, 5 or 6 heteroatoms;

any one of the heteroatoms in each saturated heterocycle is independently selected from S, N, O, P, Se, B, or Si.

6. The electrolyte of claim 5, wherein: in formula I, the saturated heterocycle is selected from: a three-membered heterocyclic ring containing 1O, 1N or 1S, a four-membered heterocyclic ring containing 1O, 1S, 1N, 2O, 2N or 1N and 1O at the same time, a five-to eight-membered heterocyclic ring containing 1S, 1N, 1O, 1 Si, 1P, 2S, 2N, 2O, 3O, 1O and 1S at the same time, 1O and 1N at the same time, 1N and 1S at the same time, 1 Si and 1N at the same time, 1O and 1P at the same time, 1N and 1P at the same time, 2N and 1P at the same time, 3N and 3P at the same time, 2O and 1P at the same time, or 2O and 1 Si at the same time; a ten-to sixteen-membered heterocycle containing 1O, 1S, 1N, 3N, 4O, 4S, 4N, 5O or 5S, or an eighteen-membered heterocycle containing 5O, 5S, 6O, 6S or both 5O and 1N, in each of which there are two-OBFs₃M is directly or indirectly attached to any one or two heterocyclic ring atoms;

more preferably, the saturated heterocyclic ring includes, but is not limited to:

7. The electrolyte of claim 6, wherein: 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、E₃And E₄Independently of each other, as defined in any one of claims 1 to 4; any one H on each saturated heterocycle may be independently selected from A₁Or A₂Any one substituent of (A), A₁、A₂Are each independently selected from any one of the substituents defined in said substituent R in any one of claims 1-4.

8. The electrolyte of claim 7, wherein: in the substituent A₁、A₂Or in R, the halogen atoms comprise F, Cl, Br and I;

R₂、R₃independently H, methyl or ethyl; r₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₃₁、R₃₂、R₄₀、R₄₁、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆、R₅₀、R₅₁、R₅₂、R₅₄、R₅₅、R₅₆、R₅₇、R₇₉、R₈₀、R₈₁Independently an alkyl group containing 1-20 atoms, a heteroalkyl group containing 1-15 atoms, an alkenyl group containing 1-20 atoms, a heteroalkenyl group containing 1-15 atoms, or a CN containing group, and R₂₂、R₂₄、R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent, R₂₁、R₂₃、R₂₅、R₄₀、R₄₁、R₄₂、R₇₉、R₈₀、R₈₁Can also be H, R₂₂、R₂₄、R₃₁、R₄₄、R₄₅、R₅₀、R₅₅Can also be absent; the group directly attached to N or O can also be a metal ion; wherein the ester group can also be selected from-OCH₂COOEt or-CH₂(CH₂)₆COOEt; the amide can also be selected from

Or a fluorotolyl group; r₃₅Can also be selected from the group consisting of octyl, decyl, octadecyl, and-O- (CH)₂)₂CH(CH₃)₂(ii) a The carbonyl group can also be selected from the group consisting of-CO-CH (CH)₃)CH₂CH(CH₃)CH₂CH₃or-CO-CH (CH)₃)CH₂CH(CH₃)CCl₂CH₂Cl；

Diazo is-N ═ N-R₁₆，R₁₆Is phenyl or phenyl with methyl, halogen atom or nitro connected;

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, octadecyl; heteroalkyl is an alkyl group containing at least one of the heteroatoms;

the alkenyl group includes vinyl, 1-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;

alkynyl includes ethynyl, propynyl, butynyl, pentynyl, hexynyl, 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 ring substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and polycyclic;

preferably, any one of the H-bearing atoms on any one of the rings of the above-mentioned ring substituents is independently linked to a first substituent of the same type as defined for substituent R; more preferably, the first substituent is selected from the group consisting of H, halogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, fluoromethyl, fluoroethyl, methoxy, ethoxy, nitro, alkenyl, alkynyl, ester, sulfonate, sulfoalkane, amide, cyano, aldehyde, -SCH₃、-COOCH₃、COOCH₂CH₃、-OCF₃、＝O、-CO-N(CH₃)₂、

Or a substituent in which H on any one C of these groups is substituted with halogen; r₁₀Selected from methyl, ethyl or propyl;

any atom with H in any ring structure of the ring substituents of the ring may be independently linked to the saturated heterocycle via the following linking groups: single bond, methyl, ethyl, propyl, butyl, ethylene, propylene, butylene, acetylene, propyne, -COO-, -COCH₂-、COOCH₂CH₂-、-CH₂OCH₂-、-CH₂OCH₂CH₂-、-OCH₂CH₂O-、-OCH₂-、-OCH₂CH₂-、-N＝N-、-S-、-S-S-、-O-、-CH＝CH-COO-CH₂CH₂-、-CH₂OOC-、-CH＝CH-CO-、-CH₂N(CH₃)CH₂-、

Connecting; r₁₄Selected from H, methyl, ethyl or propyl, R₈₃Selected from alkyl or cyclic.

9. The electrolyte of claim 7, wherein: e₁、E₂And E₃Independently selected from the group consisting of none, carbonyl, keto, ester, -CH₂-, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, N-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ethenyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octenyl, nonenyl, decenyl, cyclohexyl, cyclopentyl, 1, 3-hexadienyl, -C ═ N-, -C (CH)₃)₂-、-CH(CH₃)-、-CH(CF₃)-、-C(CF₃)₂-、-CH₂CH₂CH(CH₃)-、-Z'₁CH₂CH₂-、-CH₂CH(CH₃)-、-OCH₂-、-CH＝CH-CO-、-OCH₂CH₂CH₂CO-、＝N-CH₂-CO-、-Z'₁CH₂CO-、-Z'₁CH₂CH₂CO-、-Z'₁CH₂CH₂CH₂CO-、-COOCH₂CH₂-、-CH(CH₃)CO-、-CH(CH₂Cl)-、-CH(OCH₃)-、-CH(CHO)-、-CH₂COCO-、-C(CH₃)₂CH₂CH₂-、-O-CH₂(CH₂)₄CH₂-、-CH₂CH₂CO-、-CH₂(CH₂)₅CO-、-N＝C(CH₃)-、-O-(CH₂)₆-、-CH₂Z'₁CH₂-、-CH₂(CH₃)Z'₁CH₂-、-CH₂CH₂Z'₁CH₂-、-CH₂CH(CH₃)Z'₁CH₂-、

-O-CH₂-CH₂-O-CH₂-CH₂-、

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

E₄Selected from among,

Wherein Z 'of claim'₁is-O-, -S-S-, -COO-,

-CS-, wherein R₁₁Is H, methyl, ethyl, propyl, isopropyl, butyl, ethoxy or methoxy, and the R is₁₁Any one of hydrogen and H in (1) can be replaced by F or Cl; r is₅₉、R₆₀Independently an alkyl group or a ring;

R₁₃、R₉₆independently selected from H, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, nitro, hexyl, thiazolyl, pyrrolyl, -CH (CH)₃)₂、-CH₂CH(CH₃)₂、-CH₂CH₂NO₃、-CH₂CH₂CH(CH₃)₂、

Wherein R is₉Is nothing, methylene, -CH (CH)₃)-Ph；R₈、R₁₂、R₁₇、R₁₈、R₃₅、R₈₅、R₉₄、R₉₅Independently selected from halogen atom, alkyl, fluoroalkyl, methoxyl, nitryl, aldehyde group, ketone group, ester group or-CH₂-N(CH₃)₂Optionally R being attached to thiazolyl, pyrrolyl or phenyl Ph₁₇Any one of them.

10. The electrolyte of claim 1, wherein: m of the formula I comprises Na⁺、K⁺、Li⁺、Mg²⁺Or Ca²⁺Preferably Na⁺、K⁺Or Li⁺；

Preferably, the general formula i is: a compound of formula i according to any one of claims 1-9 wherein H on any one C is substituted, wholly or partially, with halogen, preferably F.

11. A method for producing the electrolyte according to any one of claims 1 to 10, characterized in that: the method comprises the step of reacting a saturated heterocyclic ternary structure containing three-OH, a boron trifluoride compound and an M source to obtain a product, namely the product containing three-OBF₃M is a saturated heterocyclic boron trifluoride salt.

12. Use of the electrolyte of any one of claims 1 to 10 in a secondary battery, wherein: the application is as follows: the general formula I can be used as an electrolyte additive;

preferably, the application further comprises the application in a liquid electrolyte, a gel electrolyte, a mixed solid-liquid electrolyte, a quasi-solid electrolyte, an all-solid electrolyte, which each independently comprise a saturated heterocyclic boron trifluoride containing salt according to any one of claims 1 to 10;

preferably, the use further comprises use as a battery or battery, said battery comprising the saturated heterocyclic based ternary electrolyte of any of claims 1-10 and a positive electrode, a negative electrode, a separator and a packaging casing; 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.