CN114573612A - Ternary unsaturated carbocyclic boron trifluoride salt electrolyte and preparation method and application thereof - Google Patents

Ternary unsaturated carbocyclic boron trifluoride salt electrolyte and preparation method and application thereof Download PDF

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CN114573612A
CN114573612A CN202011376714.4A CN202011376714A CN114573612A CN 114573612 A CN114573612 A CN 114573612A CN 202011376714 A CN202011376714 A CN 202011376714A CN 114573612 A CN114573612 A CN 114573612A
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俞会根
杨萌
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Beijing WeLion New Energy Technology Co ltd
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Abstract

The invention relates to a ternary unsaturated carbocyclic boron trifluoride salt electrolyte, a preparation method and 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,
Figure DDA0002808368930000011
represents a carbocyclic ring containing at least one unsaturated bond on the ring; m is a metal cation; e4Is a chain without or containing at least one atom; -E2‑OBF3M is connected to E4Or unsaturated carbocyclic rings
Figure DDA0002808368930000012
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, and can also be used as a single-ion conductor and a high-molecular framework after polymerization of a polymerizable monomer. The electrolyte can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, and has good effect.
Figure DDA0002808368930000013

Description

Ternary unsaturated carbocyclic boron trifluoride salt electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a ternary unsaturated carbocyclic boron trifluoride salt electrolyte 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 film or a polypropylene porous film; 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 electrochemical window of the carbonate and ether solvents is narrow, and the solvents are easily oxidized and decomposed by high-voltage anode materials, so that the gas generation is serious, the liquid electrolyte is gradually consumed and dried, and the battery is rapidly disabled. 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. The development of single-ion conductor polymer electrolyte with higher conductivity, wide electrochemical window and high ion migration number is also very important.
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, the resistance is greatly increased, the time cost and the economic cost are possibly greatly consumed, and the result is not well predicted, so that the research team only 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 an unsaturated carbocyclic ring was independently studied. This is because the chemical properties such as electrical properties of unsaturated bonds themselves are also peculiar, and when they exist on a ring, they affect the chemical and physical properties of the whole ring, and they are substantially different from heterocyclic rings, aromatic rings, chain structures, and the like, so that the relationship or the recyclability between them is uncertain. Thus, the linkage of-OBF to the unsaturated carbocyclic ring3M, different structures may be generatedEffect, in particular connecting three-OBFs3M, it may have a more unexpected superior effect. The subject of the present application is therefore identified as a direct or indirect linkage of-O-BF to an unsaturated carbocyclic ring3M, i.e., independent study of the main ring body from aromatic ring and heterocyclic ring, etc., to more specifically determine-O-BF3The specific case when M is attached to an unsaturated carbocyclic ring.
Disclosure of Invention
The invention provides a ternary unsaturated carbon ring boron trifluoride salt 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:
an aspect of the present invention is to provide a ternary unsaturated carbocyclic boron trifluoride salt electrolyte, which includes an unsaturated carbocyclic boron trifluoride salt represented by the following general formula I:
Figure BDA0002808368910000021
in the general formula I above, the compound of formula I,
Figure BDA0002808368910000022
represents a carbocyclic ring containing at least one unsaturated bond on the ring; 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 unsaturated carbocyclic rings
Figure BDA0002808368910000023
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 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 substituent can be the same or can be substituted by two or more HIn contrast, each H may be substituted with a substituent defined for any one of R.
Further, in the general formula I, the unsaturated carbocyclic ring is a three-to twenty-membered ring.
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-OBF3The atom to which M is directly attached is a carbon atom C. Preferably, in two of the formula I-OBF3In M, at least one is attached to a carbon atom other than the carbonyl carbon, which includes-C ═ O or-C ═ S.
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, the substituent R is selected from H, a halogen atom, a carbonyl group, an ester group, an aldehyde group, an ether oxy group, an ether thio group, ═ O, ═ S, and,
Figure BDA0002808368910000038
Nitro, cyano, amino, amide, sulfonamide, sulfoalkane, hydrazino, diazo, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenylalkynyl, heteroalkynyl, cyclic substituent, salt substituent, and a group in which any one hydrogen H in these groups is substituted with a halogen atom; wherein the ester group includes carboxylate, carbonate, sulfonate and phosphate, R2、R3Independently H, hydrocarbyl, heterohydrocarbyl or cyclic.
Preferably, any one of the structures of heterohydrocarbyl, heteroalkyl, heteroalkenyl, heteroalkynyl, and heteroalkynynyl contains at least one heteroatom selected from the group consisting of 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, carbonate, carboxylate, thioether, oxoether, nitronium, hydrochloride, nitrate, azide, silicate, phosphate.
Preferably, the carbonyl group is-R10COR11The ester group is-R12COOR13、-R12OCOR17、-R12SO2OR13、R12O-CO-OR13Or
Figure BDA0002808368910000031
The ether oxygen radical is-R14OR15The etherthio radical is-R14SR15(ii) a The sulfoalkane is-R18SO2R19Amino is ═ N-R20、
Figure BDA0002808368910000032
or-CH ═ N-R24Amide is
Figure BDA0002808368910000033
Sulfonamide group of
Figure BDA0002808368910000035
Wherein R is2、R3、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 an alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenynyl, ring or a group in which H on any one of these groups on C is replaced by halogen, a heteroalkyl/alkene/alkynyl being an alkane/alkene/alkynyl group bearing at least one of the heteroatoms; and R is2、R3、R10、R12、R14、R18、R20、R21、R22、R23、R24、R25、R26、R27、R29、R30、R31、R32、R33、R35May independently be H or none; the group directly attached to N or O can also be a metal ion, such as R13、R15、R16、R22、R26、R30、R31、R35Etc. can 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,
Figure BDA0002808368910000037
Or ═ N-R6-, 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, 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 ring and E1And E2Is connected, if E1And/or E2If not, then E4Free connecting key of and-OBF3And M is connected.
Further, in the general formula i, the unsaturated carbocyclic 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, and a twelve-membered ring. Preferably, the unsaturated carbocyclic ring includes, but is not limited to, the following rings: cyclopropene, cyclobutene, cyclobutadiene, cyclopentene, cyclopentadiene, cyclohexene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, cycloheptene, 1, 3-cycloheptadiene, 1, 4-cycloheptadiene, cycloheptatriene, cyclooctene, 1, 3-cyclooctadiene, 1, 4-cyclooctadiene, 1, 5-cyclooctadiene, 1,3, 5-cyclooctatriene, 1,3, 6-cyclooctatriene, cyclooctatetraene, cyclononene, cyclononadiene, cyclononatetraene, cyclodecene. Any one H of the unsaturated carbons described in this paragraph can be independently substituted with the substituent.
Further, the general formula i includes, but is not limited to, the following compounds:
Figure BDA0002808368910000041
Figure BDA0002808368910000042
in the above structure, Q1、Q2、Q3All indicate-OBF3M; e in each ring structure1、E2、E3And E4Independently in accordance with any of the above definitions; any one H on each unsaturated carbocyclic ring may be independently selected from A1Any one substituent of (A), A1Selected from any one of the substituents defined in said substituent R in any one of the above paragraphs.
Further, in the substituent A1Or in R, the halogen atoms comprise F, Cl, Br and I.
R2、R3、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 a hydrocarbyl group of 1 to 18 atoms including alkyl, heteroalkyl, alkenyl, heteroalkenyl, and heteroalkynyl, the heteroalkyl, heteroalkenyl, or heteroalkynyl being an alkyl or alkenyl group bearing at least one heteroatom; and R is2、R3、R10、R12、R14、R18、R20、R21、R22、R23、R24、R25、R26、R27、R29、R30、R31、R32、R33、R35Can independently beH or none.
Cyano radicals selected from-CN, -CH2CN、-SCH2CH2CN 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、
Figure BDA0002808368910000051
Or
Figure BDA0002808368910000052
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、
Figure BDA0002808368910000053
Or
Figure BDA0002808368910000054
Etc. are in the category of alkenyl; heteroalkenyl is alkenyl containing at least one of the heteroatoms, preferably the heteroalkenyl 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、
Figure BDA0002808368910000056
The alkynyl group comprises ethynyl, propynyl, butynyl, pentynyl, hexynyl or heptynyl; heteroalkynyl is alkynyl containing at least one of said heteroatoms, preferably said heteroalkynyl comprises-C ≡ CCH2CH2CH2Z1CH2CH3、-C≡CCH2Z1CH2CH3or-C.ident.C-Si (CH)3)3(ii) a Alkenylalkynyl is a structure containing at least one double bond and at least one triple bond, preferably said alkenylalkynyl is selected from: -C ≡ CCH ═ CHCH3or-C ≡ CCH2CH2CH＝CHCH3(ii) a Heteroalkynyls are alkynyls 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 groups, preferably the cyclic substituents are selected from the group consisting of cyclopropyl, oxirane, thiirane, cycloazethane, cyclopropene, cyclobutylalkyl, cyclobutylheteroalkyl (e.g. as in
Figure BDA0002808368910000057
Etc.), cyclobutenyl, cyclobutadienyl, phenyl, pyridine, pyrimidine, cyclopentyl, cyclopentenyl, cyclopentadienyl, pyrrolyl, dihydropyrrolyl, tetrahydropyrryl, furyl, dihydrofuran, tetrahydrofuran, thiophene, dihydrothiophene, tetrahydrothiophene, imidazolyl, thiazolyl, dihydrothiazolyl, tetrahydrothiazolyl, isothiazolyl, dihydroisothiazolyl, tetrahydroisooxazolyl, pyrazolyl, oxazole, dihydrooxazolyl, tetrahydrooxazolyl, isoxazole, dihydroisoxazolyl, 1, 3-dioxolane, triazolyl, cyclohexyl, cyclohexenePhenyl, cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, morpholine, piperazine, pyrone, pyridazine, pyrazine, triazine, dihydropyridine, tetrahydropyridine, dihydropyrimidine, tetrahydropyridine, thiopyran, dihydrothiopyran
Figure BDA0002808368910000061
Tetrahydrothiopyrans, dithianes
Figure BDA0002808368910000062
1, 2-dithianes
Figure BDA0002808368910000063
1, 4-dithianes, oxazolidines (e.g. [1,3 ]]Oxazolidines
Figure BDA0002808368910000064
) P-diazabenzene, biphenyl, naphthyl, anthryl, phenanthryl, quinonyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, basil, benzoxazole, pyrenyl, acenaphthenyl, naphthoyl, phenanthryl, quinonyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, and acenaphthyl,
Figure BDA0002808368910000065
Figure BDA0002808368910000066
Wherein Z is1Selected from O, S, -S-S-, -CO-, -COO-or
Figure BDA0002808368910000067
Wherein R is36、R90、R91、R92Independently selected from H, methyl, ethyl, propyl, isopropyl, butyl, fluoromethyl, fluoroethyl, methoxy, ethenyl, propenyl, or metal ions.
Any one ring of the ring substituents is independently linked to the substituted unsaturated carbocyclic ring through any one of the following linking groups: -CH2-、-CH2CH2-, propyl, 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-、
Figure BDA0002808368910000068
Or a single bond, i.e. a direct ring-to-ring connection, R42Independently selected from H, methyl, ethyl, propyl or a metal ion, 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;
Figure BDA0002808368910000069
and
Figure BDA00028083689100000610
independently a monocyclic ring or a polycyclic ring composed of at least two monocyclic rings, preferably, the monocyclic ring may be a 3-8 membered ring which may be a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, the polycyclic ring may be a fused ring, a bridged ring or a spiro ring, more preferably,
Figure BDA0002808368910000071
and
Figure BDA0002808368910000072
independently is 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, cyclopentenyl, furan, thiophene, pyrrole, dihydro/tetrahydrothiophene, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrimidine, piperidine, 1, 3-dioxacycloalkane, imidazole, pyrazine, pyridazine, triazine, cyclohexane, cyclohexenyl, and the like,A cycloheptyl group.
The first substituent can be connected to any one atom with H on any one ring of the ring substituents and is selected from H, halogen atoms, 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、＝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-、
Figure BDA0002808368910000073
-O-CH2-CH2-O-CH2-CH2-、
Figure BDA0002808368910000074
Figure BDA0002808368910000075
Figure BDA0002808368910000076
-(CH3)CHCH2CH2Z’1CH2-、-O-CH(CH3)-(CH2)4CH2-、
Figure BDA0002808368910000077
Figure BDA0002808368910000078
E4Selected from among,
Figure BDA0002808368910000079
Figure BDA00028083689100000710
Figure BDA0002808368910000081
Figure BDA0002808368910000082
Wherein, Z 'is more than'1is-O-, -S-S-, -COO-,
Figure BDA0002808368910000083
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; r is39、R50Independently selected from H, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, nitro, hexyl, thiazole, -CH (CH)3)2、-CH2CH(CH3)2、-CH2CH2NO3、
Figure BDA0002808368910000084
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, amino, fluoromethyl, fluoroethyl or-CH2-N(CH3)2；R37Selected from halogen atom, alkyl, fluoroalkyl, methoxy, nitro, amino, aldehyde group, ketone group or ester group.
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.
It is another object of the present invention to provide a method for preparing an electrolyte according to any of the above paragraphs, which comprises reacting an unsaturated carbocyclic ternary structure containing three-OH groups, a boron trifluoride compound and a source of M to obtain a product containing three-OBF groups3Unsaturated carbocyclic boron trifluoride of MSalts, i.e. of formula I.
Another aspect of the present invention is to provide an application of the unsaturated carbon ring type boron trifluoride salt electrolyte as described in any one of the above paragraphs in a secondary battery, wherein the application is: the general formula I can be used as an additive, and the polymerizable monomer in the general formula I can also be used as a single-ion conductor and polymer framework after being polymerized.
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 an unsaturated carbocyclic boron trifluoride salt as described in any of the above paragraphs.
The present invention also provides a polymer electrolyte for use in a battery, which is obtained by polymerizing a polymerizable unsaturated carbocyclic boron trifluoride salt of the general formula I as described in any of the above paragraphs, and which is used as a polymer electrolyte for use in a battery after polymerization.
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 unsaturated carbon ring type boron trifluoride salt electrolyte 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 unsaturated carbon ring type boron trifluoride salt electrolyte as described in any one of the above paragraphs, a positive electrode, a negative electrode, a diaphragm 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.
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.
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 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 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 electrolyte structure in the application is a polymerizable cycloolefin functional group structure, so that the electrolyte can be used as a monomer of a single-ion conductor polymer electrolyte, can be polymerized in situ into a single-ion conductor to be assembled into a battery for use, and can also be applied to the battery to be polymerized in situ to form a quasi-solid or all-solid battery for use.
Also in this application, the salt (e.g., lithium/sodium salt) is not addedNext, the polymer electrolyte polymerized as a monomer according to the present application still has good effects, and after the conventional salt is additionally added, the battery exhibits more excellent electrochemical properties due to the increased amount of dissociated ions. Thus, the present application contains 3-OBFs3When the structure of M is used, the salt property of M and the property of a polymerized monomer serving as a polymer electrolyte can well act synergistically, namely the multiple effects of M can act synergistically, and the structure is good in effect and great in significance.
3. 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).
4. The method 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 method has great significance.
Drawings
FIGS. 1-9 are nuclear magnetic hydrogen spectra of products of some embodiments of the invention;
FIGS. 10-13 are graphs of the cycling effect of boron trifluoride salts as electrolyte additives according to the present application;
fig. 14 to 15 are graphs showing the effect of room temperature cycle of a boron trifluoride salt as a polymer electrolyte after polymerization.
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, -OBF3The number of (c) is increased correspondingly so that it exactly matches the valence of M.
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
Figure BDA0002808368910000091
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 unsaturated carbocyclic ring 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 the n-butyl group has only one linkage at the terminus, then the other linkage can be located on any of the 4 carbon atoms in the n-butyl group.
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
Figure BDA0002808368910000101
Represents that any H on the ring can be independentA is a substituted group 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
Figure BDA0002808368910000102
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
Figure BDA0002808368910000103
-CH(CH3) -is of
Figure BDA0002808368910000104
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、E2Etc., which have 2 connecting bonds.
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 which can be used as an electrolyte additive and a polymeric monomer in a polymer electrolyte, namely, the ternary organic boron trifluoride salt contains three-OBF3M is a group in which M is 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 raw material, boron trifluoride compounds and M source are obtained by reactionthe-OH in the 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
Figure BDA0002808368910000111
M1
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 of ethanol, slowly adding the mixture into the intermediate, stirring at 45 ℃ for reaction for 8 hours, drying the obtained mixed solution under reduced pressure at 45 ℃ and under the vacuum degree of-0.1 MPa, washing the obtained solid with n-butyl ether three times, filtering and drying to obtain a product M1. The yield was 86%.
Example 2: raw materials
Figure BDA0002808368910000112
M2
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 THF (tetrahydrofuran) 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. 18.80ml of butyllithium in hexane (c: 1.6mol/L) was added to the intermediate, and the mixture was stirred at room temperature for 6 hours, and the resulting mixture was dried under reduced pressure at 40 ℃ under a vacuum of about-0.1 MPa to obtain a crude product, which was washed 3 times with cyclohexane, filtered and dried to obtain M2. The yield was 89%, and the nuclear magnetization is shown in FIG. 1.
Example 3: raw materials
Figure BDA0002808368910000113
M3
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 15ml THF (tetrahydrofuran) were added to the intermediate, the reaction was stirred at room temperature for 6 hours, the resulting mixture was dried under reduced pressure at 40 ℃ under a vacuum degree of about-0.1 MPa, and the resulting solid was washed three times with isopropyl ether, filtered, and dried to give product M3. The yield was 93%.
Example 4: raw materials
Figure BDA0002808368910000114
M4
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. 18.75ml of a butyl lithium hexane solution (c ═ 1.6mol/L) was added to the intermediate, the reaction was stirred at room temperature for 6 hours, the resulting mixture was dried under reduced pressure at 30 ℃ under a vacuum degree of about-0.1 MPa, and the resulting crude product was washed with n-hexane 3 times, filtered and dried to obtain M4. The yield was 87%, and the nuclear magnetization is shown in FIG. 2.
Example 5: raw materials
Figure BDA0002808368910000121
M5
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 M6 is obtained after filtration and drying. The yield was 88%, and the nuclear magnetization is shown in FIG. 3.
Example 6: raw materials
Figure BDA0002808368910000122
M6
Preparation: the product M6 was prepared from the starting material by the method of example 3, wherein Q is OBF3And Li. The yield was 89%.
Example 7: raw materials
Figure BDA0002808368910000123
M7
Preparation: the product M7 was prepared from the starting material by the method of example 2, wherein Q is OBF3And Li. The yield was 79%.
Example 8: raw materials
Figure BDA0002808368910000124
M8
Preparation: the product M8 was prepared from the starting material by the method of example 1, wherein Q was OBF3And Li. The yield was 87%.
Example 9: raw materials
Figure BDA0002808368910000125
M9
Preparation: the product M9 was prepared from the starting material by the method of example 4, wherein Q is OBF3And Li. The yield was 86%.
Example 10: raw materials
Figure BDA0002808368910000126
M10
Preparation: the product M10 was prepared from the starting material by the method of example 3. Yield 83%, nuclear magnetization is shown in fig. 4.
Example 11: raw materials
Figure BDA0002808368910000127
M11
Preparation: the product M11 was prepared from the starting material by the method of example 2, wherein Q is OBF3And Li. The yield was 79%.
Example 12: raw materials
Figure BDA0002808368910000131
M12
Preparation: the product M12 was prepared from the starting material by the method of example 1, wherein Q is OBF3And Li. The yield was 82%.
Example 13: raw materials
Figure BDA0002808368910000132
M13
Preparation: the procedure of example 4 was followed to produce M13 wherein Q is OBF3And Li. Yield 86%, nmr is shown in figure 5.
Example 14: starting materials
Figure BDA0002808368910000133
M14
Preparation: the product M14 was prepared from the starting material by the method of example 3, wherein Q is OBF3And Li. Yield 83%, nuclear magnetization is shown in fig. 6.
Example 15: raw materials
Figure BDA0002808368910000134
M15
Preparation: the product M15 was prepared from the starting material by the method of example 3, wherein Q is OBF3And Li. The yield was 79%.
Example 16: raw materials
Figure BDA0002808368910000135
M16
Preparation: the product M16 was prepared from the starting material by the method of example 4, wherein Q is OBF3And Li. Yield 82%, nuclear magnetization is shown in fig. 7.
Example 17: raw materials
Figure BDA0002808368910000136
M17
Preparation: the product M17 was prepared from the starting material by the method of example 4, wherein Q is OBF3And Li. The yield was 86%.
Example 18: raw materials
Figure BDA0002808368910000137
M18
Preparation: the preparation of the product M18, in which Q is O, from the starting materials was carried out as in example 1BF3And Li. Yield 89%, nuclear magnetization is shown in fig. 8.
Example 19: raw materials
Figure BDA0002808368910000138
M19
Preparation: the product M19 was prepared from the starting material by the method of example 2, wherein Q is OBF3And Li. Yield 84%, nuclear magnetization is shown in fig. 9.
Example 20
The ternary unsaturated carbocyclic boron trifluoride salt protected in the invention mainly plays two roles: 1. the use as an additive in electrolytes (both in liquid and solid states) primarily serves to create a stable passivation layer, and in addition to having ions that can dissociate themselves, there is less consumption of ions from the electrodes during formation of the passivation layer, thus significantly improving the first pass and cycling performance of the battery. 2. The structure of the application contains a double-bond structure, and the double-bond structure can initiate polymerization to form a single-ion conductor polymer electrolyte which is applied to gel batteries and all-solid batteries. The properties of the present application are tested below.
Firstly, as liquid electrolyte additive
(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)0.8Co0.15Al0.05O2Abbreviated NCA) and lithium nickel manganese oxide (LiNi)0.5Mn1.5O4Abbreviated LNMO), Na0.9[Cu0.22Fe0.3Mn0.48]O2(NCFMO for short), carbon nano-tube (CNT) and Super P are selected as the electronic conductive additive, polyvinylidene fluoride (PVDF) is used as the binder, and N-methyl pyrrole is used as the solventAlkanone (NMP).
(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 Cathode 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-M19, an organic solvent, a conventional salt and a conventional additive are uniformly mixed to obtain series electrolytes E1-E19, wherein the used 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); 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
Figure BDA0002808368910000141
Figure BDA0002808368910000151
Note: 1M means 1 mol/L.
Comparison sample: and replacing M1-M19 with blanks according to the proportion of E1-E19 (namely, not adding M1-M19), thus obtaining corresponding conventional electrolyte comparison samples L1-L19.
(4) Button cell assembly
Electrolyte series E1-E19 containing the structure of the embodiment as an additive and conventional electrolytes L1-L19 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-E19 are batteries 1-19, respectively, and the battery systems prepared from L1-L19 are comparative batteries 1-19, 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 19 and the comparative batteries 1 to 19 at room temperature are shown in table 4.
Table 3 configuration and test mode of example and comparative example batteries
Figure BDA0002808368910000152
Figure BDA0002808368910000161
Table 4 comparison of test results of example cell and comparative example cell
Figure BDA0002808368910000162
Figure BDA0002808368910000171
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 lithium/sodium battery using the structure M1-M19 as the electrolyte additive has better first-cycle efficiency, discharge specific capacity and capacity retention rate than the lithium/sodium battery without the electrolyte additive, and the performance of the lithium/sodium battery is superior to that of the conventional additive at present. In addition, the boron trifluoride salt additive in the application has a synergistic effect in the presence of conventional additives, and the battery shows more excellent electrochemical performance.
Di-single ion conductor polymer electrolyte
(1) Preparation of electrolyte
Monomers (compounds M2-M11, M17-M18 in the embodiment of the application), a plasticizer, a battery additive, a lithium salt and an initiator are uniformly stirred to form a precursor solution, and precursors S2-S11 and S17-S18 are obtained, wherein the specific preparation ratio is shown in Table 5. Wherein S2, S3, S4 and S18 are prepared into polymer electrolyte by ring-opening polymerization, and the used initiator is mainly lithium salt and stannous isooctanoate (Sn (Oct)2) (ii) a S5, S6, S7, S8, S9, S10, S11 and S17 are used for preparing the polymer electrolyte through free radical polymerization, and the initiator used is Azobisisobutyronitrile (AIBN) or Benzoyl Peroxide (BPO).
TABLE 5 precursor solution composition
Figure BDA0002808368910000172
(2) Battery assembly
From the electrolyte precursor solutions S2 to S11 and S17 to S18 obtained in table 5, pouch batteries of an a2 system, i.e., batteries (i.e., example batteries) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 17, and 18, were assembled from these precursors, respectively; the method comprises the following specific steps: assembling NCM811 anode pole piece with size of 64mm multiplied by 45mm, SiOC450 cathode pole piece with size of 65mm multiplied by 46mm and diaphragm into a 2Ah soft package battery core, and performing lamination, baking, liquid injection and formation processes to obtain a secondary battery and a battery assembling systemFor A2, the separator used commercial PE/Al2O3A porous membrane.
(3) Battery testing
After the secondary batteries prepared in examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 17 and 18 were completely cured, the first-cycle discharge capacity, the first-cycle efficiency and the capacity retention rate after 50-cycle of the batteries were tested at room temperature, and the test voltage ranges from 3.0V to 4.2V, wherein the cycle modes are 0.1C/0.1C 2 cycle and 0.3C/0.3C 48 cycle (C represents the rate), and the test results are shown in table 6
Table 6 test results of the batteries of the examples
Figure BDA0002808368910000181
As shown in table 6, it is found from the test data in the example battery that the precursors S2 to S11 and S17 to S18, which are composed of the polymerizable monomers M2 to M11 and M17 to M18, are in-situ cured to serve as the polymer electrolyte, and in the solid-state battery system in which NCM811 is the positive electrode and silicon oxycarbide (SiOC450) is the negative electrode, the electrochemical performance is very excellent, and the first-pass discharge capacity, the first-week discharge capacity and the capacity retention rate are relatively high. Examples 2, 6, 9, 10, and 18 (as shown in table 5, no conventional salt was added to the system) resulted in solid electrolytes with excellent performance after polymerization, and further, when additionally used in combination with conventional salt, the batteries exhibited more excellent electrochemical performance due to the increased amount of dissociated ions.
In addition, the application also shows the effect graph of some embodiments as additives and polymer electrolytes. FIGS. 10-13 are graphs comparing the performance of battery 4/5/13/16 made with example 4/5/13/16 as an electrolyte additive to a corresponding comparative battery 4/5/13/16 that did not contain example 4/5/13/16 of the present invention. Fig. 14 and 15 are views showing effects of the battery 4 and the battery 9 manufactured as a polymer electrolyte after polymerization of the monomers in examples 4 and 9. The figures also show that the structure of the application has excellent effect. In addition, in the cycle chart, there are small squares on the top
Figure BDA0002808368910000182
The lines of (A) represent the cells of the examples, with small circles
Figure BDA0002808368910000183
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.
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. In addition, the polymer electrolyte can be used as a monomer in a single-ion conductor polymer electrolyte. 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 21:
for further study and understanding of the structural properties in the present application, the applicant evaluated the effect of the following 3 structures on the long cycle performance of the battery at room temperature as liquid electrolyte additives, respectively. The structure of the present application was selected from the structure in example 4 (i.e., M4), and the following 3 comparative example structures were structure W1, structure W2, and structure W3, respectively.
Figure BDA0002808368910000191
(1) Liquid electrolyte configuration
TABLE 7 electrolytes S1 to S4 prepared from W1 to W3 and M4 as additives
Figure BDA0002808368910000192
Wherein S0 is a control group.
(2) Button cell assembly
The obtained liquid electrolytes S0 to S4 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 cells shown in "one" of embodiment 20, i.e., batteries Y0 to Y4, respectively. The specific configuration, cycling profile and voltage range of the cell are shown in table 8, and the test results are shown in table 9.
Watch 8 button cell assembling and testing mode
Figure BDA0002808368910000193
TABLE 9 test results for batteries
Figure BDA0002808368910000194
Figure BDA0002808368910000201
The test results of the batteries Y0-Y4 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-W3 and M4 as liquid electrolyte additives. However, compared with W1-W3, M4 has more obvious improvement on the first efficiency and first cycle specific discharge capacity of the battery, probably because W1-W2 contain 1-OBF3M, W3 contains 2-NBFs3And does not contain lithium ions and contains 3-OBF3M4 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. I.e., boron trifluoride organic salts in the present application, in an electrolyteWhen the electrolyte is used, the electrolyte has the properties of both the additive and the salt, and the electrolyte can act synergistically with the electrolyte, so that the electrolyte has better effect than other components. The applicant is still in further research with a clearer and more clear mechanism. However, it is certain that, in any case, -OBF3The presence and amount of M has a substantial effect on battery performance.
In the present invention, the structures in examples 1 to 19 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 1-19, 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
Figure BDA0002808368910000202
Figure BDA0002808368910000203
Figure BDA0002808368910000204
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 connected with N, S or other atoms, or O is positioned on a ring (or O is also connected with other two groups), the structure is greatly different from the structure, therefore, whether the structure can be applied to the electrolyte of the application, what effect and application scene do not existThe inventors therefore conducted separate studies on these structures and do not go through 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.
In addition, the raw materials in the examples of the present application are all available as they are or through simple and conventional synthesis, and the synthesis of the raw materials or the raw materials does not have any innovation and is out of the scope of the present invention, so that the description is not excessive.
In the present invention, the applicant has performed a very large 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 certain errors in different tests.
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 (11)

1. A ternary unsaturated carbocyclic boron trifluoride salt electrolyte, characterized in that: the electrolyte comprises unsaturated carbon-ring boron trifluoride represented by the following general formula I:
Figure FDA0002808368900000011
in the general formula I above, the compound has the following structure,
Figure FDA0002808368900000012
represents an unsaturated carbocyclic ring containing at least one unsaturated bond on the ring; m is a metal cation;
E4is a chain of none or at least one atom;
-E2-OBF3m is connected to E4Or unsaturated carbocyclic rings
Figure FDA0002808368900000013
To any one atom of (a);
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 unsaturated carbocycle is a three-to twenty-membered ring;
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-OBF3The atom to which M is directly bonded is a carbon atom C;
preferably, H on any one C in said formula i may 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,
Figure FDA0002808368900000018
Nitro, cyano, amino, amide, sulfonamide, sulfoalkane, hydrazino, diazo, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenylalkynyl, heteroalkynyl, cyclic substituent,Salt substituents and groups in which any one of hydrogen and H in these groups is substituted with a halogen atom; wherein the ester group includes carboxylate, carbonate, sulfonate and phosphate, R2、R3Independently is H, hydrocarbyl, heterohydrocarbyl or cyclic;
preferably, any one of the structures heterohydrocarbyl, heteroalkyl, heteroalkenyl, heteroalkynyl, and heteroalkynynyl contains at least one heteroatom selected from the group consisting of 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, carboxylate, thioether, oxoether, nitrogen, hydrochloride, nitrate, azide, silicate, phosphate;
the carbonyl group is-R10COR11The ester group is-R12COOR13、-R12OCOR17、-R12SO2OR13、R12O-CO-OR13Or
Figure FDA0002808368900000014
The ether oxygen radical is-R14OR15The etherthio group being-R14SR15(ii) a The sulfoalkane is-R18SO2R19Amino is ═ N-R20、
Figure FDA0002808368900000015
or-CH ═ N-R24Amide is
Figure FDA0002808368900000016
Sulfonamide group of
Figure FDA0002808368900000017
Wherein R is2、R3、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 an alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkenynyl, ring or a group in which H on any one of these groups on C is replaced by halogen, a heteroalkyl/alkene/alkynyl being an alkane/alkene/alkynyl group bearing at least one of the heteroatoms; and R is2、R3、R10、R12、R14、R18、R20、R21、R22、R23、R24、R25、R26、R27、R29、R30、R31、R32、R33、R35May independently be H or 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,
Figure FDA0002808368900000021
Or ═ N-R6-, 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, R4、R5And R6Independently of R in claim 32、R3The species defined in (1) are consistent;
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 ring and E1And E2And (4) connecting.
5. The electrolyte of claim 4, wherein: in the general formula I, the unsaturated carbocyclic 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 and a twelve-membered ring;
preferably, the unsaturated carbocyclic ring includes, but is not limited to, the following rings: cyclopropene, cyclobutene, cyclobutadiene, cyclopentene, cyclopentadiene, cyclohexene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, cycloheptene, 1, 3-cycloheptadiene, 1, 4-cycloheptadiene, cycloheptatriene, cyclooctene, 1, 3-cyclooctadiene, 1, 4-cyclooctadiene, 1, 5-cyclooctadiene, 1,3, 5-cyclooctatriene, 1,3, 6-cyclooctatriene, cyclooctatetraene, cyclononene, cyclononadiene, cyclononatetraene, cyclodecene;
any one of the above-mentioned unsaturated carbons, H, may be independently substituted with the substituent.
6. The electrolyte of claim 5, wherein: the general formula I includes, but is not limited to, the following compounds:
Figure FDA0002808368900000022
Figure FDA0002808368900000031
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 5; any one H on each unsaturated carbocyclic ring may be independently selected from A1Any one substituent of (A), A1Selected from any one of the substituents defined in said substituent R in any one of claims 1 to 5.
7. The electrolyte of any one of claims 3-6, wherein: in the substituent A1Or in R, the halogen atom includes F, Cl, Br、I；
R2、R3、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 a hydrocarbyl group of 1 to 18 atoms including alkyl, heteroalkyl, alkenyl, heteroalkenyl, and heteroalkynyl, the heteroalkyl, heteroalkenyl, or heteroalkynyl being an alkyl or alkenyl group bearing at least one heteroatom; and R is2、R3、R10、R12、R14、R18、R20、R21、R22、R23、R24、R25、R26、R27、R29、R30、R31、R32、R33、R35Can independently be H or none;
cyano radicals selected from-CN, -CH2CN、-SCH2CH2CN 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, 1, 3-hexadienyl; 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 ring substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and polycyclic;
preferably, any one ring of the ring substituents is independently linked to the substituted unsaturated carbocyclic ring through any one of the following linking groups: -CH2-、-CH2CH2-, propyl, 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-、
Figure FDA0002808368900000032
Figure FDA0002808368900000033
Or a single bond, R42Independently selected from H, methyl, ethyl, propyl or a metal ion, R83Selected from alkyl or cyclic;
the first substituent can be connected to any one atom with H on any one ring of the ring substituents and is selected from H, halogen atoms, 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、＝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.
8. The electrolyte of any one of claims 1-6, 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-、
Figure FDA0002808368900000041
Figure FDA0002808368900000042
-O-CH2-CH2-O-CH2-CH2-、
Figure FDA0002808368900000043
Figure FDA0002808368900000044
Figure FDA0002808368900000045
-(CH3)CHCH2CH2Z’1CH2-、-O-CH(CH3)-(CH2)4CH2-、
Figure FDA0002808368900000046
E4Selected from among,
Figure FDA0002808368900000047
Figure FDA0002808368900000048
Figure FDA0002808368900000051
Wherein Z 'of claim'1is-O-, -S-S-, -COO-,
Figure FDA0002808368900000052
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、
Figure FDA0002808368900000053
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, amino, fluoromethyl, fluoroethyl or-CH2-N(CH3)2；R37Selected from halogen atom, alkyl, fluoroalkyl, methoxy, nitro, amino, aldehyde group, ketone group or ester group.
9. 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 1-8 wherein H on any one C is substituted, wholly or partially, with halogen, preferably F.
10. A method for producing the electrolyte according to any one of claims 1 to 9, characterized in that: the method comprises the step of reacting an unsaturated carbon ring ternary structure containing three-OH, a boron trifluoride compound and an M source to obtain a product, namely the product containing three-OBF3And M is an unsaturated carbocyclic boron trifluoride salt.
11. Use of an unsaturated carbon ring boron trifluoride salt electrolyte according to any one of claims 1 to 9 in a secondary battery, characterized in that: the application is as follows: the general formula I can be used as an additive, and a polymerizable monomer in the general formula I can also be polymerized and then used as a single-ion conductor and polymer framework;
preferably, the application comprises application in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes, which each independently comprise the general formula i as defined in any one of claims 1 to 9;
preferably, the application further comprises application as a battery or battery pack, the battery comprising the ternary unsaturated carbon ring boron trifluoride salt electrolyte of any one of claims 1-9 and a positive electrode, a negative electrode, a separator and a package housing; 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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