WO2022127194A1 - 一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备方法和应用 - Google Patents

一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备方法和应用 Download PDF

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WO2022127194A1
WO2022127194A1 PCT/CN2021/115604 CN2021115604W WO2022127194A1 WO 2022127194 A1 WO2022127194 A1 WO 2022127194A1 CN 2021115604 W CN2021115604 W CN 2021115604W WO 2022127194 A1 WO2022127194 A1 WO 2022127194A1
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battery
group
electrolyte
solid
boron trifluoride
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French (fr)
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杨琪
程勇斌
俞会根
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北京卫蓝新能源科技有限公司
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Priority to EP21905127.3A priority Critical patent/EP4266445A4/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte

Definitions

  • the invention relates to the technical field of batteries, in particular to a sulfur-based boron trifluoride salt electrolyte containing an unsaturated heterocycle, and a preparation method and application thereof.
  • Secondary batteries have received extensive attention over the past few decades due to the widespread application of portable electronic devices and the growing popularity of electric vehicles. Secondary batteries with high energy density occupy a large market in mobile phones, portable electronic products and electric vehicles. However, the demand for large-scale energy storage in the future will further increase the capacity and energy density of batteries, and the requirements for battery materials also keep improving.
  • lithium batteries in order to improve the energy density of the battery, it is necessary to improve the working voltage and discharge capacity of the battery, and use high-voltage high-capacity cathode materials and low-voltage high-capacity anode materials; such as high-voltage lithium cobalt oxide (LCO), high nickel Ternary (NCM811, NCM622, NCM532 and NCA), lithium nickel manganate (LNMO) and other cathode materials and metal lithium, graphite, silicon oxycarbon and other anode materials.
  • LCO lithium cobalt oxide
  • NCM811, NCM622, NCM532 and NCA high nickel Ternary
  • LNMO lithium nickel manganate
  • Electrolytes mainly include liquid electrolytes and solid electrolytes.
  • the current commercial batteries mainly use liquid electrolytes, which have significant advantages of high electrical conductivity and good wettability on the electrode surface, due to the shortcomings of liquid electrolytes such as leakage, volatility, flammability and insufficient thermal stability, the Its development is facing bottlenecks.
  • Solid-state electrolytes are a promising option to address or mitigate these problems, which offer higher safety and thermal stability compared to liquid electrolytes.
  • the solid electrolyte can effectively suppress the formation of lithium dendrites, it is possible to apply metallic lithium anodes.
  • the significant advantages of solid-state electrolytes there are still some disadvantages.
  • the polymer electrolyte has low ionic conductivity; the oxide electrolyte is too hard, brittle, and the electrolyte-electrode interface impedance is large; the sulfide electrolyte is difficult to process, high cost, high interface impedance, and sensitive to air. restricting its wide application.
  • the high-voltage positive electrode and the low-voltage negative electrode match the conventional electrolyte, part of the ions extracted from the positive electrode will be consumed in the first week, and a passivation layer that only conducts ions and does not conduct electrons is formed on the surface of the positive and negative electrode particles.
  • the formed passivation layer has a protective effect on the positive and negative electrodes, making the relationship between the positive and negative electrodes and the electrolyte more stable, thereby determining the electrochemical performance of the battery such as charge-discharge, storage, and cycle life.
  • film-forming additives are generally added to the liquid electrolyte, such as organic film-forming additives FEC (fluoroethylene carbonate), VC (vinylene carbonate), VEC (ethylene vinylene carbonate) ester), PS (propylene sulfite) and 1,3-PS (1,3-propane sultone), etc.
  • FEC fluoroethylene carbonate
  • VC vinyl carbonate
  • VEC ethylene vinylene carbonate
  • PS propylene sulfite
  • 1,3-PS 1,3-PS (1,3-propane sultone
  • the main components of the SEI passivation film formed on the surface of the negative electrode are various inorganic components Li 2 CO 3. LiF, Li 2 O, LiOH, etc. and various organic components ROCOOLi, ROLi, (ROCOOLi). Since the conventional film-forming additives do not contain dissociable ions, the surface passivation layer can only be formed by consuming the ions of the positive electrode, so the first effect and discharge specific capacity are relatively low. If the added salt/additive can form a passivation layer that conducts ions and has good stability on the electrode surface, then liquid electrolytes and polymer electrolytes with narrow electrochemical windows can be used in high-voltage battery systems, and can be more Greatly improve battery energy density and cycle life.
  • Patent No. CN105789701A discloses a kind of electrolyte additive, the additive comprises hydrogenated thiophene-boron trifluoride coordination compound and fluorolithium phosphate, wherein the hydrogenated thiophene-boron trifluoride coordination compound is selected from formula (1 ) at least one of the compounds represented by the structural formula: wherein, R 1 , R 2 , R 3 , R 4 are each independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-20 alkyl group, Substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-26 aryl; substituents are selected from halogen and cyano.
  • R 1 , R 2 , R 3 , R 4 are each independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted
  • the present application independently studies the structure of -SBF 3 M attached to a heterocycle, especially an unsaturated heterocycle. This is because the chemical properties of heteroatoms and unsaturated bonds themselves are also special. When they exist in the ring, they will affect the chemical and physical properties of the entire ring. and so on are substantially different, so their relevance or inferability to each other is uncertain. Therefore, when -SBF 3 M is attached to the unsaturated heterocycle, it may produce different effects than other structures, especially when two -SBF 3 M is attached, it may have more unexpected and excellent effects. Therefore, this application determines that the research object is directly or indirectly connected to -S-BF 3 M on the unsaturated heterocycle, so as to be more targeted and more clearly determined when -S-BF 3 M is connected to the unsaturated heterocycle. specific situation.
  • the present invention provides a sulfur-based boron trifluoride salt electrolyte containing an unsaturated heterocycle and its preparation and application, which have multiple effects, and can be used as both an electrolyte additive and a salt.
  • a sulfur-based boron trifluoride salt electrolyte containing an unsaturated heterocycle and its preparation and application, which have multiple effects, and can be used as both an electrolyte additive and a salt.
  • it can also be used as a single-ion conductor polymer electrolyte and polymer backbone after polymerization.
  • a stable passivation layer is formed on the surface of the electrode, and itself contains M ions, which consumes less ions provided by the electrode during the film formation process. Therefore, when used as an additive, it can significantly improve the battery's first efficiency and efficiency.
  • the boron trifluoride salt synthesized by this patent has good ion transport and stable electrochemical performance.
  • the battery shows very good cycling performance.
  • the electrolyte can be used in liquid batteries, solid-liquid hybrid batteries, semi-solid batteries, gel batteries, quasi-solid-state batteries and all-solid-state batteries, and helps to improve the energy density, cycle stability, and lifespan of batteries.
  • the present invention aims to overcome the deficiencies in the prior art.
  • An inventive point of the present invention is to provide an unsaturated heterocyclic sulfur-based boron trifluoride salt-based electrolyte, the electrolyte comprising an unsaturated heterocyclic sulfur-based boron trifluoride salt represented by the following general formula I:
  • R' represents an unsaturated heterocycle, and the unsaturated heterocycle contains at least one heteroatom and at least one unsaturated bond;
  • the heteroatom is selected from S, N, O, P, Se, Ca, Al, B or Si;
  • M is a metal cation;
  • E 1 , E 2 are independently none, a group, a chain structure containing at least one atom or a structure containing a ring;
  • R is a substituent, representing the Any one H can be substituted by a substituent, and the substituent can replace one H or two or more Hs. If two or more Hs are substituted, the substituents can be the same or different, that is, each H can be substituted by any of the substituents defined in R.
  • the unsaturated heterocycle is a three- to twenty-membered ring; the unsaturated bond is a double bond; the two -SBF 3 M in the general formula I can be ortho and meta bit, separated by 2 atoms, or separated by more than two atoms.
  • the heteroatom is selected from S, N, O, P or Si.
  • the carbon atom C connected to -SBF 3 M includes carbonyl carbon and non-carbonyl carbon
  • any H on C in the general formula I can be independently substituted by halogen, preferably F, that is, any H on C in the ring, substituent, E 1 , E 2 etc. can be substituted, therefore , in the following limitations, some technical features no longer specifically describe the case where any H on C is substituted by halogen.
  • any one of the heteroalkyl, heteroalkenyl, heteroalkynyl and heteroalkenynyl structures contains at least one non-carbon atom selected from the group consisting of halogen, S, N, O, P, Se, Ca, Al, B or Si;
  • the cyclic substituents include three- to eight-membered rings and polycyclic rings composed of at least two single rings;
  • the salts substituents include but are not limited to sulfate (such as lithium sulfate, sodium sulfate, potassium sulfate), sulfonate (such as lithium sulfonate), sulfonimide salt (such as lithium sulfonimide), carbonate, carboxylate (such as lithium, sodium, potassium, etc.), thioether salts (eg -SLi), oxyether salts (eg -OLi), ammonium salts (eg -NLi), hydrochlorides, nitrates, azides, silicate
  • the carbonyl group is -R 10 COR 11
  • the ester group is -R 12 COOR 13 , -R 12 OCOR 17 , -R 12 SO 2 OR 13 , R 12 O-CO-OR 13 or
  • the etheroxy group is -R 14 OR 15
  • the ether thio group is -R 14 SR 15
  • the sulfoalkane is -R 18 SO 2 R 19
  • the amide is Sulfonamide is
  • the unsaturated heterocycle R' is a three- to twelve-membered ring; a three-membered ring: contains one double bond and one heteroatom; a four-membered ring: contains one double bond, Contains 1 or 2 heteroatoms at the same time; five-membered ring: contains 1 or 2 double bonds, and contains 1, 2 or 3 heteroatoms at the same time; six-membered ring: contains 1 or 2 double bonds, at the same time containing 1, 2, 3, 4, 5 or 6 heteroatoms; seven-membered rings: containing 1, 2 or 3 double bonds and 1, 2 or 3 heteroatoms; eight-membered Rings and nine-membered rings: contain 1, 2, 3 or 4 double bonds, and contain 1, 2 or 3 heteroatoms; ten-membered, eleven-membered and twelve-membered rings: contain 1, 2, 3, 4 or 5 double bonds, while containing 1, 2 or 3 heteroatoms; two -SBF 3 M are directly or indirectly attached to any one or
  • the unsaturated heterocycle R' includes but is not limited to the following rings: furan, 3,4-dihydrofuran, 2,3-dihydrofuran, thiophene, 2,3-dihydrothiophene, 3,4- Dihydrothiophene, pyrrole, 3,4-dihydropyrrole, 2,3-dihydropyrrole, imidazole, pyrazole, thiazole, oxazole, isoxazole, triazole, dihydrotriazole, thiadiazole, 1, 3-dihydropyridine, 1,4-dihydropyridine, dihydropyrimidine, tetrahydropyrimidine, dihydropyrazine, tetrahydropyrazine, dihydropyridazine, tetrahydropyridazine, dihydrotriazine, tetrahydrotriazine oxazine, pyran, dihydro
  • the general formula I includes but is not limited to the following compounds:
  • -SBF 3 refers to -SBF 3 M;
  • E 1 and E 2 in each cyclic structure are independently consistent with E 1 and E 2 as defined in any of the above paragraphs; on each unsaturated heterocycle
  • Any one of H can be independently selected from any one of the substituents in A 1 , A 2 , A 3 or A 4 , and
  • a 1 , A 2 , A 3 and A 4 are independently selected from any of the above Any of the substituents defined in Substituent R.
  • the halogen atom includes F, Cl, Br, I; R 2 , R 3 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 are independently C 1-10 alkyl, C 1-10 heteroalkyl, C 1-10 alkenyl or C 1-10 heteroene and R 2 , R 3 , R 10 , R 12 , R 14 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 , R 30 , R 31 , R 32 , R 3 , R 10 , R 12 , R 14 , R 18 , R 20 , R
  • the alkyl group is selected from the alkyl group of 1-18 C; the heteroalkyl group is selected from the alkyl group containing at least one of the heteroatoms; the alkenyl group is selected from the alkenyl group of 1-18 C; the heteroalkenyl group is selected from From alkenyl groups containing at least one of said heteroatoms; alkynyl groups are selected from alkynyl groups of 1-10 C; heteroalkynyl groups are selected from alkynyl groups containing at least one of said heteroatoms; alkenyl groups are selected from alkynyl groups containing both triple bonds and double-bonded alkenynyl groups containing 1-10 Cs; heteroalkenynyl groups are selected from alkenynyl groups containing at least one of said heteroatoms.
  • 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 or pentadecyl, eg -C(CH 3 ) 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 2 CH 2 C(CH 3 ) 3 , -C(CH 3 ) 2 CH 2 CH 3 and so on belong to the category of alkyl; heteroalkyl includes -CH 2 NO 2 , -CH 2 Z 1 CH 3 , -CH 2 CH 2 Z 1 , -Z 1 (CH 2 CH 3 ) 2 , -
  • the cyclic substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and polycyclic; preferably, the cyclic substituents are selected from cyclopropane, ethylene oxide, cyclobutyl Alkyl, cyclobutaalkyl, cyclobutenyl, cyclobutanyl, phenyl, pyridine, pyrimidine, cyclopentyl, cyclopentenyl, cyclopentadienyl, pyrrolyl, dihydropyrrolyl , tetrahydropyrrolyl, furanyl, dihydrofuran, tetrahydrofuran, thiophene, dihydrothiophene, tetrahydrothiophene, imidazolyl, thiazolyl, dihydrothiazolyl, isothiazolyl, dihydroisothiazolyl, pyr
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, trifluoromethyl, alkenyl, and R 10 , R 12 , R 14 , R 16 , R 18 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 29 , and R 30 can be independently H or none; the haloalkyl and haloheteroalkyl include groups in which any one of H in
  • E 1 or E 2 is selected from none, -CH 2 -, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl base, hexyl, vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl, dienyl, -CO-, -CH 2 CO-, -CH 2 CH 2 CO- , -CH 2 CH 2 CH 2 CO-, -C(CH 3 ) 2 -, -CH(CH 3 )-, -CH(CF 3 )-, -C(CF 3 ) 2 -, -Z' 1 CH 2 -, -Z' 1 CH 2 CH 2 -, -CH 2 Z' 1 CH 2 -, CH 2 CH 2 Z' 1 CH 2 -, CH 2 CH 2
  • M of the general formula I includes Na + , K + , Li + , Mg 2+ or Ca 2+ , preferably Na + , K + or Li + .
  • the general formula I is a compound in which all or part of the H on any one C in the general formula I described in any of the above paragraphs is substituted by halogen, preferably by F.
  • Another inventive point of the present invention is to provide a method for preparing an electrolyte according to any of the above paragraphs, the method is an unsaturated heterocyclic mercapto binary structure containing two -SH, a boron trifluoride compound and M
  • the source reaction yields the product, an unsaturated heterocyclic thio-like boron trifluoride salt containing two -SBF3Ms .
  • Another inventive point of the present invention is to provide an application of the unsaturated heterocyclic-containing sulfur-based boron trifluoride salt electrolyte in a secondary lithium battery according to any one of the above, wherein the application is: the The general formula I can be used both as a salt and as an additive. For a polymerizable monomer, it can also be used as a single-ion conductor polymer electrolyte and polymer backbone after polymerization.
  • Another inventive point of the present invention is to provide an additive for use in a battery, the additive comprising the unsaturated heterocyclic thio-based boron trifluoride salt described in any of the above general formulas, that is, general formula I.
  • Another inventive point of the present invention is to provide a salt for use in a battery, the salt is a salt in an electrolyte, and the salt includes the unsaturated heterocyclic sulfur-based boron trifluoride salt described in any one of the above general formulas , namely general formula I.
  • Another inventive point of the present invention is to provide a polymer for use in a polymer electrolyte, the polymer is an unsaturated heterocyclic thioboron trifluoride represented by the general formula I described in any of the above paragraphs It is formed by polymerizing salt, and after polymerization, it is used in batteries as a single-ion conductor polymer electrolyte and polymer skeleton.
  • Another inventive point of the present invention is to provide an electrolyte, which includes liquid electrolyte, gel electrolyte, mixed solid-liquid electrolyte, quasi-solid-state electrolyte or all-solid-state electrolyte, and these electrolytes include the unsaturated heterocycles described in any of the above paragraphs Sulfuryl boron trifluoride salt.
  • the battery includes a liquid battery, a mixed solid-liquid battery, a semi-solid battery, a gel battery, a quasi-solid-state battery and an all-solid-state battery; the battery includes any of the above-mentioned paragraphs.
  • Sulfur-based boron trifluoride salt electrolytes containing unsaturated heterocycles, as well as positive electrodes, negative electrodes, separators and packaging shells; the liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid-state electrolytes or all-solid-state electrolytes can be applied to Liquid batteries, hybrid solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid-state batteries or all-solid-state batteries.
  • the last inventive point of the present invention is to provide a battery pack including the battery.
  • the electrolyte in the present application creatively combines two -SBF 3 M in an unsaturated heterocyclic ring, preferably -SBF 3 M is connected to a carbon atom C, and the S is an atom in an acyclic ring.
  • the unsaturated heterocyclic sulfur-based boron trifluoride salt can be used as an additive in the electrolyte, which can form a stable and dense passivation film on the electrode surface of the battery, hinder the direct contact between the electrolyte and the electrode active material, and inhibit the components of the electrolyte.
  • the decomposition of ions broadens the electrochemical window of the entire electrolyte system, which can significantly improve the cycle performance, specific discharge capacity and Coulomb efficiency of the battery; in addition, the unsaturated heterocyclic sulfur-based boron trifluoride salt itself is a metal ion Conductor, as an additive, forms a stable passivation layer on the electrode surface and consumes less metal ions released from the positive electrode, which can significantly improve the first Coulomb efficiency and the first cycle discharge specific capacity of the battery.
  • the electrochemical performance of the battery is improved.
  • the structure of the present application can also be used in combination with conventional additives, that is, dual additives or multi-additives, and the batteries using dual-additives or multi-additives show more excellent electrochemical performance.
  • the unsaturated heterocyclic thio-based boron trifluoride salt containing 2 -SBF 3 M in this application can be used as a salt in electrolytes (including liquid electrolytes, mixed solid-liquid electrolytes and all-solid-state electrolytes).
  • electrolytes including liquid electrolytes, mixed solid-liquid electrolytes and all-solid-state electrolytes.
  • the ions are easily solvated, providing high ionic conductivity for batteries, and has the advantages of not corroding current collectors, being able to withstand high voltages, and it can convert polymers with narrow electrochemical windows (such as PEO) and high voltage (>3.9V) cathode matching, significantly improve the electrochemical performance of the battery.
  • the salts in the present application can be used in combination with the conventional salts as double salts or polysalts, and the effect is also very good.
  • the use of the structures in the present application in electrolytes can synergize both as an additive property and as a salt property, giving it an excellent, superior effect over conventional additives or salts, eg, when used as a salt, not only It has good ion transport.
  • a stable passivation layer can be formed on the surface of the electrode to prevent the polymer (such as PEO) or other components with a narrow electrochemical window from being further decomposed, so the battery It exhibits more excellent long-cycle stability.
  • the structure in this application contains polymerizable functional groups (such as cyclic ethers, cyclic carbonates, etc.), which can be used as monomers of single-ion conductor polymer electrolytes, and can also be used as single-ion conductor polymers after polymerization.
  • polymerizable functional groups such as cyclic ethers, cyclic carbonates, etc.
  • Electrolyte applications when applied as single-ion conductor polymer electrolytes, the batteries show very good cycling performance. It can be ex-situ polymerized into a single ion conductor and assembled into a battery, or it can be polymerized in-situ in a battery to form a quasi-solid or all-solid-state battery.
  • the polymer electrolyte polymerized by this application as a monomer still has an excellent effect, and after additionally adding a conventional salt, due to the increased The number of ions dissociated, and thus the battery exhibits more excellent electrochemical performance. Therefore, when the boron trifluoride salt containing 2-SBF 3 M in the present application is used, its own salt properties and the properties of polymerized monomers as polymer electrolytes can synergize well, that is, its own multiple The effect can be synergistic, the effect is good, and the significance is great.
  • salt such as lithium/sodium salt
  • the raw materials used for preparing the sulfur-based boron trifluoride salt in this application are rich in sources, wide in selectivity of raw materials, low in cost, and very simple in the preparation process, and only need to combine the compound containing two-SH with boron trifluoride organic compounds It can be reacted with M source (M is a metal cation), the reaction conditions are simple and mild, and it has an excellent industrial application prospect.
  • the present application can also use sodium, potassium and other metals other than traditional lithium to form salts, which provides more possibilities for later application, cost control or raw material selection, and is of great significance.
  • the unsaturated heterocyclic sulfur-based boron trifluoride salt electrolyte provided in this application can be applied to liquid batteries, mixed solid-liquid batteries, and all-solid-state batteries, and can improve the electrochemical performance of the battery, including improving the energy density of the battery. , improve the cycle stability, prolong the service life of the battery, and the synthesis process is simple, the raw material price is low, and it has good economic benefits.
  • Figures 1 to 11 are respectively the hydrogen NMR spectra of the products shown in Examples 1-11 of the present invention.
  • Fig. 12 is the carbon nuclear magnetic spectrum of the product shown in Example 12 of the present invention.
  • Figures 13 to 15 are respectively the hydrogen NMR spectra of the products shown in Examples 13-15 of the present invention.
  • FIGS 16 to 19 are respectively the cycle effect diagrams of the batteries prepared as the additives in the liquid electrolyte in Examples 2/4/10/15 of the present application;
  • Figures 20 to 21 are respectively the cycle effect diagrams of the battery made of the salt in the liquid electrolyte of Example 7/11 of the application;
  • Fig. 22 is the cycle effect diagram of the battery made of the salt in the solid electrolyte in Example 8 of the application;
  • FIG. 23 is a cycle effect diagram of a battery prepared by polymerizing the monomer in Example 13 of the present application as a polymer electrolyte.
  • connection position in the substituent with the substituted structure is not clearly indicated, it means that any atom in the substituent can be connected with the substituted atom or structure, for example: if the substituent is Then any atom on any benzene or any atom in R 43 can be connected with the substituted structure.
  • the connected structure can be connected with any one of the connecting bonds, such as If R 93 is "-OCH 2 CH 2 -", the connecting bond on O can be connected to the left benzene ring or the right benzene ring, and similarly, the connecting bond on the methylene group is also.
  • any one contains Atoms of H can be connected.
  • E 1 in the claims of the present application is n-butyl group, since E 1 has 2 connecting bonds to be connected (one is connected with -SBF 3 M and the other is connected with the main structure), and n-butyl group has only at the end One linkage, then the other linkage can be on any of the 4 carbon atoms in the n-butyl group.
  • substituents on the ring are represented by codes such as A or R, such as Then if there are two Hs on the C connected to A 1 , then these two hydrogen Hs can be replaced by substituents, or only one, and the substituents on the two hydrogens can be the same or different, such as two hydrogens. Both Hs may be substituted with methyl groups, or one of them may be substituted with methyl and one with ethyl. In addition, the substituents may be attached to the ring via a double bond, see the examples earlier in this paragraph.
  • the xx group may have one connecting bond connected to the substituted structure, or there may be two or three, depending on the actual needs. For example, if it is a general substituent, it has only one linkage, if it is E 1 , E 2 , E 3 or some R in the second substituent, etc., it has 2 or 3 linkages.
  • M in -SBF 3 M can be a monovalent, divalent, trivalent or multivalent metal cation, if it is a non-monovalent ion, the amount of -SBF 3 increases correspondingly It is sufficient to make it fit exactly with the valence of M.
  • boron trifluoride compound refers to boron trifluoride, a compound containing boron trifluoride, a boron trifluoride complex, and the like.
  • the inventive point of the present invention is to provide a dibasic sulfur-based boron trifluoride salt that can be used as an electrolyte additive, an electrolyte salt and a polymerizable monomer, that is, the boron trifluoride salt contains two -SBF 3 M group, wherein M is Li + or Na + etc.
  • the binary boron trifluoride salt can be used in liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid-state batteries and all-solid-state batteries.
  • the preparation method of the compound is simple, ingenious and has high yield. It is obtained by reacting the raw material, boron trifluoride compound and M source, specifically -SH in the raw material participates in the reaction, and other structures do not participate in the reaction.
  • the specific preparation methods mainly include two types:
  • M source and raw materials are added to the solvent, mixed, and reacted at 5-50 °C for 5-24 hours, and the obtained mixed solution is reduced under the conditions of 20-80 °C and vacuum degree of about -0.1MPa. Press drying to remove the solvent to obtain an intermediate; add boron trifluoride compounds, stir and react at 5-50 °C for 6-24 hours, and dry the obtained mixed solution under reduced pressure at 20-80 °C and a vacuum degree of about -0.1MPa , to obtain a crude product, and the crude product is washed, filtered and dried to obtain the final product binary organic boron trifluoride salt, and the yield is 74-95%.
  • the raw materials and boron trifluoride compounds are added to the solvent, mixed evenly, and reacted at 5-50 ° C for 6-24 hours, the obtained mixed solution is at 20-80 ° C and the vacuum degree is about -
  • the solvent is dried under reduced pressure to remove the solvent, and the intermediate is obtained by the reaction; the M source is added to the solvent, and then the solvent containing the M source is added to the intermediate, and the reaction is stirred at 5-50 ° C for 5-24 hours to obtain
  • the crude product is directly washed or washed after drying under reduced pressure, then filtered and dried to obtain the final product binary organic boron trifluoride salt, and the yield is 74-95%.
  • the boron trifluoride compounds may include boron trifluoride ethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride butyl ether complex, boron trifluoride acetic acid complex, boron trifluoride monoethylamine complex, boron trifluoride phosphoric acid complex and the like.
  • M sources include, but are not limited to, metallic lithium/sodium flakes, lithium/sodium methoxide, lithium/sodium hydroxide, lithium/sodium ethoxide, butyllithium/sodium, lithium/sodium acetate, and the like.
  • the solvents described in each place are independently alcohols (some raw materials of liquid alcohols can also be solvents at the same time), ethyl acetate, DMF, acetone, hexane, dichloromethane, tetrahydrofuran, ethylene glycol dimethyl ether, etc. .
  • Small polar solvents such as diethyl ether, n-butyl ether, isopropyl ether, n-hexane, cyclohexane, diphenyl ether, etc. can be used for washing.
  • Preparation method under argon atmosphere, mix 0.01 mol of raw material and boron trifluoride ether complex (2.98 g, 0.021 mol) in 15 ml of THF, and react at room temperature for 12 hours. The obtained mixed solution was dried under reduced pressure under the conditions of 30° C. and a vacuum degree of about -0.1 MPa to remove the solvent to obtain an intermediate.
  • Preparation method under nitrogen atmosphere, take 0.01 mol of raw material and lithium methoxide (0.76 g, 0.02 mol), mix well with 20 ml of methanol, and react at room temperature for 18 hours. The obtained mixed solution was dried under reduced pressure under the conditions of 40° C. and a vacuum degree of about -0.1 MPa to remove the solvent to obtain an intermediate.
  • Preparation method under argon atmosphere, mix 0.01 mol of raw material and boron trifluoride tetrahydrofuran complex (3.07 g, 0.022 mol) in 15 ml of THF, and react at room temperature for 12 hours.
  • the obtained mixed solution was dried under reduced pressure under the conditions of 30° C. and a vacuum degree of about -0.1 MPa to remove the solvent to obtain an intermediate.
  • Preparation method under argon atmosphere, mix 0.01 mol of raw material and boron trifluoride acetic acid complex (3.83 g, 0.0204 mol) in 15 ml of THF, and react at 40 ° C for 12 hours. The solvent was removed by drying under reduced pressure at about -0.1 MPa to obtain an intermediate. Sodium acetate (1.64g, 0.0204mol) was dissolved in 10ml of DMF and added to the intermediate, and the reaction was stirred at 45°C for 8 hours, and the resulting mixture was dried under reduced pressure at 80°C and a vacuum of about -0.1MPa. , the obtained solid was washed three times with diphenyl ether, filtered and dried to obtain the product M5, where Q was -S-BF 3 Na. The yield was 80%, and the NMR is shown in Figure 5.
  • the product M6 is prepared from the raw materials by the method of Example 3, and Q is -S-BF 3 Li. The yield is 85%, and the NMR is shown in Figure 6.
  • the product M10 is prepared from the raw materials by the method of Example 3, and Q is -S-BF 3 Li. The yield is 81%, and the NMR is shown in Figure 10.
  • the product M11 is prepared from the raw materials by the method of Example 2, and Q is -S-BF 3 Li. The yield is 86%, and the NMR is shown in Figure 11.
  • the product M12 is prepared from the raw materials by the method of Example 1, and Q is -S-BF 3 Li. The yield is 85%, and the NMR is shown in Figure 12.
  • the product M14 is prepared from the raw materials by the method of Example 1, and Q is -S-BF 3 Li. The yield was 79%, and the NMR is shown in Figure 14.
  • the product M15 is prepared from the raw materials by the method of Example 3, and Q is -S-BF 3 Li. The yield is 88%, and the NMR is shown in Figure 15.
  • the unsaturated heterocyclic boron trifluoride salt protected in the present invention mainly plays three roles: 1. It is used as an additive in the electrolyte (including liquid and solid state), and it mainly plays the role of generating a passivation layer, and Since it can dissociate ions and supplement the consumed ions, the first cycle efficiency, first cycle discharge specific capacity, long cycle stability and rate performance of the battery are greatly improved. 2. As a salt in the electrolyte (including liquid and solid state), it mainly plays the role of providing ion transport and passivating the electrode. It can be used alone as a salt or combined with a traditional salt as a double salt, and the effect is good. 3.
  • the polymerizable monomer it can also be used as a single ion conductor polymer electrolyte after polymerization.
  • the battery shows very excellent cycle performance. The performance of the present application is described below in an experimental manner.
  • the active material of the positive electrode main material, the electronically conductive additive and the binder are added to the solvent according to the mass ratio of 95:2:3, and the solvent accounts for 65% of the total slurry. material; coating the positive electrode slurry on aluminum foil, drying, compacting and cutting to obtain a usable positive electrode sheet.
  • the active materials here are selected from lithium cobalt oxide (LiCoO 2 , abbreviated as LCO), nickel cobalt lithium manganate (NCM811), nickel cobalt lithium aluminate (LiNi 0.8 Co 0.15 Al 0.05 O 2 , abbreviated as NCA), nickel manganese oxide ( LiNi 0.5 Mn 1.5 O 4 , abbreviated as LNMO), Na 0.9 [Cu 0.22 Fe 0.3 Mn 0.48 ]O 2 (abbreviated as NCFMO), carbon nanotubes (CNT) and Super P are selected as electronic conductive additives, and polypolarized as the binder. Vinyl fluoride (PVDF), and N-methylpyrrolidone (NMP) was used as the solvent.
  • VDF vinyl fluoride
  • NMP N-methylpyrrolidone
  • the active material of the negative electrode main material (except metal Li), electronic conductive additives and binders are added to the solvent deionized water according to 95:2.5:2.5, the solvent accounts for 42% of the total slurry, and the mixture is evenly mixed to obtain a certain fluidity.
  • the active materials here are graphite (C), silicon carbon (SiOC450), lithium metal (Li), soft carbon (SC), CNT and Super P as conductive agents, and carboxymethyl cellulose (CMC) and butyl acetate as binders. Styrene rubber (SBR).
  • the positive and negative electrode systems selected by the present invention are shown in Table 1:
  • M1 ⁇ M15 organic solvent, conventional salt and conventional additives are mixed uniformly to obtain a series of electrolytes E1 ⁇ E15.
  • the solvents used here are ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC). , ethylene carbonate (EC), propylene carbonate (PC).
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • TMP trimethyl phosphate
  • PFPN ethoxy pentafluorocyclotriphosphazene
  • DTD vinyl sulfate
  • Lithium Bisoxalate Borate Lithium Difluorooxalate Borate
  • LiFSI Lithium Bisfluorosulfonimide
  • LiPF 6 Lithium Hexafluorophosphate
  • LiTFSI Lithium Bis(trifluoromethyl)sulfonimide
  • NaPF 6 sodium hexafluorophosphate
  • Table 2 The specific components and proportions are shown in Table 2.
  • Comparative samples According to the ratio of E1 to E15, replace M1 to M15 with blanks (ie, do not add M1 to M15), and then the corresponding conventional liquid electrolyte comparative samples L1 to L15 can be obtained.
  • the liquid electrolyte series E1-E15 containing the structures in the examples of the present application as additives and the conventional liquid electrolyte L1-L15 comparative samples were assembled into a button battery, as follows: negative electrode shell, negative electrode sheet, PE/Al 2 O 3 separator, electrolyte , positive pole piece, stainless steel piece, spring piece, and positive electrode shell are assembled into a button battery, and the long cycle test is carried out at room temperature.
  • C represents magnification
  • the positive pole piece is a circular piece with a diameter of 12 mm
  • the negative pole piece is a circular piece with a diameter of 14 mm
  • the separator is a circular piece with a diameter of 16.2 mm, which is a commercial Al 2 O 3 / PE porous membrane.
  • the battery systems prepared from E1 to E15 are Battery 1 to Battery 15, respectively, and the battery systems prepared from L1 to L15 are Comparative Battery 1 to Comparative Battery 15, respectively.
  • the specific configuration and voltage range of the battery are shown in Table 3.
  • Table 4 shows the results of the first-cycle discharge specific capacity, first-cycle efficiency, and 50-cycle capacity retention rate of batteries 1 to 15 and comparative batteries 1 to 15 at room temperature.
  • Example batteries and comparative batteries Discharge specific capacity in the first week (mAh/g) First week efficiency (%) 50-cycle capacity retention rate (%) battery 1 160.9 82.7 89.0 Comparative battery 1 127.3 74.3 77.3 battery 2 161.0 82.8 88.7 Contrast battery 2 127.4 74.4 77.5 battery 3 161.2 83.3 89.3 Contrast battery 3 154.4 81.1 83.4 battery 4 161.5 83.2 89.2 Contrast battery 4 154.3 81.2 83.6 battery 5 109.6 81.1 91.5 Comparative battery 5 95.5 70.3 86.3 battery 6 171.4 83.5 89.4 Contrast battery 6 141.3 75.4 77.4
  • M2, M3, M7, M11, organic solvents, conventional additives and conventional salts are mixed uniformly to obtain a series of liquid electrolytes R2, R3, R7, R11, and conventional salts, organic solvents and conventional additives are mixed uniformly to obtain a series of conventional liquid electrolytes Q2, Q3, Q7 , Q11, the solvent and conventional additives used are all included in the solvent and conventional additives described in the "1" of this embodiment.
  • the specific components and proportions of the liquid electrolyte are shown in Table 5.
  • the obtained series of liquid electrolytes R (shown in Table 5) and conventional liquid electrolytes Q (shown in Table 5) were assembled into a button battery.
  • the positive and negative electrodes, the size of the diaphragm, the assembly method, and the cycle of the battery were the same as those in this example "1"
  • the button batteries shown in the figure are batteries 2, 3, 7, 11 and the corresponding comparative batteries, respectively.
  • the specific configuration, cycle mode and voltage range of the battery are shown in Table 6.
  • the results of the first cycle discharge specific capacity, the first cycle efficiency, and the 50-cycle capacity retention rate of the battery and the comparative battery at room temperature are shown in Table 7.
  • the boron trifluoride salt provided by the present invention is easily solvated in non-aqueous solvent, provides high ionic conductivity for the battery, and has high stability.
  • the liquid battery system with Li as the negative electrode all of them show very excellent electrochemical performance, the first effect, the first cycle discharge specific capacity, and the capacity retention rate are relatively high, and the performance is basically not inferior to the battery corresponding to the traditional salt.
  • the structure, polymer and inorganic filler provided by the present invention are dissolved in DMF according to the proportion, and the polymer electrolyte is obtained after stirring and mixing, coating to form a film, rolling and drying.
  • Membranes G8, G10, G13, G15 and polymer contrast electrolyte membranes G'1-G'2, the specific components, proportions, etc. are shown in Table 8.
  • Polyethylene oxide (PEO, molecular weight is 1 million) is selected as the polymer, and LLZO of 160 nm is selected as the inorganic filler, that is, the crystal form with a median particle size of 160 nm is a cubic phase Li 7 La 3 Zr 2 O 12 inorganic oxide solid state electrolyte.
  • the active material of the positive electrode main material, polymer + salt (the ratio is the same as that of the polymer electrolyte membrane), electronic conductive additives, and binder are mixed in a solvent according to the mass ratio of 91.3:4.8:2.1:1.8 After stirring and mixing, coating on aluminum foil, drying and rolling, an all-solid positive electrode sheet is obtained.
  • the active material is selected to use lithium cobalt oxide (LiCoO 2 , LCO for short), nickel cobalt lithium manganate (NCM811), the electronic conductive additive is Super P, and the binder is polyvinylidene fluoride (PVDF)
  • a metal lithium flake with a thickness of 50 ⁇ m was pressed onto a copper foil as a negative electrode piece.
  • the polymer electrolyte membrane and the positive and negative electrode sheets were cut and assembled into a 1Ah all-solid-state soft-pack battery.
  • the battery was subjected to a long cycle test at 50 °C, and the cycle mode was 0.1C/0.1C for 2 weeks and 0.3C/0.3C for 48 weeks.
  • the specific assembly system and test method of the battery are shown in Table 9, and the test results are shown in Table 10.
  • the batteries prepared by M8, M10, M13, and M15 of the present application have excellent long-term cycle stability and the performance is better than that of the corresponding LiTFSI battery. It may be because the sulfur-based boron trifluoride salt of the present invention not only has excellent ion transport performance, but also can form a denser and more stable passivation layer on the surface of the positive electrode, preventing the catalytic decomposition of each component of the electrolyte by the positive electrode active material, In addition, the boron trifluoride salt of the present invention does not corrode the current collector and thus exhibits superior performance over conventional salts.
  • precursor solution is formed to obtain precursors S2, S12, S13, and S14.
  • the specific proportions are shown in Table 11.
  • the initiator used was azobisisobutyronitrile (AIBN).
  • the electrolyte precursor solutions S2, S12, S13, and S14 obtained from Table 11 are assembled into soft-pack batteries from these precursors, namely batteries (ie, batteries in the example) 2, 12, 13, and 14; the details are as follows: the size of A 64mm ⁇ 45mm positive pole piece, a 65mm ⁇ 46mm negative pole piece, and a diaphragm are assembled into a 2Ah soft-packed cell, and a secondary battery is obtained through the process of lamination, baking, liquid injection, and formation.
  • the battery assembly system is A2, The separator used a commercial PE/Al 2 O 3 porous membrane.
  • FIGS. 20 to 21 are respectively the effect comparison diagrams of the battery 7/11 made of the example 7/11 as the electrolyte salt and the corresponding comparative battery 7/11 without the example 7/11 of the present invention.
  • FIG. 22 is a comparison diagram of the effects of battery 8 using Example 8 as the solid electrolyte salt and comparative battery 1 using LiTFSI as the salt.
  • Example 23 is an effect diagram of the battery 13 prepared as a polymer electrolyte after the monomer in Example 13 is polymerized. It can also be seen from the figure that the structure of the present application has an excellent effect. Also, in the loop graph, there are little squares on it The lines represent the example batteries, with small circles The lines representing the comparative battery, it can be seen from the figure that the lines representing the battery of the example are above the lines representing the battery of the comparative example, and the battery of the example has better effect.
  • the performance of the first week efficiency, the first week discharge specific capacity, the first week discharge capacity, and the capacity retention rate have a direct and significant impact on the overall performance of the battery, which directly determines whether the battery can be applied. Therefore, improving these properties is the goal or direction of many researchers in the field, but in this field, it is very difficult to improve these properties, and generally, an improvement of about 3-5% is a great progress.
  • the example section only shows the additives used as liquid electrolytes, and the boron trifluoride salts in this application can also be used as additives for solid electrolytes. Due to space reasons, they will not be shown here one by one. What is even more surprising is that this component can also be used as a salt in the electrolyte, and the effect is very good.
  • the test shows that its performance is basically not inferior to or even better than the battery corresponding to the traditional lithium salt, and the structure in this application can be applied in solid-state electrolytes, and showed excellent results.
  • the present application can also be used as a monomer in a single-ion conductor polymer electrolyte, which will not be shown here for space reasons. More importantly, the structure type of the present application is also greatly different from the conventional structure, which provides a new direction and idea for the research and development in the field, and also brings a lot of space for further research, and A structure in this application has multiple uses and is of great significance.
  • the applicant used it and the following structures as electrolyte additives to evaluate their effects on the long-cycle performance of the battery at room temperature.
  • the structure of the present application selects the following structure M16, and the following comparative example structure is the structure W.
  • S0 is the control group.
  • the obtained electrolytes S0-S2 are assembled into a button battery, the positive and negative electrodes, the size of the diaphragm, the assembly method, and the battery cycle are the same as the button batteries shown in "1" of this Example 16, which are batteries Y0-Y2 respectively.
  • the specific configuration, cycle mode and voltage range of the battery are shown in Table 14, and the test results are shown in Table 15.
  • W and M16 as electrolyte additives, can improve the battery's first efficiency, 1-50-cycle discharge specific capacity and capacity retention rate.
  • M16 has a more obvious improvement in the first effect and first-week discharge specific capacity of the battery.
  • W is a non-salt complex, which is very different from the structure of the present application, and it does not contain -SBF 3 Li can not form a good passivation layer in the positive and negative electrodes when the additive accounts for 1% of the salt by mass.
  • the M16 containing two -SBF 3 M itself contains a lithium source, which consumes less lithium ions from the positive electrode during the process of forming a good passivation layer, thereby improving the first efficiency of the battery, and maintaining the specific capacity and capacity of the first cycle discharge. Rate. That is, the boron trifluoride organic salt in the present application can be used as both an additive and a salt in the electrolyte, such as M16, its dual role in the electrolyte can play a synergistic role, so the effect is better than other components. For a clearer and clearer mechanism, the applicant is still in the process of further research. But in any case, it is certain that the presence and quantity of SBF 3 M has a substantial impact on battery performance.
  • the structures in Examples 1-15 are selected as representatives to illustrate the preparation method and effect of the present application.
  • Other structures not listed can be prepared by the method described in any one of Examples 1-5.
  • the preparation method is that the raw material, boron trifluoride compound and M source are reacted to obtain the product boron trifluoride organic salt, that is, -SH in the raw material becomes -SBF 3 M, and M can be Li + , Na + , etc., Other structures remain unchanged.
  • the applicant's research team has done serialized effect tests, and the effects are very good, similar to those in the above-mentioned embodiments, such as:
  • the boron trifluoride salts in the present application prepared by etc. have good effects, but due to space constraints, only part of the structure data is recorded.
  • the -BF 3 in 1-SBF 3 M must be connected to the sulfur atom S, and the sulfur atom is connected to the carbon atom C by a single bond. Therefore, S cannot be located in the ring Sulfur on. If S is connected to a non-C atom, or if S is located on the ring (or S is also connected with other two groups), the structure is quite different from this application. Therefore, whether this structure can be applied to the application It is impossible to predict what effects and application scenarios will be in the electrolyte.
  • the salt electrolyte is preferably a non-polymerized organic substance, and the polymerized state has its unique characteristics and characteristics. The applicant may conduct research on the polymerized state in the future, and the present application is in the non-polymerized state.
  • the applicant has done a lot of experiments on this series of structures. After the effect of the first structure is obtained, the follow-up experimental exploration and data supplementation will add up to a span of about two years. Compared with the existing systems, there are cases where the same structure and system have been tested more than once. Therefore, there may be certain errors in different tests.
  • the raw materials in the examples of the present application can be directly purchased or obtained through simple and conventional synthesis, and the raw materials or the synthesis of the raw materials do not have any innovation, therefore, they are not described too much.

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Abstract

本发明涉及一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备方法和应用，所述电解质包括以下通式I所表示的三氟化硼盐：R'代表不饱和杂环，该不饱和杂环上至少含有一个杂原子，且同时至少含有一个不饱和键；M为金属阳离子；E1、E2独立地为无、基团、链式结构或含有环的结构；R为取代基。本申请中的三氟化硼盐在电解质中既可作为添加剂应用又可作为盐应用，对于可聚合的单体，聚合后还可作为单离子导体聚合物电解质兼高分子骨架应用。本申请提供的三氟化硼盐可以应用于液态电池、固液混合电池、半固态电池、凝胶电池、准固态电池和全固态电池中，有助于提高电池的能量密度、循环稳定性、寿命。并且原料价格低廉、合成工艺简单，具有良好的经济效益。

Description

一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备方法和应用 技术领域
本发明涉及电池技术领域，具体涉及一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备方法和应用。
背景技术
由于便携式电子设备的广泛应用和电动汽车的日益普及，二次电池在过去几十年中受到了广泛的关注。高能量密度的二次电池在手机、便携式电子产品和电动汽车中占据了很大的市场，然而，未来大规模储能等的需求对电池的容量和能量密度要求进一步放大，对电池材料的要求也不断提高。
以锂电池为例，为了提高电池的能量密度，需要提高电池的工作电压和放电容量，使用高电压高容量正极材料和低电压高容量负极材料；如高电压钴酸锂(LCO)、高镍三元(NCM811、NCM622、NCM532和NCA)、镍锰酸锂(LNMO)等正极材料和金属锂、石墨、硅氧碳等负极材料。同时要匹配电化学窗口宽的电解质或在电极的表面形成稳定的钝化层从而提高电池的循环稳定性。
电解质主要包括液态电解质和固态电解质。尽管目前商用的电池主要采用液态电解质，其具有导电率高、在电极表面具有良好润湿性的显著优势，但由于液态电解质存在漏泄、易挥发、易燃性和热稳定性不足等缺点，使其发展面临瓶颈。固态电解质是解决或减轻这些问题的一种很有前途的选择，与液体电解质相比，固态电解质具有更高的安全性和热稳定性。此外，由于固态电解质能有效抑制锂枝晶的形成，使得应用金属锂负极成为可能。尽管固态电解质具有显著的优势，但仍存在一些不足。如聚合物电解质离子电导率低；氧化物电解质硬度太大、脆性大、电解质-电极界面阻抗较大；硫化物电解质加工处理难度高、成本高、界面阻抗大、对空气及其敏感等问题，制约了其广泛应用。
在电池中，当高电压正极、低电压负极匹配常规电解质时，在首周会消耗部分从正极脱出的离子，而在正负极颗粒表面形成只导离子、不导电子的钝化层。形成的钝化层对正负极产生保护作用，使正负极与电解质之间更加稳定，从而决定电池的充放电、存储和循环寿命等电化学性能。若形成的钝化层不稳定，随着循环次数的增加，钝化层不断破坏、形成，因此不断消耗电池中的活性离子，导致电池首周放电容量较低、容量衰减严重，电池很快失效。为了提高电池在循环过程中的稳定性，一般会在液态电解质中加入成膜添加剂，如有机成膜添加剂FEC(氟代碳酸乙烯酯)、VC(碳酸亚乙烯酯)、VEC(碳酸乙烯亚乙烯酯)、PS(亚硫酸丙烯酯)和1,3-PS(1,3-丙烷磺酸内酯)等，如在负极表面形成的SEI钝化膜的主要成分有各种无机成分Li 2CO 3、LiF、Li 2O、LiOH等和各种有机成分ROCOOLi、ROLi、(ROCOOLi)。常规成膜添加剂中由于不含可以解离的离子，只能通过消耗正极的离子来形成表面钝化层，因此首效和放电比容均比较低。若添加的盐/添加剂能在电极表面形成一层传导离子、且稳定性好的钝化层，那么可以将电化学窗口窄的液态电解质、聚合物电解质应用于高电压电池体系中，且能较大提高电池能量密度和循环寿命。此外，目前商用电解质的盐合成/提纯工艺复杂、价格很高，造成整个电池的成本也比较高，若有一类新电解质的盐合成/提纯工艺简单、价格稍低，使其部分或全部代替现有技术电解质的盐，因而能够兼顾优异的性能和较低的成本。
本申请人的其中一个研究团队一直在对有机盐类结构进行研究。在偶然的研究中意外的发现硫基三氟化硼有机盐，尤其是双-SBF 3M取代的有机物在应用于电池的液态电解质和固态电解质中时，经测试，性能优异，效果很惊喜。而在现有技术中，还没有针对双取代的硫基三氟化硼有机盐在电池中应用的研究，仅有极个别研究者在探索对含有-S-BF 3基团的化合 物进行零星的研究。
专利号为CN105789701A的专利了公开了一种电解液添加剂，该添加剂包括氢化噻吩-三氟化硼配位化合物和氟代磷酸锂，其中氢化噻吩-三氟化硼配位化合物选自如式(1)所示结构式的化合物中的至少一种：其中，R 1，R 2，R 3，R 4各自独立地选自氢原子、卤原子、氰基、取代或未取代的C1～20烷基、取代或未取代的C2～20烯基、取代或未取代的C6～26的芳基；取代基选自卤素、氰基。但其为络合物类化合物，并非硫基盐类，且目前并没有太大研究成果，更没有工业应用的成果。
Figure PCTCN2021115604-appb-000001
而本申请人惊喜的发现-SBF 3M双取代的盐在电池中具有较好的效果，因此，专门成立团队进行专门研究-SBF 3M双取代的盐，并取得了较好的研究成果。
本申请针对-SBF 3M连接于杂环尤其是不饱和杂环上的结构进行独立研究。这是因为，杂原子以及不饱和键等本身的电性等化学性质也是比较特殊的，其存在于环上时，会影响整个环的化学和物理性质，其与碳环、芳香环、链结构等等都有实质性不同的地方，故彼此之间的关联性或可推断性不确定。因此，在不饱和杂环上连接-SBF 3M时，可能会产生不同于其他结构的效果，尤其连接两个-SBF 3M时，其可能具有更意想不到的优异效果。故本申请将研究对象确定为在不饱和杂环上直接或间接连接-S-BF 3M，以此来更加有针对性更明确的确定-S-BF 3M连接于不饱和杂环时的具体情况。
发明内容
本发明针对现有技术的缺陷提供了一种含有不饱和杂环的硫基三氟化硼盐类电解质及其制备和应用，其具有多重的效果，既可作为电解质添加剂又可作为盐应用，对于可聚合的单体，聚合后还可作为单离子导体聚合物电解质兼高分子骨架应用。当作为电解质添加剂时，在电极表面形成一层稳定的钝化层，且其本身含M离子，在成膜过程中较少消耗电极提供的离子，因此作为添加剂时可以显著提高电池的首效和循环性能；当作为电解质中的盐时，本专利合成的三氟化硼盐具有较好的离子传输性、稳定的电化学性能。当作为单离子导体聚合物电解质应用时，电池显示出非常优异的循环性能。该电解质可以应用于液态电池、固液混合电池、半固态电池、凝胶电池、准固态电池和全固态电池中，有助于提高电池的能量密度、循环稳定性、寿命。本发明旨在克服现有技术中的不足。
本发明的目的是通过以下技术方案来实现：
本发明的一个发明点为提供一种含有不饱和杂环的硫基三氟化硼盐类电解质，所述电解质包括以下通式I所表示的不饱和杂环类硫基三氟化硼盐：
Figure PCTCN2021115604-appb-000002
在以上通式Ⅰ中，R’代表不饱和杂环，该不饱和杂环上至少含有一个杂原子，且同时至少含有一个不饱和键；所述杂原子选自S、N、O、P、Se、Ca、Al、B或Si；M为金属阳离子；E 1、E 2独立地为无、基团、含有至少一个原子的链式结构或含有环的结构；R为取代基，代 表环上任意一个H都可以被取代基取代，且取代基可取代一个H也可以取代两个或多个H，若两个或多个H被取代，则取代基可相同也可不同，即每个H均可被R中的任意一个所限定的取代基取代。
优选地，在通式Ⅰ中，所述不饱和杂环为三元～二十元环；所述不饱和键为双键；通式Ⅰ中的两个-SBF 3M可为邻位、间位、间隔2个原子或间隔超过两个原子。
优选地，在通式Ⅰ中，与-SBF 3M直接连接的原子为碳原子C；更优选地，在通式Ⅰ的两个-SBF 3M中，至少一个与非羰基碳的碳原子连接，该羰基碳包括-C＝O或-C＝S。
优选地，所述杂原子选自S、N、O、P或Si。
优选地，与-SBF 3M连接的碳原子C包括羰基碳和非羰基碳，所述羰基碳包括-C＝O或-C＝S，所述非羰基碳为C原子上不含有＝O或＝S的结构。
优选地，所述通式Ⅰ中任意一个C上的H均可独立地被卤素取代，优选F，即环、取代基、E 1、E 2等中的任意C上H均可被取代，因此，在后述限定中，有些技术特征不再特别说明任意一个C上H被卤素取代的情况。
优选地，所述取代基R选自H、卤素原子、羰基、酯基、醛基、醚氧基、醚硫基、＝O、＝S、
Figure PCTCN2021115604-appb-000003
硝基、氰基、氨基、酰胺、磺酰胺基、磺基烷、磺酸基、肼基、重氮基、烷基、杂烷基、烯基、杂烯基、炔基、杂炔基、烯炔基、杂烯炔基、环类取代基、盐类取代基以及这些基团中任意一个氢H被卤素原子取代后的基团；其中，所述酯基包括羧酸酯、碳酸酯、磺酸酯和磷酸酯，R 2、R 3独立地为H、烷基、杂烷基、烯基、杂烯基、炔基、杂炔基、烯炔基、杂烯炔基或环。
优选地，所述杂烷基、杂烯基、杂炔基和杂烯炔基中的任何一个结构均含有至少一个所述非碳原子，该非碳原子选自卤素、S、N、O、P、Se、Ca、Al、B或Si；所述环类取代基包括三元～八元环以及至少由两个单环构成的多环；所述盐类取代基包括但不限于硫酸盐(如硫酸锂、硫酸钠、硫酸钾)、磺酸盐(如磺酸锂)、磺酰亚胺盐(如磺酰亚胺锂)、碳酸盐、羧酸盐(如羧酸锂、钠、钾等)、硫醚盐(如-SLi)、氧醚盐(如-OLi)、铵盐(如-NLi)、盐酸盐、硝酸盐、叠氮盐、硅酸盐、磷酸盐。
优选地，所述羰基为-R 10COR 11，酯基为-R 12COOR 13、-R 12OCOR 17、-R 12SO 2OR 13、R 12O-CO-OR 13或
Figure PCTCN2021115604-appb-000004
醚氧基为-R 14OR 15，醚硫基为-R 14SR 15；磺基烷为-R 18SO 2R 19，氨基为＝N-R 20、
Figure PCTCN2021115604-appb-000005
或-CH＝N-R 24，酰胺为
Figure PCTCN2021115604-appb-000006
磺酰胺基为
Figure PCTCN2021115604-appb-000007
其中，R 2、R 3、R 10、R 11、R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 28、R 29、R 30、R 31、R 32、R 33、R 34、R 35独立地为烷基、杂烷基、烯基、杂烯基、炔基、杂炔基或环，杂烷基、杂烯基、杂炔基或杂烯炔基均为带有至少一个杂原子的烷基、烯基、炔基和烯炔基；且R 2、R 3、R 10、R 12、R 14、R 18、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 29、R 30、R 31、R 32、R 33、R 35可独立地为H或无；与N或O直接相连的基团还能够为金属离子，如R 13、R 15、R 16、R 22、R 26、R 30、R 31、R 35等等可为金属离子，如Li +、Na +、K +、Ca 2+等，该环与所述环类取代基一致。
且可选择地，所述取代基还包括以上任意一个基团中的任意一个C＝O被C＝S替代后的取代基，如羰基、酯基、醛基、酰胺等中的C＝O被C＝S替代后的基团。
优选地，E 1或E 2选自无、羰基、酯基、烷基、杂烷基、烯基、杂烯基、含有环状结构 的基团、
Figure PCTCN2021115604-appb-000008
＝N-R 6-、这些基团中任意一个C＝O被C＝S替代后的基团以及这些基团中任意一个C-O被C-S替代后的基团，所述杂烯基中的双键包括含有碳碳双键C＝C的结构和含有碳氮双键C＝N的结构，R 4、R 5和R 6独立地与以上段落中的R 2、R 3中限定的种类一致。
优选地，在通式Ⅰ中，所述不饱和杂环R’为三～十二元环；三元环：含有1个双键和1个杂原子；四元环：含有1个双键，同时含有1个或2个杂原子；五元环：含有1个或2个双键，同时含有1个、2个或3个杂原子；六元环：含有1个或2个双键，同时含有1个、2个、3个、4个、5个或6个杂原子；七元环：含有1、2或3个双键，同时含有1个、2个或3个杂原子；八元环和九元环：含有1、2、3或4个双键，同时含有1、2或3个杂原子；十元环、十一元环和十二元环：含有1、2、3、4或5个双键，同时含有1、2或3个杂原子；两个-SBF 3M直接或间接连接于以上所述杂环R’的任意一个或两个原子上。非碳的原子均可称为杂原子。
优选地，所述不饱和杂环R’包括但不限于以下环：呋喃、3,4-二氢呋喃、2,3-二氢呋喃、噻吩、2,3-二氢噻吩、3,4-二氢噻吩、吡咯、3,4-二氢吡咯、2,3-二氢吡咯、咪唑、吡唑、噻唑、恶唑、异恶唑、三唑、二氢三唑、噻二唑、1,3-二氢吡啶、1,4-二氢吡啶、二氢嘧啶、四氢嘧啶、二氢吡嗪、四氢吡嗪、二氢哒嗪、四氢哒嗪、二氢三嗪、四氢三嗪、吡喃、二氢吡喃、硫吡喃、二氢硫吡喃
Figure PCTCN2021115604-appb-000009
Figure PCTCN2021115604-appb-000010
上述杂环R’中，可连接所述取代基R；两个-SBF 3M直接连接或分别通过E 1、E 2间接的连接于上述各个环R’中的任意两个或一个原子上。
优选地，所述通式Ⅰ包括但不限于以下化合物：
Figure PCTCN2021115604-appb-000011
Figure PCTCN2021115604-appb-000012
Figure PCTCN2021115604-appb-000013
Figure PCTCN2021115604-appb-000014
在以上结构中，-SBF 3指-SBF 3M；每个环状结构中的E 1和E 2均独立地与以上任意一段所限定的E 1和E 2一致；每个不饱和杂环上的任意一个H均可独立地选自A 1、A 2、A 3或A 4中的任意一个取代基，A 1、A 2、A 3和A 4均独立地选自以上任意一段所述的取代基R中所限定的任意一个取代基。
优选地，在所述取代基R、A 1、A 2、A 3或A 4中，所述卤素原子包括F、Cl、Br、I；R 2、R 3、R 10、R 11、R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 28、R 29、R 30、R 31、R 32、R 33、R 34、R 35独立地为C 1-10烷基、C 1-10杂烷基、C 1-10烯基或C 1-10杂烯基，杂烷基或杂烯基为带有至少一个杂原子的烷基或烯基；且R 2、R 3、R 10、R 12、R 14、R 18、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 29、R 30、R 31、R 32、R 33、R 35可独立地为H或无，与N或O直接相连的基团还能够为金属离子，如R 13、R 15、R 16、R 20、R 22、R 24、R 26、R 30、R 31、R 35等等可为锂/钠离子；氰基选自-CN、-CH 2CN、-SCH 2CH 2CN或-CH 2CH 2CN。
所述烷基选自1-18个C的烷基；所述杂烷基选自含有至少一个所述杂原子的烷基；烯基选自1-18个C的烯基；杂烯基选自含有至少一个所述杂原子的烯基；炔基选自1-10个C的炔基；杂炔基选自含有至少一个所述杂原子的炔基；烯炔基选自同时含有三键和双键的含有1-10个C的烯炔基；杂烯炔基选自含有至少一个所述杂原子的烯炔基。
优选地，所述烷基包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基或十五烷基，例如-C(CH 3) 3、-CH(CH 3) 2、-C(CH 3) 2CH 2C(CH 3) 3、-C(CH 3) 2CH 2CH 3等便属于烷基范畴；杂烷基包括-CH 2NO 2、-CH 2Z 1CH 3、-CH 2CH 2Z 1、-Z 1(CH 2CH 3) 2、-CH 2N(CH 3) 2、-CH 2CH 2-O-NO 2、-CH 2S-S-CH 3、-CH 2Z 1CH(CH 3) 2、-COCH 2CH(CH 3) 2、-OCH 2(CH 2) 6CH 3、-CH 2(CH 3)Z 1CH 3、-CH 2(CH 3)Z 1CH 2CH 3、-CH 2CH 2Z 1CH 3、-CH 2CH(CH 3)Z 1CH 3、-CH(CH 3)CH 2Z 1CH 3、-CH 2CH 2Z 1CH 2CH 3、-CH 2CH 2CH 2Z 1CH 3、 -CH 2CH 2CH 2Z 1CH 2CH 3、-CH 2CH(CH 3)CH 2Z 1CH 3、
Figure PCTCN2021115604-appb-000015
等；烯基和杂烯基选自乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、己二烯基、-C(CH 3)＝CH 2、-CH 2CH＝CH(CH 3) 2、-C(CH 3)＝CH 2、-COCH 2CH(CH 3) 2、-CH＝CHCOOCH 2CH 3、-CH 2CH＝CHCH 2CH 3、-C(CH 3) 2CH＝CH 2、-N＝CHCH 3、-OCH 2CH＝CH 2、-CH 2-CH＝CH-Z 1CH 3、
Figure PCTCN2021115604-appb-000016
等；炔基和杂炔基选自乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基、-C≡CCH 2CH 2CH 2Z 1CH 2CH 3、-C≡CCH 2Z 1CH 2CH 3、-C≡C-Si(CH 3) 3等。
所述环类取代基包括环丙基、环丁基、环戊基、环己基、环庚基和多环；优选地，该环类取代基选自环丙烷基、环氧乙烷、环丁烷基、环丁杂烷基、环丁烯基、环丁杂烯基、苯基、吡啶、嘧啶、环戊烷基、环戊烯基、环戊二烯基、吡咯基、二氢吡咯基、四氢吡咯基、呋喃基、二氢呋喃、四氢呋喃、噻吩、二氢噻吩、四氢噻吩、咪唑基、噻唑基、二氢噻唑基、异噻唑基、二氢异噻唑基、吡唑基、恶唑、二氢恶唑基、四氢恶唑基、异恶唑、二氢异恶唑基、1,3-二氧环戊烷、三唑基、环己烷基、环己烯基、环己二烯、哌啶、吡喃、二氢吡喃、四氢吡喃、硫吡喃、二氢硫吡喃
Figure PCTCN2021115604-appb-000017
四氢硫吡喃、二噻烷
Figure PCTCN2021115604-appb-000018
1,2-二噻烷
Figure PCTCN2021115604-appb-000019
[1,3]恶唑烷
Figure PCTCN2021115604-appb-000020
二恶烷
Figure PCTCN2021115604-appb-000021
吗啉、哌嗪、吡喃酮、哒嗪、吡嗪、三嗪、二氢吡啶、四氢吡啶、二氢嘧啶、四氢嘧啶、六氢嘧啶、联苯基、萘基、蒽基、菲基、醌基、咔唑基、吲哚基、异吲哚基、喹啉基、嘌呤基、碱基基、苯并恶唑、对二氮杂苯、芘基、苊基、
Figure PCTCN2021115604-appb-000022
Figure PCTCN2021115604-appb-000023
其中，Z 1选自-O-、-S-、-S-S-、-CO-、
Figure PCTCN2021115604-appb-000024
R 36、R 37、R 38、R 43、R 90、R 91、R 92独立地选自H、甲基、乙基、丙基、异丙基、丁基、氟代甲基、氟代乙基、甲氧基、乙烯基、丙烯基或金属离子；所述环类取代基中的任意一个环独立地通过以下任意一个连接基团与被取代的不饱和杂环连接：-CH 2-、-CH 2CH 2-、丙基、丁基、乙烯、丙烯、丁烯、乙炔、丙炔、-COO-、-CO-、-SO 2-、-N＝N-、-O-、-OCH 2-、-OCH 2CH 2-、-CH 2OCH 2-、-COCH 2-、-CH 2OCH 2CH 2-、-OCH 2CH 2O-、-COOCH 2CH 2-、-S-、-S-S-、-CH 2OOC-、-CH＝CH-CO-、
Figure PCTCN2021115604-appb-000025
Figure PCTCN2021115604-appb-000026
或单键，单键即为通过化学键直接连接，即环与环直接连接；R 42独立地选自H、甲基、乙基或丙基；R 47、R 93、R 97独立地选自
Figure PCTCN2021115604-appb-000027
或所述连接基团中的任意一种，R 83选自烃基、杂烃基、环或金属阳离子；所述环类取代基中的任意一个环上的任意一个带有H的原子上均可连接第一取代基，该第一取代基与所述取代基R所限定的类型一致；优选地，该第一取代基选自H、卤素原子、甲基、乙基、丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、氟代甲基、氟代乙基、甲氧基、乙氧基、硝基、烯基、炔基、酯基、磺酸盐、磺基烷、酰胺基、氰基、醛基、-SCH 3、-COOCH 3、COOCH 2CH 3、-OCF 3、＝O、-N(CH 3) 2、-CON(CH 3) 2、-SO 2CH 3或-SO 2CH 2CH 3，该酯基包括以上任意一项所述的碳酸酯、磺酸酯、羧酸酯和磷酸酯。
优选地，所述取代基R选自H、卤素原子、-R 12COOR 13、-R 12OCOR 13、-R 12SO 2OR 13、R 12O-CO-OR 13、醛基、-R 14OR 15、-R 16SR 17、＝O、＝S、＝CH 2、硝基、-CN、-CH 2CN、-CH 2CH 2CN、
Figure PCTCN2021115604-appb-000028
-CH＝N-R 24、
Figure PCTCN2021115604-appb-000029
-R 18SO 2R 19、硫酸盐、磺酸盐、磺酰亚胺盐、碳酸盐、羧酸盐、甲基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、正己基、异己基、仲己基、新己基、庚基、辛基、壬基、乙烯基、丙烯基、丁烯基、戊烯基、己烯基、己二烯基、乙炔基、丙炔基、丁炔基、-C(CH 3) 2CH 2C(CH 3) 3、-C(CH 3) 2CH 2CH 3、-C≡C-Si(CH 3) 3、卤代烷基、卤代杂烷基、
Figure PCTCN2021115604-appb-000030
以及环类取代基。
其中，R 10、R 11、R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 28、R 29、R 30、R 31、R 32独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、三氟甲基、烯基，且R 10、R 12、R 14、R 16、R 18、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 29、R 30可独立地为H或无；所述卤代烷基和卤代杂烷基包括烷基和烷氧基中任意一个H被卤素取代后的基团。
所述环类取代基选自环丙烷基、环氧乙烷、苯基、吡啶、嘧啶、环戊烷基、环戊烯基、环戊二烯基、吡咯基、呋喃基、噻吩、咪唑基、噻唑基、恶唑、二氢恶唑基、1,3-二氧环戊烷、环己烷基、环己烯基、环己二烯、哌啶、吡喃、二氢吡喃、四氢吡喃、联苯基、萘基、吲哚基、苯并恶唑、
Figure PCTCN2021115604-appb-000031
其中，所述环类取代基中的任意一个环可通过-CH 2-、-CH 2CH 2-、-CH 2CH 2CH 2-、-COO-、-CO-、-SO 2-、-N＝N-、-O-、-OCH 2-、-OCH 2CH 2-、-CH 2OCH 2-、-COCH 2-、-S-、-S-S-、-CH 2OOC-或单键与被取代的不饱和杂环连接；R 43选自H、甲基、乙基或丙基。
所述第一取代基优选为H、卤素原子、甲基、乙基、丙基、异丙基、丁基、戊基、氟代甲基、氟代乙基、甲氧基、乙氧基、硝基、乙烯基、乙炔基、氰基、醛基、-SCH 3、-COOCH 3、COOCH 2CH 3、-OCF 3、＝O、-N(CH 3) 2、-CON(CH 3) 2、-SO 2CH 3。
优选地，E 1或E 2选自无、-CH 2-、羰基、酯基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、己基、乙烯基、丙烯基、丁烯基、戊烯基、乙炔基、丙炔基、丁炔基、环己基、环戊基、1,3-己二烯基、-C＝N-、-C(CH 3) 2-、-CH(CH 3)-、-CH(CF 3)-、-C(CF 3) 2-、-SCH 2CH 2-、-CH 2CH 2SCH 2CH 2-、-CH 2CH 2CH(CH 3)-、-Z' 1CH 2CH 2-、 -O-CH 2(CH 2) 4CH 2-、-N＝C(CH 3)-、-O-(CH 2) 6-、-CH 2Z' 1CH 2-、-CH 2(CH 3)Z' 1CH 2-、-CH 2CH 2Z' 1CH 2-、
Figure PCTCN2021115604-appb-000032
Figure PCTCN2021115604-appb-000033
-O-CH 2-CH 2-O-CH 2-CH 2-、、
Figure PCTCN2021115604-appb-000034
这些基团中任意一个C＝O被C＝S替代后的基团以及这些基团中任意一个C-O被C-S替代后的基团；所述羰基包括-CO-、-CH 2CO-、-CH 2CH 2CO-、-CH 2CH 2CH 2CO-、-CH 2COCH 2-、-CH 2CH 2COCH 2-、-CH＝CH-CO-、-OCH 2CH 2CH 2CO-、＝N-CH 2-CO-、-Z' 1CH 2CO-、-Z' 1CH 2CH 2CO-、-Z' 1CH 2CH 2CH 2CO-、-CH 2(CH 2) 5CO-、-CH 2(CH 2) 6CO-、
Figure PCTCN2021115604-appb-000035
Figure PCTCN2021115604-appb-000036
所述酯基包括-COOCH 2-、-COOCH 2CH 2-和-CH 2COOCH 2-；其中，此段中的Z' 1选自-O-、-S-、-S-S-、
Figure PCTCN2021115604-appb-000037
磺酰基、磺酰亚胺基或磺酰氧基，其中，R 41为H、甲基、乙基、丙基、异丙基、丁基、乙氧基或甲氧基，且该R 41中的任意一个氢H均可被F或Cl取代；R 44、R 45独立地为烷基或环；R 39选自H、甲基、乙基、丙基、丁基、戊基、环丙基、环戊基、环己基、硝基、噻唑、-CH(CH 3) 2、-CH 2CH(CH 3) 2、-CH 2CH 2NO 3、
Figure PCTCN2021115604-appb-000038
其中，R 8、R 37、R 38和R 40独立地为无、卤素原子、甲基、乙基、丙基、丁基、氟代甲基、氟代乙基、甲氧基、硝基、醛基、酮基、酯基、-CH 2-N(CH 3) 2或-CH(CH 3)-Ph，R 9为无或亚甲基。
优选地，E 1或E 2选自无、-CH 2-、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、己基、乙烯基、丙烯基、丁烯基、戊烯基、乙炔基、丙炔基、丁炔基、二烯基、-CO-、-CH 2CO-、-CH 2CH 2CO-、-CH 2CH 2CH 2CO-、-C(CH 3) 2-、-CH(CH 3)-、-CH(CF 3)-、-C(CF 3) 2-、-Z' 1CH 2-、-Z' 1CH 2CH 2-、-CH 2Z' 1CH 2-、CH 2CH 2Z' 1CH 2-、-CH 2CH 2Z' 1CH 2CH 2-、-COOCH 2-、-COOCH 2CH 2-、-CH 2COOCH 2-、
Figure PCTCN2021115604-appb-000039
Figure PCTCN2021115604-appb-000040
其中，此段中的Z' 1为O、S；R 39独立地选自H、甲基、乙基、丙基、环丙基、环戊基、环己基、硝基、-CH(CH 3) 2、-CH 2CH(CH 3) 2、
Figure PCTCN2021115604-appb-000041
其中，R 9为无或亚甲基；R 8和R 37独立地选自无、甲基、乙基、丙基、卤素原子、甲氧基、硝基、醛基、氟代甲基、氟代乙基、酮基或酯基。
优选地，所述通式Ⅰ的M包括Na +、K +、Li +、Mg 2+或Ca 2+，优选Na +、K +或Li +。
优选地，所述通式Ⅰ为：以上任意一段中所述的通式Ⅰ中的任意一个C上的H全部或部分被卤素取代后的化合物，优选被F取代。
本发明的另一个发明点为提供一种根据以上任意一段所述的电解质的制备方法，该方法为含有两个-SH的不饱和杂环类巯基二元结构、三氟化硼类化合物和M源反应得到产物，即含有两个-SBF 3M的不饱和杂环类硫基三氟化硼盐。
本发明还有一个发明点为提供一种根据以上任意一项所述的含有不饱和杂环的硫基三氟化硼盐类电解质在二次锂电池中的应用，所述应用为：所述通式I既能够作为盐应用也能 够作为添加剂应用，对于可聚合的单体，聚合后还能够作为单离子导体聚合物电解质兼高分子骨架应用。
本发明还有一个发明点为提供一种应用于电池中的添加剂，该添加剂包括以上任意一项通式所述的含有不饱和杂环类硫基三氟化硼盐，即通式Ⅰ。
本发明还有一个发明点为提供一种应用于电池中的盐，该盐为电解质中的盐，该盐包括以上任意一项通式所述的不饱和杂环类硫基三氟化硼盐，即通式Ⅰ。
本发明还有一个发明点为提供一种应用于聚合物电解质中的聚合物，该聚合物为由以上任意一段中所述的通式I所表示的不饱和杂环类硫基三氟化硼盐聚合而成，聚合后作为单离子导体聚合物电解质兼高分子骨架应用于电池中。
本发明还有一个发明点为提供一种电解质，该电解质包括液态电解质、凝胶电解质、混合固液电解质、准固态电解质或全固态电解质，这些电解质包括以上任意一段所述的不饱和杂环类硫基三氟化硼盐。
本发明还有一个发明点为提供一种电池，所述电池包括液态电池、混合固液电池、半固态电池、凝胶电池、准固态电池和全固态电池；该电池包括以上任意一段所述的含有不饱和杂环的硫基三氟化硼盐类电解质以及正极、负极、隔膜和封装外壳；所述液态电解质、凝胶电解质、混合固液电解质、准固态电解质或全固态电解质均可应用于液态电池、混合固液电池、半固态电池、凝胶电池、准固态电池或全固态电池中。
本发明最后一个发明点为提供一种电池组，所述电池组包括所述电池。
本发明的有益效果为：
本申请中的电解质创造性的将两个-SBF 3M复合于一个不饱和杂环中，优选-SBF 3M与碳原子C连接，且该S为非环中的原子。该不饱和杂环类硫基三氟化硼盐可作为电解质中的添加剂，其能够在电池的电极表面形成稳定、致密的钝化膜，阻碍电解质与电极活性物质直接接触，抑制电解质各组分的分解，扩宽了整个电解质体系的电化学窗口，可显著提高电池的循环性能、放电比容量和库伦效率；此外，该不饱和杂环类硫基三氟化硼盐本身是一种金属离子导体，作为添加剂，其在电极表面形成稳定钝化层的同时较少消耗从正极脱出的金属离子，能够对电池的首次库伦效率、首周放电比容量有明显的提升。含有该硫基三氟化硼盐的电解质和现有的高电压高比容的正极材料及低电压高比容负极材料装配成二次电池时，电池的电化学性能均有改善。此外，本申请结构还能与常规添加剂混合使用，即双添加剂或多添加剂，使用双添加剂或多添加剂的电池显示出更优异的电化学性能。
更重要的是，本申请含有2个-SBF 3M的不饱和杂环类硫基三氟化硼盐可作为电解质(包括液态电解质、混合固液电解质和全固态电解质)中的盐，本申请的盐在非水溶剂中，离子容易被溶剂化，为电池提供较高的离子电导率，且具有不腐蚀集流体、可耐高电压的优点，并且其可将窄电化学窗口的聚合物(如PEO)与高电压(＞3.9V)正极匹配，显著提高电池的电化学性能。而且，本申请中的盐可以与传统中的盐作为双盐或多盐联合应用，效果也很好。此外，在电解质中使用本申请中的结构，其自身作为添加剂属性和作为盐属性也能够协同作用，使其具有极佳的、优于传统添加剂或盐的效果，如，其作为盐时，不仅有较好的离子传输性，在电池循环过程中，在电极表面可以形成一层稳定的钝化层，阻止窄电化学窗口的聚合物(如PEO)或其他组分等被进一步分解，因此电池展现出更加优异的长循环稳定性。
而且，本申请中的结构中含有可以聚合的官能团(如环醚、环状碳酸酯等基团)，其可以作为单离子导体聚合物电解质的单体，聚合后还可作为单离子导体聚合物电解质应用，当作为单离子导体聚合物电解质应用时，电池显示出非常优异的循环性能。其可以非原位聚合成单离子导体组装成电池使用，也可以在电池中原位聚合形成准固态或全固态电池使用。且在本申请中，在不加入盐(如锂/钠盐)的情况下，由本申请作为单体聚合而成的聚合物电解质仍然具有极好的效果，而额外加入常规的盐以后，由于提高了解离的离子数量，因而电池展现出更加优异的电化学性能。因此，本申请含有2个-SBF 3M的三氟化硼盐在使用时，其自身的盐属性与作为聚合物电解质的聚合单体属性能够很好的协同作用，即其自身所具有的多 重效果便可进行协同作用，效果好，意义大。
此外，本申请中用于制备硫基三氟化硼盐的原料来源丰富，原料选择性广，成本低，制备过程非常简单，仅需要将含有两个-SH的化合物与三氟化硼类有机物和M源(M为金属阳离子)进行反应便可，反应简单条件温和，具有极佳的工业应用前景。
另外，本申请还能采用钠、钾等除了传统锂以外的金属来形成盐，这为本申请后期的应用、成本控制或原料选择等提供了更多可能性，意义较大。
所以，本申请提供的含有不饱和杂环类硫基三氟化硼盐电解质可以应用于液态电池、混合固液电池、全固态电池中，可以改善电池的电化学性能，包括提高电池的能量密度、提升循环稳定性、延长电池的使用寿命，并且合成工艺简单、原料价格低廉，具有良好的经济效益。
附图说明
图1～图11分别为本发明实施例1-11所示产物的核磁氢谱图；
图12为本发明实施例12所示产物的核磁碳谱图；
图13～图15分别为本发明实施例13-15所示产物的核磁氢谱图；
图16～图19分别为本申请实施例2/4/10/15作为液态电解质中添加剂所制成的电池的循环效果图；
图20～图21分别为本申请实施例7/11作为液态电解质中盐所制成的电池的循环效果图；
图22为本申请实施例8作为固态电解质中盐所制成的电池的循环效果图；
图23为本申请实施例13中的单体聚合后作为聚合物电解质所制成的电池的循环效果图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明具体实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明中，若无明确指出取代基中与被取代结构的连接位置，则表示取代基中的任何一个原子均可与被取代的原子或结构进行连接，例如：若取代基为
Figure PCTCN2021115604-appb-000042
则任意一个苯上的任意一个原子或R 43中的任意一个原子均可与被取代的结构进行连接。此外，在一个取代基中含有两个连接键时，则被连接结构可与任意一个连接键相连，如
Figure PCTCN2021115604-appb-000043
若R 93为“-OCH 2CH 2-”在O上的连接键既可与左边苯环连接，也可与右边苯环连接，同理，亚甲基上的连接键也是。
在本发明中，若某一个基团需要与两部分结构相连，故其有两个待连接的连接键或自由基，若没有明确指出是哪两个原子与被连接部分连接，则任意一个含有H的原子均可进行连接。如，若本申请权利要求中的E 1为正丁基，由于E 1有2个待连接的连接键(一个与-SBF 3M连接一个与主结构连接)，而正丁基只在末端有一个连接键，那么另一个连接键可位于正丁基中4个碳原子中的任意一个上。
在本发明中，若化学键没有画在原子上，而是画在了与键相交的位置上，如
Figure PCTCN2021115604-appb-000044
代表环上任意一个H都可以被取代基A 1取代，且可取代一个H也可以取代两个或多个H，取代基可相同也可不同。若环上的某个原子(也可以是其它杂原子)上还有多个氢或还可连接 有多个键，则该原子上可同时连接多个相同或不同的取代基，且所连接的取代基均选自A 1。例如：若A 1为甲基、F或＝O，则上述通式可为
Figure PCTCN2021115604-appb-000045
等。此外，环上若以A或R等代号表示了取代基，如
Figure PCTCN2021115604-appb-000046
则若与A 1连接的C上有两个H，则这两个氢H可全部被取代基取代，也可以仅取代1个，两个氢上的取代基可相同也可不同，如两个H可都被甲基取代，也可以一个被甲基取代，一个被乙基取代。此外，取代基还可通过双键与环连接，参见本段前述的举例。
所述“Et”为乙基。“Ph”为苯基。
在本发明的结构式中，若某个原子后面含有位于括号“()”中的基团，则表示括号里的基团与其前面的原子连接。如-C(CH 3) 2-为
Figure PCTCN2021115604-appb-000047
-CH(CH 3)-为
Figure PCTCN2021115604-appb-000048
在本申请中，对于xx基，其可以有一个与被取代结构连接的连接键，也可以有二个或三个，根据实际需要而定。如，若为一般的取代基，则其只有一个连接键，若为E 1、E 2、E 3或第二取代基中的一些R等，其有2个或3个连接键。
在本发明的所有权项和说明书中，-SBF 3M中的M可以为一价、二价、三价或多价的金属阳离子，若为非一价离子，则-SBF 3的数量对应的增加以使其与M的价数恰好配合便可。
所述“三氟化硼类化合物”指三氟化硼、含有三氟化硼的化合物或三氟化硼络合物等等。
本发明的发明点为提供了一种可作为电解质添加剂、电解质盐以及可聚合单体的的二元硫基三氟化硼盐，即在该三氟化硼盐中含有两个-SBF 3M基团，其中，M为Li +或Na +等。该二元的三氟化硼盐可应用于液态电池、混合固液电池、半固态电池、凝胶电池、准固态电池和全固态电池中。该化合物的制备方法简单、巧妙，得率高。即将原料、三氟化硼类化合物和M源进行反应所得，具体为原料中的-SH参与反应，其他结构不参与反应。具体的制备方法主要包括两种：
一、氮气/氩气气氛下，M源与原料加入到溶剂中，混合，在5～50℃反应5-24小时，所得混合溶液于20-80℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体；加三氟化硼类化合物，5-50℃搅拌反应6-24小时，将所得混合液于20-80℃、真空度约-0.1MPa的条件下减压干燥，得到粗产物，将粗产物洗涤、过滤、干燥，得终产物二元有机三氟化硼盐，得率为74～95％。
二、氮气/氩气气氛下，原料与三氟化硼类化合物加入到溶剂中，混合均匀，在5-50℃下反应6-24小时，所得混合溶液于20-80℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，反应得中间体；将M源加入至溶剂中，然后将含有M源的溶剂加入到中间体中，5-50℃搅拌反应5-24小时，即得粗产物，将粗产物直接洗涤或减压干燥后洗涤，然后过滤、干燥，得终产物二元有机三氟化硼盐，得率为74～95％。
以上两种具体的制备方法中，三氟化硼类化合物可包括三氟化硼乙醚络合物、三氟化硼四氢呋喃络合物、三氟化硼丁醚络合物、三氟化硼乙酸络合物、三氟化硼单乙胺络合物、三氟化硼磷酸络合物等等。M源包括但不限于金属锂/钠片、甲醇锂/钠、氢氧化锂/钠、乙醇锂/钠、丁基锂/钠、乙酸锂/钠等。每一处所述的溶剂独立地为醇类(有些液体醇类的原料也可同时为溶剂)、乙酸乙酯、DMF、丙酮、己烷、二氯甲烷、四氢呋喃、乙二醇二甲醚等。洗涤可用小极性溶剂，如乙醚、正丁醚、异丙醚、正己烷、环己烷、二苯醚等。
实施例1：原料
Figure PCTCN2021115604-appb-000049
制备方法：氮气气氛下，将0.01mol原料和三氟化硼四氢呋喃络合物(2.8g，0.02mol)在15ml乙二醇二甲醚中混合均匀，室温反应12小时。所得混合溶液于40℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体。将乙醇锂(1.04g，0.02mol)溶解在10ml的乙醇中缓慢加入到中间体中，室温下搅拌反应8小时，将所得混合液于40℃、真空度约-0.1MPa的条件下减压干燥，得到的固体用正丁醚洗涤三次，经过滤、干燥，得到产物M1，Q为-S-BF 3Li。产率为77％，核磁如图1所示。
实施例2：原料
Figure PCTCN2021115604-appb-000050
制备方法：氩气气氛下，将0.01mol原料和三氟化硼乙醚络合物(2.98g,0.021mol)在15ml THF中混合均匀，室温反应12小时。所得混合溶液于30℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体。将14ml丁基锂的己烷溶液(c＝1.6mol/L)加入到中间体中，室温搅拌反应6小时，将所得混合液于40℃、真空度约-0.1MPa的条件下减压干燥，得到的粗产物用环己烷洗涤3次，过滤、干燥，得到产物M2，Q为-S-BF 3Li。产率为85％，核磁如图2所示。
实施例3：原料
Figure PCTCN2021115604-appb-000051
制备方法：氮气气氛下，取0.01mol原料和甲醇锂(0.76g,0.02mol)，用20ml甲醇混合均匀，室温反应18小时。所得混合溶液于40℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体。将三氟化硼四氢呋喃络合物(3.07g，0.022mol)加入到中间体中，室温搅拌反应12小时，将所得混合液于40℃、真空度约-0.1MPa的条件下减压干燥，得到的固体用异丙醚洗涤三次、经过滤、干燥，得到产物M3，Q为-S-BF 3Li。产率84％，核磁如图3所示。
实施例4：原料
Figure PCTCN2021115604-appb-000052
制备方法：氩气气氛下，将0.01mol原料和三氟化硼四氢呋喃络合物(3.07g，0.022mol)在15ml THF中混合均匀，室温反应12小时。所得混合溶液于30℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体。将14ml丁基锂的己烷溶液(c＝1.6mol/L)加入到中间体中，室温搅拌反应6小时，将所得混合液于35℃、真空度约-0.1MPa的条件下减压干燥，得到的粗产物用正己烷洗涤3次，过滤、干燥，得到产物M4，Q为-S-BF 3Li。产率为84％，核磁如图4所示。
实施例5：原料
Figure PCTCN2021115604-appb-000053
制备方法：氩气气氛下，将0.01mol原料和三氟化硼乙酸络合物(3.83g，0.0204mol)在15ml THF中混合均匀，40℃反应12小时，所得混合溶液于40℃、真空度约-0.1MPa的条件下减压干燥除去溶剂，得到中间体。将乙酸钠(1.64g，0.0204mol)溶解在10ml的DMF中并加入到中间体中，45℃搅拌反应8小时，将所得混合液于80℃、真空度约-0.1MPa的条件下减压 干燥，得到的固体用二苯醚洗涤三次、经过滤、干燥，得到产物M5，Q为-S-BF 3Na。产率为80％，核磁如图5所示。
实施例6：原料
Figure PCTCN2021115604-appb-000054
制备：由原料通过实施例3的方法制备得到产物M6，Q为-S-BF 3Li。产率85％，核磁如图6所示。
实施例7：原料
Figure PCTCN2021115604-appb-000055
制备：由原料通过实施例1的方法制备得到产物M7，Q为-S-BF 3Li。产率79％，核磁如图7所示。
实施例8：原料
Figure PCTCN2021115604-appb-000056
制备：由原料通过实施例2的方法制备得到产物M8，Q为-S-BF 3Li。产率82％，核磁如图8所示。
实施例9：原料
Figure PCTCN2021115604-appb-000057
制备：由原料通过实施例4的方法制备得到产物M9，Q为-S-BF 3Li。产率84％，核磁如图9所示。
实施例10：原料
Figure PCTCN2021115604-appb-000058
制备：由原料通过实施例3的方法制备得到产物M10，Q为-S-BF 3Li。产率81％，核磁如图10所示。
实施例11：原料
Figure PCTCN2021115604-appb-000059
制备：由原料通过实施例2的方法制备得到产物M11，Q为-S-BF 3Li。产率86％，核磁如图11所示。
实施例12：原料
Figure PCTCN2021115604-appb-000060
制备：由原料通过实施例1的方法制备得到产物M12，Q为-S-BF 3Li。产率85％，核磁如图12所示。
实施例13：原料
Figure PCTCN2021115604-appb-000061
制备：由原料通过实施例2的方法制备得到产物M13，Q为-S-BF 3Li。产率87％，核磁如图13所示。
实施例14：原料
Figure PCTCN2021115604-appb-000062
制备：由原料通过实施例1的方法制备得到产物M14，Q为-S-BF 3Li。产率79％，核磁如图14所示。
实施例15：原料
Figure PCTCN2021115604-appb-000063
制备：由原料通过实施例3的方法制备得到产物M15，Q为-S-BF 3Li。产率88％，核磁如图15所示。
实施例16
本发明中所保护的不饱和杂环的三氟化硼盐主要起三个方面的作用：1、在电解质(包括液态和固态)中用作添加剂，主要起到生成钝化层的作用，并且由于本身可以解离离子，起到补充所消耗的离子作用，因此对于电池的首周效率、首周放电比容量、长循环稳定性、倍率性能均有很大提升。2、在电解质(包括液态和固态)中作为盐，主要起到提供离子传输兼顾钝化电极的作用，单独作为盐或与传统的盐配合作为双盐应用，效果好。3、对于可聚合的单体，聚合后还可作为单离子导体聚合物电解质应用，当作为单离子导体聚合物电解质应用时，电池显示出非常优异的循环性能。下面以试验的方式来说明本申请的性能。
一、作为液态电解质添加剂
(1)正极极片
将正极主材活性物质、电子导电添加剂、粘结剂按照质量比95:2:3加入到溶剂中，溶剂占总浆料的质量分数为65％，混合搅拌均匀得到具有一定流动性的正极浆料；将正极浆料涂布在铝箔上，烘干、压实、裁切后，得到可用的正极极片。这里活性物质选择使用钴酸锂(LiCoO 2，简写LCO)、镍钴锰酸锂(选用NCM811)、镍钴铝酸锂(LiNi 0.8Co 0.15Al 0.05O 2，简写NCA)、镍锰酸锂(LiNi 0.5Mn 1.5O 4，简写LNMO)、Na 0.9[Cu 0.22Fe 0.3Mn 0.48]O 2(简写NCFMO)，电子导电添加剂均选择使用碳纳米管(CNT)和Super P，粘结剂使用聚偏氟乙烯(PVDF)，溶剂使用N-甲基吡咯烷酮(NMP)。
(2)负极极片
将负极主材活性物质(金属Li除外)、电子导电添加剂、粘结剂按照95:2.5:2.5加入到溶剂去离子水中，溶剂占总浆料的42％，混合搅拌均匀得到具有一定流动性的负极浆料；将负极浆料涂布在铜箔上，烘干、压实后得到可用的负极极片。这里活性物质选择使用石墨(C)、硅碳(SiOC450)、金属锂(Li)、软碳(SC)，导电剂为CNT和Super P，粘结剂为羧甲基纤维素(CMC)和丁苯橡胶(SBR)。
本发明选用的正负极体系如表1所示：
表1正负极体系
电池正负极体系 正极主材 负极主材
A1 LCO SiOC450
A2 NCM811 SiOC450
A3 NCM811 Li
A4 NCA C
A5 LNMO C
A6 LCO Li
A7 NCFMO SC
(3)配制液态电解质
M1～M15、有机溶剂、常规盐、常规添加剂混合均匀得到系列电解质E1～E15，这里所用到的溶剂为碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)。常规添加剂为氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)、磷酸三甲酯(TMP)、乙氧基五氟环三磷腈(PFPN)、硫酸乙烯酯(DTD)；常规盐为双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiODFB)、双氟磺酰亚胺锂(LiFSI)、六氟磷酸锂(LiPF 6)、双(三氟甲基)磺酰亚胺锂(LiTFSI)、四氟硼酸锂(LiBF 4)、六氟磷酸钠(NaPF 6)。具体成分、配比等如表2所示。
表2本申请结构作为添加剂配制液态电解质
Figure PCTCN2021115604-appb-000064
注：1M指1mol/L。
对比样：按照E1～E15的比例，将M1～M15换成空白(即不添加M1～M15)，即可得到对应的常规液态电解质对比样L1～L15。
(4)扣式电池装配
含有本申请实施例中结构作为添加剂的液态电解质系列E1～E15和常规液态电解质L1～L15对比样组装成扣式电池，具体如下：负极壳、负极极片、PE/Al 2O 3隔膜、电解质、正极极片、不锈钢片、弹簧片、正极壳装配成扣式电池，室温进行长循环测试，其中循环方式0.1C/0.1C 1周、0.2C/0.2C 5周、1C/1C 44周(C代表倍率)，所述正极极片是直径为12mm的圆片，所述负极极片是直径为14mm的圆片，所述隔膜是直径为16.2mm的圆片，为商用Al 2O 3/PE多孔隔膜。
由E1～E15配制的电池体系分别为电池1～电池15，由L1～L15配制的电池体系分别为对比电池1～对比电池15。电池具体配置和电压范围如表3所示。电池1～15和对比电池1～15室温下的首周放电比容量、首周效率、循环50周容量保持率结果如表4所示。
表3实施例电池和对比例电池的配置和测试方式
Figure PCTCN2021115604-appb-000065
表4实施例电池和对比例电池测试结果对比
实施例电池和对比例电池 首周放电比容量(mAh/g) 首周效率(％) 循环50周容量保持率(％)
电池1 160.9 82.7 89.0
对比电池1 127.3 74.3 77.3
电池2 161.0 82.8 88.7
对比电池2 127.4 74.4 77.5
电池3 161.2 83.3 89.3
对比电池3 154.4 81.1 83.4
电池4 161.5 83.2 89.2
对比电池4 154.3 81.2 83.6
电池5 109.6 81.1 91.5
对比电池5 95.5 70.3 86.3
电池6 171.4 83.5 89.4
对比电池6 141.3 75.4 77.4
电池7 172.3 84.2 89.7
对比电池7 164.2 82.1 87.0
电池8 171.6 83.7 89.6
对比电池8 141.3 75.4 77.4
电池9 199.7 92.1 90.5
对比电池9 180.0 84.3 82.1
电池10 201.6 92.5 91.3
对比电池10 197.3 90.3 87.2
电池11 199.8 92.2 90.5
对比电池11 180.1 84.4 82.0
电池12 201.9 92.5 91.4
对比电池12 197.3 90.3 87.3
电池13 168.4 81.7 89.6
对比电池13 146.2 73.5 82.1
电池14 168.2 81.8 89.5
对比电池14 146.3 73.4 82.2
电池15 139.7 89.5 89.8
对比电池15 135.3 87.0 87.0
从上述电池和对比电池测试结果来看，在扣式电池中，正负极体系相同时，使用该发明的结构M1～M15作为液态电解质添加剂的电池首周效率、首周放电比容量、容量保持率均比不添加的效果要好很多，且性能优于目前的常规添加剂。此外，在有常规添加剂存在的情况下，使用本申请的三氟化硼盐添加剂的电池显示出更优异的电化学性能。
二、作为液态电解质中的盐
(1)配制液态电解质
M2、M3、M7、M11、有机溶剂、常规添加剂、常规盐混合均匀得到系列液态电解质R2、R3、R7、R11，常规盐、有机溶剂、常规添加剂混合均匀得到系列常规液态电解质Q2、Q3、Q7、Q11，使用的溶剂和常规添加剂均包含在本实施例“一”中所述的溶剂和常规添加剂。液态电解质具体成分、配比等如表5所示。
表5合成的含硼有机物作为盐配制的液态电解质
Figure PCTCN2021115604-appb-000066
(2)电池装配
获得的系列液态电解质R(表5所示)和常规液态电解质Q(表5所示)组装成扣式电池，正 负极、隔膜大小、装配方法、电池的循环方式同本实施例“一”中所示的扣式电池，分别为电池2、3、7、11以及对应的对比电池。电池具体配置、循环方式和电压范围如表6所示，电池和对比电池室温下的首周放电比容量、首周效率、循环50周容量保持率结果如表7所示。
表6实施例电池和对比电池的配置和测试方式
Figure PCTCN2021115604-appb-000067
表7表6所示的实施例电池和对比电池测试结果对比
Figure PCTCN2021115604-appb-000068
综上，本发明所提供的三氟化硼盐在非水溶剂中，离子容易被溶剂化，为电池提供较高的离子电导率，且稳定性较高，在LCO、NCM811为正极，SiOC450、Li为负极的液态电池体系中，均显示出非常优异的电化学性能，首效、首周放电比容量、容量保持率均比较高，且性能基本不次于传统盐对应的电池。
三、作为固态电解质中的盐
(1)制备聚合物电解质膜
在露点低于-60℃的环境中，将本发明提供的结构、聚合物、无机填料按照比例溶解在DMF中，经搅拌混合、涂覆成膜、辊压、烘干后，得到聚合物电解质膜G8、G10、G13、G15和聚合物对比电解质膜G’1～G’2，具体成分、配比等如表8所示。聚合物选用聚环氧乙烷(PEO，分子量为100万)，无机填料选用160nm的LLZO，即中值粒径为160nm的晶型为立方相的Li 7La 3Zr 2O 12无机氧化物固态电解质。
表8聚合物电解质的具体成分和配比
聚合物电解质膜 聚合物 盐 无机填料 前者质量比 溶剂
G8 PEO 100万 M8 160nm LLZO 4.2：1：0.8 DMF
G10 PEO 100万 M10 / 4.2：1 DMF
G13 PEO 100万 M13 160nm LLZO 4.2：1：0.8 DMF
G15 PEO 100万 M15 / 4.2：1 DMF
G’1 PEO 100万 LiTFSI 160nm LLZO 4.2：1：0.8 DMF
G’2 PEO 100万 LiTFSI / 4.2：1 DMF
(2)正极极片的制备
在露点低于-60℃的环境中，将正极主材活性物质、聚合物+盐(比例同聚合物电解质膜)、电子导电添加剂、粘结剂按照质量比91.3:4.8:2.1:1.8在溶剂中经搅拌混合、涂覆于铝箔、烘干、辊压，得到全固态正极极片。这里活性物质选择使用钴酸锂(LiCoO 2，简写LCO)、镍钴锰酸锂(选用NCM811)，电子导电添加剂使用Super P，粘结剂使用聚偏氟乙烯(PVDF)
将50μm厚的金属锂薄片压制于铜箔上作为负极极片。
(3)电池装配及测试
将聚合物电解质膜和正负极极片经裁切后组装成1Ah全固态软包电池，电池进行50℃长循环测试，循环方式为0.1C/0.1C 2周，0.3C/0.3C 48周。电池具体的装配体系和测试方法如表9所示，测试结果如表10所示。
表9实施例电池和对比例电池的配置和测试方式
Figure PCTCN2021115604-appb-000069
表10表9中实施例电池和对比电池的测试结果对比
Figure PCTCN2021115604-appb-000070
通过表9和表10的数据，可以看出本申请的M8、M10、M13、M15制备而成的电池具有优异的长循环稳定性且性能均优于LiTFSI对应电池的循环性能。可能是由于本发明的硫基三氟化硼盐不仅具有优异的离子传输性能，且可以在正极表面形成一层更加致密稳定的钝化层，阻止正极活性材料对电解质各组分的催化分解，此外，本发明的三氟化硼盐不会腐蚀集流体，因而展现出优于传统盐的性能。
四、单离子导体聚合物电解质
(1)配制电解质
将单体M2、M12、M13、M14、塑化剂、电池添加剂、盐、引发剂搅拌均匀后，形成前驱体溶液，获得前驱体S2、S12、S13、S14，具体配比如表11。使用的引发剂为偶氮二异丁 腈(AIBN)。
表11前驱体溶液组成
Figure PCTCN2021115604-appb-000071
(2)电池装配
由表11获得的电解质前驱体溶液S2、S12、S13、S14，由这些前驱体分别组装成软包电池，即为电池(即实施例电池)2、12、13、14；具体如下：将尺寸为64mm×45mm的正极极片、65mm×46mm的负极极片、隔膜装配成2Ah软包电芯，经叠片、烘烤、注液、化成过程，得到二次电池，电池装配体系为A2，隔膜使用商业PE/Al 2O 3多孔膜。
(3)电池测试
由实施例2、12、13、14制备的二次电池固化完全后，室温下对电池的首周放电容量、首周效率、循环50周容量保持率进行测试，测试电压范围为3.0～4.2V，其中循环方式0.1C/0.1C2周、0.3C/0.3C 48周(C代表倍率)，测试结果如表12所示。
表12实施例电池的测试结果
Figure PCTCN2021115604-appb-000072
如表12，通过实施例电池中的测试数据发现可聚合单体M2、M12、M13、M14构成的前驱体S2、S12、S13、S14经过原位固化之后作为聚合物电解质，在NCM811为正极、SiOC450为负极的固态电池体系中，显示出非常优异的电化学性能，首效、首周放电容量、容量保持率均比较高。实施例2聚合之后可得到性能优异的固态电解质，此外当额外匹配常规盐使用时，由于提高了解离的离子数量，因而电池展现出更加优异的电化学性能。
此外，附图部分挑选了一些不饱和杂环硫基三氟化硼盐作为添加剂和盐的效果图作为展示。图16～图19分别为实施例2/4/10/15作为电解质添加剂所制成的电池2/4/10/15与对应的不含有本发明实施例2/4/10/15的对比电池2/4/10/15的效果对比图。图20～图21分别为实施例7/11作为电解质盐所制成的电池7/11与对应的不含有本发明实施例7/11的对比电池7/11的效果对比图。图22为实施例8作为固态电解质盐的电池8和以LiTFSI作为盐的对比电池1的效果对比图。图23为实施例13中的单体聚合后作为聚合物电解质所制成的电池13的效果图。由图也可知本申请结构具有极佳的效果。此外，在循环图中，上面有小方块
Figure PCTCN2021115604-appb-000073
的线条代表实施例电池，有小圆圈
Figure PCTCN2021115604-appb-000074
的线条代表对比例电池，由图可知，代表实施例电池的线条均在代表对比例电池的线条上方，实施例电池效果更优。
综上，首周效率、首周放电比容量、首周放电容量、容量保持率等性能对于电池的整体性能具有直接且显著的影响，其直接决定着电池能否应用。因此，提高这些性能是众多本领域研究者的目标或方向，但在本领域中，这些性能的提高是非常不易的，一般能提高3-5％ 左右便是较大的进展。本申请在前期试验数据中，很惊喜的发现，这些数据与常规的数据相比，具有很大的提高，尤其是作为电解质添加剂时，性能提高了5-30％左右，且本申请中的添加剂与常规添加剂联合应用也表现出了较佳的效果。实施例部分只展示了作为液态电解质的添加剂，而本申请中的三氟化硼盐也是可以作为固态电解质的添加剂，由于篇幅原因，这里就不一一展示。更惊喜的是，该组分还可作为电解质中的盐，且效果非常好，试验中显示，其性能基本不次于甚至还优于传统锂盐对应的电池，而且本申请中的结构可应用于固态电解质中，并显示出了优异的效果。此外，本申请还可作为单离子导体聚合物电解质中的单体，由于篇幅原因，这里就不一一展示。更重要的是，本申请的结构类型也与常规的结构具有巨大的区别，这为本领域的研发提供了一种新的方向和思路，也为进一步的研究带来了很大的空间，且本申请中的一个结构有多种用途，意义极大。
实施例17
为了进一步研究和了解本申请中的结构性能，本申请人将其与以下结构分别作为电解质添加剂评测其对电池在室温下的长循环性能的影响。本申请的结构选择以下结构M16，以下对比例结构为结构W。
(1)液态电解质配制
Figure PCTCN2021115604-appb-000075
表13 W、M16作为添加剂配制电解质
Figure PCTCN2021115604-appb-000076
在上表中，S0为对照组。
(2)扣式电池装配
获得的电解质S0～S2组装成扣式电池，正负极、隔膜大小、装配方法、电池的循环方式同本实施例16“一”中所示的扣式电池，分别为电池Y0～Y2。电池具体配置、循环方式和电压范围如表14所示，测试结果如表15所示。
表14电池的装配和测试方式
Figure PCTCN2021115604-appb-000077
表15电池的测试结果
Figure PCTCN2021115604-appb-000078
Figure PCTCN2021115604-appb-000079
从电池Y0～Y2测试结果可以看出，W、M16作为电解质添加剂，均能提升电池的首效、1～50周放电比容量和容量保持率。但与W相比，M16对电池的首效和首周放电比容量的提升更明显，究其原因，可能是由于W为非盐的络合物，与本申请结构区别大，且其不含-SBF 3Li，当作为添加剂占盐质量比为1％时在正负极中不能形成很好的钝化层。而含两个-SBF 3M的M16本身含锂源，在形成良好钝化层的过程中同时较少消耗从正极脱出的锂离子，从而提高电池的首效，首周放电比容量和容量保持率。即本申请中的三氟化硼有机盐在电解质中既可作为添加剂又可作为盐，如M16，其本身在电解质中的双重作用可起协同作用，故效果比其他组分好。更清晰明确的机理，本申请人还在进一步研究中。但无论如何，可以肯定的是，SBF 3M的存在以及数量对于电池性能是有实质性影响的。
在本发明中，选择了实施例1-15中的结构作为代表来说明本申请的制备方法和效果。其他没有列举的结构均可采用实施例1-5中任意一个中所记载的方法来进行制备。其制备方法均为由原料、三氟化硼类化合物以及M源反应得到产物三氟化硼有机物盐，即原料中的-SH变为-SBF 3M，M可为Li +、Na +等，其它结构不变。另外，还有很多结构本申请人的研究团队已经做了系列化效果试验，效果都很不错，与上述实施例中的效果类似，如：由原料
Figure PCTCN2021115604-appb-000080
Figure PCTCN2021115604-appb-000081
等等所制成的本申请中的三氟化硼盐，效果均很好，但由于篇幅关系，只记载了部分结构的数据。
在本发明中，还需要注意的是，①-SBF 3M中的-BF 3须与硫原子S连接，且硫原子再以一个单键与碳原子C连接，因此，S不可以是位于环上的硫。S如果与非C原子连接后，或者S位于环上(或S上还连接有其它两个基团)时，结构均与本申请区别较大，因此，这种结构是否可以应用在本申请的电解质中、会有什么效果、应用场景等均无法预测，因此，对于这些结构本发明人会进行单独研究，这里不会进行过多探讨；②本申请中的不饱和杂环类三氟化硼盐电解质优选为非聚合态的有机物，聚合态有其独特的特性和特点，本申请人以后可能会专门对聚合态进行研究，本申请为非聚合态。
对于本申请而言，以上两种情况均需要满足，因为，若不满足，则与本申请的性质会有较大区别，故改变以后的应用场景或效果不好预测，可能会有较大改变，若有价值，以后本发明人会另行进行专门研究。
在本发明中，本申请人对该系列结构做了极大量的试验，在第一个结构效果出来以后，后续的试验探索以及数据补充加起来跨度为两年左右，有时候为了更好的与现有体系进行对比，存在同一个结构和体系，做了不止一次试验的情况，因此，不同次的试验可能会存在一定的误差。
此外，本申请实施例中的原料均为可直接购买得到或经过简单常规的合成可以得到的，原料或原料的合成不具有任何创新，因此，不过多记载。
最后应说明的是：以上所述的各实施例仅用于说明本发明的技术方案，而非对其限制； 尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或全部技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (11)

  1. 一种含有不饱和杂环的硫基三氟化硼盐类电解质，其特征在于：所述电解质包括以下通式I所表示的不饱和杂环类硫基三氟化硼盐：
    Figure PCTCN2021115604-appb-100001
    在以上通式Ⅰ中，R’代表不饱和杂环，该不饱和杂环上至少含有一个杂原子，且同时至少含有一个不饱和键；所述杂原子选自S、N、O、P、Se、Ca、Al、B或Si；M为金属阳离子；E 1、E 2独立地为无、基团、链式结构或含有环的结构；
    R为取代基，代表环上任意一个H都可以被取代基取代，且取代基可取代一个H也可以取代两个或多个H，若两个或多个H被取代，则取代基可相同也可不同。
  2. 根据权利要求1所述的电解质，其特征在于：在通式Ⅰ中，所述不饱和杂环为三元～二十元环；所述不饱和键为双键；
    通式Ⅰ中的两个-SBF 3M可为邻位、间位、间隔2个原子或间隔超过两个原子；
    优选地，在通式Ⅰ中，与-SBF 3M直接连接的原子为碳原子C；所述杂原子选自S、N、O、P或Si；
    优选地，与-SBF 3M连接的碳原子C包括羰基碳和非羰基碳，所述羰基碳包括-C＝O或-C＝S，所述非羰基碳为C原子上不含有＝O或＝S的结构；
    优选地，所述通式Ⅰ中任意一个C上的H均可独立地被卤素取代。
  3. 根据权利要求2所述的电解质，其特征在于：所述取代基R选自H、卤素原子、羰基、酯基、醛基、醚氧基、醚硫基、＝O、＝S、
    Figure PCTCN2021115604-appb-100002
    硝基、氰基、氨基、酰胺、磺酰胺基、磺基烷、磺酸基、肼基、重氮基、烷基、杂烷基、烯基、杂烯基、炔基、杂炔基、烯炔基、杂烯炔基、环类取代基、盐类取代基以及这些基团中任意一个氢H被卤素原子取代后的基团；
    其中，所述酯基包括羧酸酯、碳酸酯、磺酸酯和磷酸酯，R 2、R 3独立地为H、烷基、杂烷基、烯基、杂烯基、炔基、杂炔基、烯炔基、杂烯炔基或环；
    优选地，所述杂烷基、杂烯基、杂炔基和杂烯炔基中的任何一个结构均含有至少一个所述非碳原子，该非碳原子选自卤素、S、N、O、P、Se、Ca、Al、B或Si；所述环类取代基包括三元～八元环以及至少由两个单环构成的多环；所述盐类取代基包括但不限于硫酸盐、磺酸盐、磺酰亚胺盐、碳酸盐、羧酸盐、硫醚盐、氧醚盐、铵盐、盐酸盐、硝酸盐、叠氮盐、硅酸盐、磷酸盐；
    所述羰基为-R 10COR 11，酯基为-R 12COOR 13、-R 12OCOR 17、-R 12SO 2OR 13、R 12O-CO-OR 13或
    Figure PCTCN2021115604-appb-100003
    醚氧基为-R 14OR 15，醚硫基为-R 14SR 15；磺基烷为-R 18SO 2R 19，氨基为＝N-R 20、
    Figure PCTCN2021115604-appb-100004
    或-CH＝N-R 24，酰胺为
    Figure PCTCN2021115604-appb-100005
    磺酰胺基为
    Figure PCTCN2021115604-appb-100006
    其中，R 2、R 3、R 10、R 11、R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 28、R 29、R 30、R 31、R 32、R 33、R 34、R 35独立地为烷基、杂烷基、烯基、杂烯基、炔基、杂炔基、烯炔基、杂烯炔基或环，杂烷/烯/炔/烯炔基为带有至少一个所述非碳原子的烷/烯/炔/烯炔基；所述环与所述环类取代基所限定的种类一致；且R 2、R 3、R 10、R 12、R 14、R 18、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 29、R 30、R 31、R 32、R 33、R 35可独立地为H或无；与N或O直接相连的基团还能够为金属离子；
    且可选择地，所述取代基还包括以上任意一个基团中的任意一个C＝O被C＝S替代后的取代基。
  4. 根据权利要求3所述的电解质，其特征在于：E 1或E 2选自无、羰基、酯基、烷基、杂烷基、烯基、杂烯基、含有环状结构的基团、
    Figure PCTCN2021115604-appb-100007
    ＝N-R 6-和这些基团中任意一个C＝O被C＝S替代后的基团以及这些基团中任意一个C-O被C-S替代后的基团，所述杂烯基中的双键包括含有碳碳双键C＝C的结构和含有碳氮双键C＝N的结构，R 4、R 5和R 6独立地与权利要求3中的R 2、R 3中限定的种类一致。
  5. 根据权利要求4所述的电解质，其特征在于：在通式Ⅰ中，所述不饱和杂环R’为三～十二元环；其中，三元环：含有1个双键和1个杂原子；四元环：含有1个双键，同时含有1个或2个杂原子；五元环：含有1个或2个双键，同时含有1个、2个或3个杂原子；六元环：含有1个或2个双键，同时含有1个、2个、3个、4个、5个或6个杂原子；七元环：含有1、2或3个双键，同时含有1个、2个或3个杂原子；八元环和九元环：含有1、2、3或4个双键，同时含有1、2或3个杂原子；十元环、十一元环和十二元环：含有1、2、3、4或5个双键，同时含有1、2或3个杂原子；两个-SBF 3M直接或间接连接于以上所述杂环R’的任意一个或两个原子上；
    优选地，所述不饱和杂环R’包括但不限于以下环：呋喃、3,4-二氢呋喃、2,3-二氢呋喃、噻吩、2,3-二氢噻吩、3,4-二氢噻吩、吡咯、3,4-二氢吡咯、2,3-二氢吡咯、咪唑、吡唑、噻唑、恶唑、异恶唑、三唑、二氢三唑、噻二唑、1,3-二氢吡啶、1,4-二氢吡啶、二氢嘧啶、四氢嘧啶、二氢吡嗪、四氢吡嗪、二氢哒嗪、四氢哒嗪、二氢三嗪、四氢三嗪、吡喃、二氢吡喃、硫吡喃、二氢硫吡喃、
    Figure PCTCN2021115604-appb-100008
    Figure PCTCN2021115604-appb-100009
    上述杂环R’中，可连接所述取代基R；两个-SBF 3M直接连接或分别通过E 1、E 2间接的连接于上述各个杂环R’中的任意两个或一个原子上。
  6. 根据权利要求5所述的电解质，其特征在于：所述通式Ⅰ包括但不限于以下化合物：
    Figure PCTCN2021115604-appb-100010
    Figure PCTCN2021115604-appb-100011
    在以上结构中，-SBF 3指-SBF 3M；每个环状结构中的E 1和E 2均独立地与权利要求1-5中任意一项所限定的E 1和E 2一致；
    每个不饱和杂环上的任意一个H均可独立地选自A 1、A 2、A 3或A 4中的任意一个取代基，A 1、A 2、A 3和A 4均独立地选自权利要求1-5中任意一项所述的取代基R中所限定的任意一个取代基。
  7. 根据权利要求3-6中任意一项所述的电解质，其特征在于：在所述取代基R、A 1、A 2、A 3或A 4中，所述卤素原子包括F、Cl、Br、I；
    R 2、R 3、R 10、R 11、R 12、R 13、R 14、R 15、R 16、R 17、R 18、R 19、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 28、R 29、R 30、R 31、R 32、R 33、R 34、R 35独立地为C 1-10烷基、C 1-10杂烷基、C 1-10烯基或C 1-10杂烯基，杂烷基或杂烯基为带有至少一个杂原子的烷基或烯基；且R 2、R 3、R 10、R 12、R 14、R 18、R 20、R 21、R 22、R 23、R 24、R 25、R 26、R 27、R 29、R 30、R 31、R 32、R 33、R 35可独立地为H或无，与N或O直接相连的基团还能够为金属离子；
    氰基选自-CN、-CH 2CN、-SCH 2CH 2CN或-CH 2CH 2CN；
    所述烷基选自1-18个C的烷基；所述杂烷基选自含有至少一个所述杂原子的烷基；烯基选自1-18个C的烯基；杂烯基选自含有至少一个所述杂原子的烯基；炔基选自1-10个C的炔基；杂炔基选自含有至少一个所述杂原子的炔基；烯炔基选自同时含有三键和双键的含有1-10个C的烯炔基；杂烯炔基选自含有至少一个所述杂原子的烯炔基；
    所述环类取代基包括环丙基、环丁基、环戊基、环己基、环庚基和多环；优选地，所述环类取代基中的任意一个环独立地通过以下任意一个连接基团与被取代的不饱和杂环连接：-CH 2-、-CH 2CH 2-、丙基、丁基、乙烯、丙烯、丁烯、乙炔、丙炔、-COO-、-CO-、-SO 2-、 -N＝N-、-O-、-OCH 2-、-OCH 2CH 2-、-CH 2OCH 2-、-COCH 2-、-CH 2OCH 2CH 2-、-OCH 2CH 2O-、-COOCH 2CH 2-、-S-、-S-S-、-CH 2OOC-、-CH＝CH-CO-、
    Figure PCTCN2021115604-appb-100012
    或单键；R 42独立地选自H、甲基、乙基或丙基；R 36、R 37独立地选自甲基、乙基、丙基、异丙基、丁基、氟代甲基、氟代乙基、乙烯基或丙烯基；所述环类取代基中的任意一个环上的任意一个带有H的原子上均可连接第一取代基，该第一取代基与所述取代基R所限定的类型一致；优选地，该第一取代基选自H、卤素原子、甲基、乙基、丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、氟代甲基、氟代乙基、甲氧基、乙氧基、硝基、烯基、炔基、酯基、磺酸盐、磺基烷、酰胺基、氰基、醛基、-SCH 3、-COOCH 3、COOCH 2CH 3、-OCF 3、＝O、-N(CH 3) 2、-CON(CH 3) 2、-SO 2CH 3或-SO 2CH 2CH 3，该酯基包括所述的碳酸酯、磺酸酯、羧酸酯和磷酸酯。
  8. 根据权利要求1-6中任意一项所述的电解质，其特征在于：E 1或E 2选自无、-CH 2-、羰基、酯基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、己基、乙烯基、丙烯基、丁烯基、戊烯基、乙炔基、丙炔基、丁炔基、环己基、环戊基、1,3-己二烯基、-C＝N-、-C(CH 3) 2-、-CH(CH 3)-、-CH(CF 3)-、-C(CF 3) 2-、-SCH 2CH 2-、-CH 2CH 2SCH 2CH 2-、-CH 2CH 2CH(CH 3)-、-Z' 1CH 2CH 2-、-O-CH 2(CH 2) 4CH 2-、-N＝C(CH 3)-、-O-(CH 2) 6-、-CH 2Z' 1CH 2-、-CH 2(CH 3)Z' 1CH 2-、-CH 2CH 2Z' 1CH 2-、
    Figure PCTCN2021115604-appb-100013
    Figure PCTCN2021115604-appb-100014
    -O-CH 2-CH 2-O-CH 2-CH 2-、
    Figure PCTCN2021115604-appb-100015
    和这些基团中任意一个C＝O被C＝S替代后的基团以及这些基团中任意一个C-O被C-S替代后的基团；所述羰基包括-CO-、-CH 2CO-、-CH 2CH 2CO-、-CH 2CH 2CH 2CO-、-CH 2COCH 2-、-CH 2CH 2COCH 2-、-CH＝CH-CO-、-OCH 2CH 2CH 2CO-、＝N-CH 2-CO-、-Z' 1CH 2CO-、-Z' 1CH 2CH 2CO-、-Z' 1CH 2CH 2CH 2CO-、-CH 2(CH 2) 5CO-、-CH 2(CH 2) 6CO-、
    Figure PCTCN2021115604-appb-100016
    所述酯基包括-COOCH 2-、-COOCH 2CH 2-和-CH 2COOCH 2-；
    其中，此权利要求中的Z' 1选自-O-、-S-、-S-S-、
    Figure PCTCN2021115604-appb-100017
    磺酰基、磺酰亚胺基或磺酰氧基，其中，R 41为H、甲基、乙基、丙基、异丙基、丁基、乙氧基或甲氧基，且该R 41中的任意一个氢H均可被F或Cl取代；R 44、R 45独立地为烷基或环；
    R 39选自H、甲基、乙基、丙基、丁基、戊基、环丙基、环戊基、环己基、硝基、噻唑、-CH(CH 3) 2、-CH 2CH(CH 3) 2、-CH 2CH 2NO 3、
    Figure PCTCN2021115604-appb-100018
    其中，R 8、R 37、R 38和R 40独立地为无、卤素原子、甲基、乙基、丙基、丁基、氟代甲基、氟代乙基、甲氧基、硝基、醛基、酮基、酯基、-CH 2-N(CH 3) 2或-CH(CH 3)-Ph，R 9为无或亚甲基；
    优选地，E 1或E 2选自无、-CH 2-、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、异戊基、仲戊基、新戊基、己基、乙烯基、丙烯基、丁烯基、戊烯基、乙炔基、丙炔基、丁炔基、二烯基、-CO-、-CH 2CO-、-CH 2CH 2CO-、-CH 2CH 2CH 2CO-、-C(CH 3) 2-、-CH(CH 3)-、-CH(CF 3)-、-C(CF 3) 2-、-Z' 1CH 2-、-Z' 1CH 2CH 2-、-CH 2Z' 1CH 2-、CH 2CH 2Z' 1CH 2-、 -CH 2CH 2Z' 1CH 2CH 2-、-COOCH 2-、-COOCH 2CH 2-、-CH 2COOCH 2-、
    Figure PCTCN2021115604-appb-100019
    Figure PCTCN2021115604-appb-100020
    其中，此段中的Z' 1为O、S；R 39独立地选自H、甲基、乙基、丙基、环丙基、环戊基、环己基、硝基、-CH(CH 3) 2、-CH 2CH(CH 3) 2、
    Figure PCTCN2021115604-appb-100021
    其中，R 9为无或亚甲基；R 8和R 37独立地选自无、甲基、乙基、丙基、卤素原子、甲氧基、硝基、醛基、氟代甲基、氟代乙基、酮基或酯基。
  9. 根据权利要求1所述的电解质，其特征在于：所述通式Ⅰ的M包括Na +、K +、Li +、Mg 2+或Ca 2+，优选Na +、K +或Li +；
    优选地，所述通式Ⅰ为：权利要求1-8中任意一项所述的通式Ⅰ中的任意一个C上的H全部或部分被卤素取代后的化合物，优选被F取代。
  10. 一种根据权利要求1-9中任意一项所述的电解质的制备方法，其特征在于：该方法为含有两个-SH的不饱和杂环类二元结构、三氟化硼类化合物和M源反应得到产物，即含有两个-SBF 3M的不饱和杂环类硫基三氟化硼盐。
  11. 一种权利要求1-9中任意一项所述的含有不饱和杂环的硫基三氟化硼盐类电解质在二次锂电池中的应用，其特征在于：所述应用为：所述通式I既能够作为盐应用也能够作为添加剂应用，对于可聚合的单体，聚合后还能够作为单离子导体聚合物电解质兼高分子骨架应用；
    优选地，所述应用包括在液态电解质、凝胶电解质、混合固液电解质、准固态电解质、全固态电解质中的应用，所述液态电解质、凝胶电解质、混合固液电解质、准固态电解质、全固态电解质均独立地包括权利要求1-9中任意一项所述的不饱和杂环类硫基三氟化硼盐；
    优选地，所述应用还包括作为电池或电池组的应用，所述电池包括权利要求1-9中任意一项所述的含有不饱和杂环的硫基三氟化硼盐类电解质以及正极、负极、隔膜和封装外壳；该电池包括液态电池、混合固液电池、半固态电池、凝胶电池、准固态电池和全固态电池，所述液态电解质、凝胶电解质、混合固液电解质、准固态电解质或全固态电解质均可应用于液态电池、混合固液电池、半固态电池、凝胶电池、准固态电池或全固态电池中；
    所述电池组包括所述电池。
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