CN114649581B - Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof - Google Patents
Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114649581B CN114649581B CN202011496920.9A CN202011496920A CN114649581B CN 114649581 B CN114649581 B CN 114649581B CN 202011496920 A CN202011496920 A CN 202011496920A CN 114649581 B CN114649581 B CN 114649581B
- Authority
- CN
- China
- Prior art keywords
- salt
- batteries
- boron trifluoride
- electrolyte
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte containing a five-membered cyclic nitrogen-based salt structure, and a preparation method and application thereof. Wherein the electrolyte comprises boron trifluoride salt, and the structure of the boron trifluoride salt is shown as a general formula I. When the nitrogen-based boron trifluoride salt is used as an additive of an electrolyte, a stable passivation layer is formed on the surface of the electrode, M ions are contained in the nitrogen-based boron trifluoride salt, and ions provided by the electrode are less consumed in the film forming process, so that the first cycle efficiency and the cycle performance of the battery can be remarkably improved; when the boron trifluoride salt is used as salt in electrolyte, the boron trifluoride salt provided by the application has good ion transmission property and stable electrochemical performance. The nitrogen-based boron trifluoride salt can be applied to liquid batteries, solid-liquid hybrid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, is beneficial to improving the energy density, the circulation stability and the service life of the batteries, and has low raw material price, simple synthesis and purification process and good economic benefit.
Description
Technical Field
The application relates to the technical field of batteries, in particular to an electrolyte containing a five-membered ring nitrogen-based salt structure, and a preparation method and application thereof.
Background
Batteries have become a traditional way of storing energy in portable devices. The development of intelligent electronics has placed higher demands on the energy density of batteries. In addition, with the further promotion of automobile manufacturers such as Tesla (Tesla), electric automobiles are becoming a new battery application field. Each field of application of a battery requires consideration of electrochemical performance, safety and cost of the battery. In any event, it is imperative to use batteries with higher energy density and longer life to meet the ever-increasing energy demands.
Taking a lithium battery as an example, in order to increase the energy density of the battery, a high-voltage high-specific-volume positive electrode material and a low-voltage high-capacity negative electrode material, such as a high-voltage Lithium Cobalt Oxide (LCO), a high-nickel ternary (NCM 811, NCM622, NCM532, and NCA), a positive electrode material such as Lithium Nickel Manganese Oxide (LNMO), and a negative electrode material such as metallic lithium, graphite, silicon oxycarbon, are required. And meanwhile, the electrolyte with a wide electrochemical window is matched or a stable passivation layer is formed on the surface of the electrode, so that the cycling stability of the battery is improved.
The electrolyte is largely classified into a liquid electrolyte and a solid electrolyte, and the liquid electrolyte has the remarkable advantages of high conductivity and good wettability to the inside of the electrode. However, the organic solvent in the liquid electrolyte is inflammable, uncontrollable side reactions are easy to occur, the electrode interface is unstable, gas production is serious, the capacity is seriously declined, the cycle life of the battery is low, and the safety is poor. The above problems can be significantly suppressed by using a nonflammable solid electrolyte, and in addition, it has also been proposed to suppress the growth of lithium dendrites with a solid electrolyte. Solid electrolytes can be divided into two broad categories, organic polymer electrolytes and inorganic (sulfide and oxide) electrolytes. The polymer has better flexibility, is easy to process and is beneficial to interface contact with an electrode, but has lower ionic conductivity at room temperature, limited thermal stability and narrower electrochemical window; sulfide has higher ionic conductivity and better processing capability, but most sulfides are unstable in air and generate toxic H with water molecules 2 S gas, thus requiring a very demanding processing environment; the oxide has excellent chemical and thermal stability, high voltage resistance, high ionic conductivity, poor flexibility and large interface impedance. Therefore, the liquid electrolyte is still the main material, and in order to improve the cycle stability of the liquid battery, various functional additives such as FEC (fluoroethylene carbonate), VC (vinylene carbonate), VEC (vinylene carbonate) and DTD (ethylene sulfate) are required to be added into the electrolyte, for example, the SEI passivation film formed on the surface of the negative electrode has various inorganic components Li 2 CO 3 、LiF、Li 2 O, liOH, etc., and various organic components ROCOOLi, ROLi, ROCOOLi, the first cycle efficiency and specific discharge volume remain somewhat low due to the consumption of active ions from the positive electrode. If addedThe additive can form a passivation layer with good ion conduction and stability on the surface of the electrode, and less consumption of ions from the electrode, so that the oxidation/reduction decomposition of anode and cathode materials to electrolyte can be effectively prevented, and therefore, the liquid electrolyte and the polymer electrolyte with narrow electrochemical windows can be applied to a high-voltage battery system, and the energy density and the cycle life of the battery can be improved to a great extent. In addition, the salt synthesis/purification process of the current commercial electrolyte is complex and has high price, so that the cost of the whole battery is relatively high, and if the salt synthesis/purification process of a new electrolyte is simple and has low price, the salt of the electrolyte in the prior art is partially or completely replaced, so that the excellent performance and lower cost can be simultaneously achieved.
-NBF 3 Is a strongly polar group capable of forming a salt with a cation, and therefore, -NBF 3 M has a strong sense of presence in the molecular structure, and its addition may change the properties of the whole molecular structure. In the prior art, only very individual researchers have been directed to BF-containing 3 The group compound is subjected to sporadic researches, and no industrial application results are found at present.
Patent No. CN108878975a discloses an electrolyte additive comprising a pyridine-boron trifluoride complex compound and a halosilane, wherein the pyridine-boron trifluoride complex compound is selected from at least one of compounds of the structural formula shown in formula (1): wherein R is 11 、R 12 、R 13 、R 14 、R 15 Each independently selected from hydrogen atom, halogen, cyano, sulfonic acid group, sulfonyl group, substituted or unsubstituted C 1～20 Alkyl, substituted or unsubstituted C 2～20 Alkenyl, substituted or unsubstituted C 6～26 Aryl, substituted or unsubstituted C 1～20 Alkoxy, substituted or unsubstituted C 6～26 An aryloxy group; the substituent is selected from halogen, sulfonic group or sulfonyl. However, the compound is a complex compound and is not an azote salt, and at present, great research results are not available, and industrial application results are not available.
The applicant has surprisingly found that Li is contained + /Na + is-NBF of 3 M salts have good effects in batteries, and thus, a specialised team is working on specializing in-NBF-containing studies 3 M salt and obtains better research results.
The present application is directed to-NBF 3 Independent studies were performed on the structure of M on the five-membered ring. The presence of-NBF on the five-membered ring 3 M, effects different from other structures may occur. The subject of the present application is therefore defined as the direct or indirect attachment of the-N-BF to the five-membered ring structure 3 M, thereby more specifically determining-N-BF 3 M is present in the five-membered ring.
Disclosure of Invention
In view of the above, the embodiments of the present application provide an electrolyte containing a five-membered cyclic nitrogen-based salt structure, and a preparation method and application thereof, so as to solve the technical defects existing in the prior art.
The application provides an electrolyte containing five-membered cyclic nitrogen-based salt structure, which comprises boron trifluoride salt, wherein the structure of the boron trifluoride salt is shown as a general formula I:
wherein M is a metal cation; r is R 1 、R 2 、R 3 、R 4 Is a carbon atom or a heteroatom selected from S, N, O, P, se, ca, al, B or Si; r is R 5 For the substituent, it means that any one H on the ring can be independently substituted with a substituent, and the substituent replaces one H or two H, in the case where the substituent replaces two H, each substituent is the same or different.
Further, N and R 1 Between and N and R 4 Is connected by single bond, R 1 And R is R 2 Between, R 2 And R is R 3 Between, R 3 And R is R 4 Is connected by single bond or double bond。
Further, the substituent is selected from a chain substituent, a ring substituent, a salt substituent, and a group in which any one or more of these groups is substituted with a halogen atom by H bonded to a C atom.
Further, the chain substituent is selected from the group consisting of H, a halogen atom, a carbonyl group, an ester group, an aldehyde group, an ether oxygen group, an ether sulfur group, =O, =S,Nitro, cyano, amide, primary amine, tertiary amine, secondary amine, sulfonamide, sulfoalkane, hydrazino, diazo, hydrocarbyl, heterohydrocarbyl;
wherein R is 11 And R is 12 Independently H or hydrocarbyl; ester groups include carboxylic acid esters, carbonic acid esters, sulfonic acid esters, and phosphoric acid esters; hydrocarbyl groups include alkyl, alkenyl, alkynyl and alkenynyl groups; heterohydrocarbyl is a hydrocarbyl containing at least one heteroatom; the heteroatoms in the heterohydrocarbyl are selected from halogen, N, P, S, O, se, al, B and Si;
the ring substituent comprises a ternary-octamembered ring and a polycyclic ring formed by at least two monocyclic rings;
the salt substituent comprises sulfate, sulfonate, sulfonylimide salt, carbonate, carboxylate, thioether salt, oxyether salt, nitrogen salt, hydrochloride, nitrate, azide salt, silicate and phosphate;
preferably, the carbonyl group isThe ester group is-R 13 COOR 14 、-R 13 OCOR 14 、-R 13 SO 2 OR 14 、 -R 13 O-CO-OR 14 Or->Amide is->Sulfonamide group asSulfoalkanes being/>Diazo is-n=n-R 16 The ether oxygen radical is-R 13 OR 14 The ether thio is-R 13 SR 14 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 Independently is no, a ring, or a hydrocarbyl or heterohydrocarbyl group containing 1 to 20 carbon atoms, the hydrocarbyl group including alkyl, alkenyl, alkynyl, or alkinyl groups, the heterohydrocarbyl group including heteroalkyl, heteroalkenyl, or heteroalkynyl groups, the ring being capable of optional attachment of a substituent; r directly connected to N 16 、R 17 、R 18 、 R 19 The radicals can also be H or metal ions, R being directly attached to O 11 、R 12 、R 13 The groups can also be metal ions.
Further, the halogen atom includes F, cl, br, I;
diazo-n=n-R 16 R in (a) 16 But also phenyl or phenyl to which substituents are attached;
cyano is selected from-CN, -CH 2 CN、-CH 2 CH 2 CN or-N (CH) 3 )CH 2 CH 2 CN；
Preferably, the alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, -CH 2 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 、-CH 2 (CH 2 ) 4 CH(CH 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the The heteroalkyl group is selected from the group consisting of-CH 2 CH 2 -O-NO 2 、-CO-CH 2 -Cl、-CO-CH 2 -Br、-COCH 2 (CH 2 ) 5 CH 3 、 -COCH(CH 3 )CH 2 CH(CH 3 )CHCl 2 CH 2 Cl、-CH 2 NO 2 、-Z 2 CF 3 、-CH 2 Z 2 、-CH 2 Z 2 CH 3 、-CH 2 CH 2 Z 2 、 -Z 2 (CH 2 CH 3 ) 2 、-CH 2 N(CH 3 ) 2 、-CH 2 Z 2 CH(CH 3 ) 2 、-COCH 2 CH(CH 3 ) 2 、-OCH 2 (CH 2 ) 6 CH 3 、 -CH 2 (CH 3 )Z 2 CH 2 -、-CH 2 (CH 3 )Z 2 CH 2 (CH 3 )-、-CH 2 CH 2 Z 2 CH 2 -、-CH 2 CH(CH 3 )Z 2 CH 2 -、 -CH(CH 3 )CH 2 Z 2 CH 2 -；
Alkenyl is selected from ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, 1, 3-hexadienyl, -C (CH) 3 )＝CH 2 、-C(CH 3 )＝CH 2 、-CH 2 CH＝C(CH 3 )CH 2 CH 2 CH＝C(CH 3 ) 2 、 -CH 2 CH＝CH(CH 3 ) 2 、-CH 2 CH＝CH-CH 2 CH 2 -；
The heteroalkenyl is selected from-n=chch 3 、-OCH 2 CH＝CH 2 、-CH 2 -CH＝CH-Z 2 CH 2 -、-CH＝CHCH 2 -CH 2 Z 2 CH 2 -；
Alkynyl is selected from ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl;
heteroalkynyl is selected from-C.ident.CCH 2 CH 2 CH 2 Z 2 CH 2 CH 2 -、-N(CH 3 )CH 2 CH 2 CN、-C≡CCH 2 Z 2 CH 2 CH 2 -、 -C≡C-Si(CH 3 ) 3 ；
Alkenynyl is selected from-c≡cch=chch 2 -、-C≡CCH 2 CH＝CHCH 2 Z 2 CH 2 -、-C≡CCH 2 CH 2 CH＝CHCH 2 -；
The cyclic substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and polycyclic; wherein the cyclopropyl group is selected from the group consisting of cyclopropane group, ethylene oxide,Cyclobutyl is selected from cyclobutyl, cyclo Ding Za alkyl, cyclobutenyl, cyclo Ding Za alkenyl; the cyclopentyl group is selected from the group consisting of cyclopentenyl, cyclopentadienyl, pyrrolyl, dihydropyrrolyl, tetrahydropyrrolyl, furanyl, dihydrofuranyl, tetrahydrofuranyl, thienyl, dihydrothienyl, tetrahydrothienyl, imidazolyl, thiazolyl, dihydrothiazolyl, tetrahydrothiazolyl, isothiazolyl, dihydroisothiazolyl, triazolyl, tetrazolyl, pyrazolyl, oxazolyl, dihydrooxazolyl, tetrahydrooxazolyl, isoxazole, dihydroisoxazole, thiadiazole, selenadiazole, 1, 3-dioxacycloalkane, 1, 3-dithiocycloalkane, and,The cyclohexyl is selected from phenyl, pyridyl, dihydropyridyl, tetrahydropyridyl, pyrimidinyl, dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl, p-diazabenzene, cyclohexaalkyl, cyclohexenyl, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, morpholine, piperazine, pyrone, pyridazine, dihydropyridazine, tetrahydropyridazine, pyrazine, dihydropyrazine, tetrahydropyrazin, triazine, and combinations thereof>The polycyclic ring is selected from biphenyl, naphthyl, anthryl, phenanthryl, quinolyl, pyrenyl, acenaphthenyl, carbazolyl, indolyl, isoindolyl, quinolinyl, purinyl, base, benzoxazole, and/or the like>
Wherein Z is 2 is-O-, -S-S-,R 29 、R 30 、R 31 、R 32 independently selected from methyl, ethyl, propyl, isopropyl, butyl, fluoromethyl, fluoroethyl, methoxy, ethenyl, propenyl, or metal ions;
any one of the rings of the ring substituent can be connected with a first substituent, and the type of the first substituent and R 2 Defined substituents are identical; preferably, the first substituent is selected from H, halogen atom, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, fluoromethyl, fluoroethyl, methoxy, ethoxy, nitro, alkenyl, alkynyl, ester, sulfonate, sulfoalkane, amide, cyano, aldehyde, -SCH 3 、-COOCH 3 、COOCH 2 CH 3 、 -OCF 3 、＝O、-N(CH 3 ) 2 、-CON(CH 3 ) 2 、-SO 2 CH 3 or-SO 2 CH 2 CH 3 ；
Any one ring of the ring substituents is independently linked to the substituted unsaturated heterocycle through any one of the following linking groups: -CH 2 -、-CH 2 CH 2 -, propyl, butyl, ethylene, propylene, butylene, acetylene, propyne, -COO-, -CO-, -SO 2 -、-N＝N-、-O-、-OCH 2 -、-OCH 2 CH 2 -、-CH 2 OCH 2 -、-COCH 2 -、-CH 2 OCH 2 CH 2 -、-OCH 2 CH 2 O-、 -COOCH 2 CH 2 -、-S-、-S-S-、-CH 2 OOC-、-CH＝CH-CO-、Or a single bond; r is R 29 Independently selected from methyl, ethyl or propyl; r is R 33 Independent and independentAny one of the linking groups; r is R 34 、R 35 Independently an alkyl group or a ring.
Preferably, R 1 、R 4 Is a carbon atom, and R 1 、R 4 Attached substituent R 5 Is=o. In this case, the structure of the electrolyte may be expressed asR 5 Selected from the substituents described in any of the preceding paragraphs.
More preferably, R 2 、R 3 Is a carbon atom, in which case the structure of the electrolyte may be expressed asR 5 Selected from the substituents described in any of the preceding paragraphs.
Further, M in the general formula I comprises Na + 、K + 、Li + 、Mg 2+ Or Ca 2+ Preferably Na + 、K + Or Li (lithium) + 。
All or part of the hydrogen atoms on all carbon atoms in any one general formula I are independently replaced by halogen atoms; preferably, all or part of the hydrogen atoms on all carbon atoms in any one of the formulae I are independently replaced by fluorine atoms.
The application also provides a preparation method of the five-membered cyclic nitrogen-based salt structure, wherein the nitrogen-based salt is obtained by reacting a raw material containing-NH with a boron trifluoride compound and an M source.
The application also provides an application of the electrolyte containing the pentabasic cyclic nitrogen-based salt structure in a secondary battery, wherein the application is as follows: the boron trifluoride salt can be used both as an additive and as a salt of an electrolyte.
Further, the applications include applications in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes, which independently include electrolytes containing nitrogen-based salt structures as described in any one of the above paragraphs.
Further, the application also includes application as a battery or battery pack including the electrolyte containing the nitrogen-based salt structure as described in any one of the above paragraphs, and the positive electrode, the negative electrode, and the package can, the electrolyte being applicable to liquid batteries, hybrid solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries, and all-solid batteries; the battery pack includes the battery.
The invention has the following main beneficial effects:
the electrolyte in the present application creatively will be-NBF 3 M is compounded in a five-membered ring structure, and the structure effect protected by the invention is more remarkable.
1. The nitrogen-based boron trifluoride 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 electrolyte from being in direct contact with electrode active substances, inhibits decomposition of each component of the electrolyte, widens an electrochemical window of the whole electrolyte system, and can remarkably improve the discharge specific capacity, coulomb efficiency and cycle performance of the battery; in addition, the nitrogen-based boron trifluoride compound is an ion conductor, and as an additive, active ions which are extracted from a positive electrode are rarely consumed while a passivation layer is formed on the surface of an electrode, so that the first coulomb efficiency and the first-week discharge specific capacity of a battery can be obviously improved. And when the electrolyte containing the nitrogen-based boron trifluoride 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 structures of the present application can also be used in combination with conventional additives, i.e., dual or multi-additive, batteries using dual or multi-additive exhibit more excellent electrochemical performance.
2. The boron-containing organic compound can be used as a main salt of an electrolyte, can be used as a main salt alone, and can be used as a main salt to form double salts or multiple salts together with other conventional salts. The structure contains ions which are easy to dissociate, so that the structure can provide higher ion conductivity and higher stability, and does not corrode the current collector, so that the assembled battery has excellent electrochemical performance.
3. The boron trifluoride salt has the advantages of abundant raw material sources, wide raw material selectivity, low cost, simple preparation process, mild reaction conditions and excellent industrial application prospect.
4. The application can also adopt metals such as sodium, potassium and the like except for traditional lithium to form salts, which provides more possibility, great significance for later application, cost control or raw material selection and the like.
Therefore, the nitrogen-based boron trifluoride compound provided by the application has multiple purposes in batteries, can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, can improve the electrochemical performance of the batteries, and comprises the steps of improving the energy density of the batteries, improving the circulation stability, prolonging the service life of the batteries, and has simple synthesis process, low raw material price and good economic benefit.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product of example 1 of the present application; FIG. 2 is a nuclear magnetic resonance spectrum of the product of example 3 of the present application; FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the product of example 6 of the present application; FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the product of example 13 of the present application;
FIGS. 5 to 8 are graphs showing the effect of the battery 1/2/5/13 produced by example 1/2/5/13 as electrolyte additive and the corresponding comparative battery 1/2/5/13 not containing example 1/2/5/13 of the present invention;
FIGS. 9 to 10 are graphs showing the effect of the battery 1/3 produced as a liquid electrolyte salt in example 1/3 and the corresponding comparative battery 1/3 not containing example 1/3 of the present invention, respectively;
fig. 11 is a graph showing the effect of the battery 1 made of the salt as the solid electrolyte in example 1 compared with the comparative battery 1 made of LiTFSI as the salt.
Detailed Description
The following describes specific embodiments of the present application with reference to the drawings.
In the present invention, unless otherwise indicated, scientific and technical terms used herein have the meanings commonly understood by one of ordinary skill in the art. Also, reagents, materials, and procedures used herein are reagents, materials, and conventional procedures widely used in the corresponding field. Meanwhile, in order to better understand the present invention, definitions and explanations of related terms are provided below.
In the present invention, if a group is required to be linked to a two-part structure, it has two linkages to be linked, and if it is not explicitly indicated which two atoms are linked to the linked part, any one of the atoms containing H may be linked.
In the present invention, if the chemical bond is not drawn on an atom, but is drawn at a position intersecting the bond, e.g.Represents any H on cyclohexane which may be substituted by a substituent R 04 Substituted, and may be substituted for one H or two or more H, and the substituents may be the same or different. If two H are contained in one C of cyclohexane, the two H may be substituted by all substituents, or may be substituted by only 1, for example, both H may be substituted by methyl, or one may be substituted by methyl, and one may be substituted by ethyl. In addition, substituents may also be attached to the ring by double bonds. For example, in this structure, if R 04 Methyl, = O, F, the above structure may be +.>
In the structural formula of the present invention, if a group located in a bracket "()" is contained after a certain atom, it means that the group in the bracket is linked to the atom in front of it. Such as-C (CH) 3 ) 2 -is-CH(CH 3 ) -is->
In the ownership and description of the present invention, -NBF 3 M in M may be a monovalent, divalent, trivalent or multivalent metal cation, if it is a non-monovalent ion, -NBF 3 The corresponding increase in the number of (c) is such that it fits exactly with the valence of M.
In the specific structural formulae set forth in the claims, only one substituent is depicted on each C to illustrate that H on that C may be either partially or fully substituted. For example in the case of structural typeWherein R is 1 、R 2 All means that it can replace one H on the C, or can replace two H on the C.
The "boron trifluoride-like compound" means boron trifluoride, a compound containing boron trifluoride, a boron trifluoride complex or the like.
In the present invention, the terms "structure provided by the present invention", "boron trifluoride salt", "boron trifluoride organic salt", "five-membered ring nitrogen salt", "boron trifluoride salt", "nitrogen salt", "boron trifluoride compound", and the like are used in the present invention, although they are different from each other.
The invention provides a monobasic organic boron trifluoride salt which can be used as electrolyte additive and electrolyte salt, namely, the organic matter contains-NBF 3 M is a group, wherein M is Li + 、Na + Etc. The boron trifluoride salt can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries. The preparation method of the compound is simple and ingenious, and the yield is high. Namely, raw materials, boron trifluoride compounds and an M source react to obtain the boron trifluoride compound, specifically, -NH in the raw materials participates in the reaction, and other structures do not participate in the reaction. The specific preparation method mainly comprises two steps:
1. under the atmosphere of nitrogen/argon, adding an M source and raw materials into a solvent, mixing, reacting for 5-24 hours at 5-60 ℃, and drying the obtained mixed solution under reduced pressure at 20-80 ℃ and a vacuum degree of about-0.1 MPa to remove the solvent to obtain an intermediate; then adding boron trifluoride compound, stirring at 5-60 ℃ for reaction for 6-24 hours, drying the obtained mixed solution under reduced pressure at 20-80 ℃ and a vacuum degree of about-0.1 MPa to obtain a crude product, washing, filtering and drying the crude product to obtain the final product of unitary organic boron trifluoride salt, wherein the yield is 70-95%.
2. Adding the raw materials and boron trifluoride compound into a solvent under the atmosphere of nitrogen/argon, uniformly mixing, reacting for 6-24 hours at 5-60 ℃, drying the obtained mixed solution under reduced pressure at 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, adding the solvent containing the M source into an intermediate, stirring and reacting for 5-24 hours at 5-60 ℃ to obtain a crude product, directly washing the crude product or drying the crude product under reduced pressure, washing, filtering and drying to obtain the final product, namely the unitary organic boron trifluoride salt, wherein the yield is 70-95%.
In the above two specific preparation methods, the boron trifluoride-type compound may include boron trifluoride diethyl etherate, boron trifluoride tetrahydrofuran complex, boron trifluoride butyl etherate, boron trifluoride acetic acid complex, boron trifluoride monoethylamine complex, boron trifluoride phosphoric acid complex, etc. M sources include 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 liquid alcohols may also be used as the starting materials at the same time), ethyl acetate, DMF, acetone, hexane, dichloromethane, tetrahydrofuran, ethylene glycol dimethyl ether, and the like. The washing can be performed with small polar solvents such as diethyl ether, n-butyl ether, cyclohexane, diphenyl ether, etc.
Example 1
Raw materials
The preparation method comprises the following steps: under a nitrogen atmosphere, 0.02mol of the starting material and boron trifluoride tetrahydrofuran complex (2.8 g,0.02 mol) were uniformly mixed in 15ml of ethylene glycol dimethyl ether and reacted at room temperature for 12 hours. The resulting mixed solution was dried under reduced pressure at 40℃and a vacuum of about-0.1 MPa to remove the solvent, thereby obtaining an intermediate. Lithium ethoxide (1.04 g,0.02 mol) is dissolved in 10ml of ethanol and slowly added into the intermediate, the mixture is stirred and reacted for 8 hours at 45 ℃, the obtained mixture is dried under reduced pressure under the condition of 45 ℃ and the vacuum degree of about-0.1 MPa, and the obtained solid is washed three times by n-butyl ether, filtered and dried to obtain the product P1. The yield of the product P1 is 89%, and the nuclear magnetic hydrogen spectrum is shown in figure 1.
Example 2
Raw materials
The preparation method comprises the following steps: under an argon atmosphere, 0.02mol of the starting material and boron trifluoride diethyl etherate (2.98 g,0.021 mol) were mixed uniformly in 15ml of THF (tetrahydrofuran) and reacted at room temperature for 18 hours. The resulting mixed solution was dried under reduced pressure at 50℃and a vacuum of about-0.1 MPa to remove the solvent, thereby obtaining an intermediate. 13ml of a hexane solution of butyllithium (c=1.6 mol/L) was added to the intermediate, the reaction was stirred at room temperature for 6 hours, the obtained mixture was dried under reduced pressure at 40℃under a vacuum of about-0.1 MPa, and the obtained crude product was washed 3 times with cyclohexane, filtered and dried to obtain product P2. The yield of product P2 was 83%.
Example 3
Raw materials
The preparation method comprises the following steps: under nitrogen atmosphere, 0.02mol of the raw material and lithium methoxide (0.76 g,0.02 mol) were taken and mixed well with 20ml of methanol, and reacted at room temperature for 24 hours. The resulting mixed solution was dried under reduced pressure at 40℃and a vacuum of about-0.1 MPa to remove the solvent, thereby obtaining an intermediate. Boron trifluoride tetrahydrofuran complex (3.07 g,0.022 mol) and 15ml of THF (tetrahydrofuran) were added to the intermediate, the reaction was stirred at room temperature for 16 hours, the resulting mixture was dried under reduced pressure at 40℃under a vacuum of about-0.1 MPa, and the obtained solid was washed three times with isopropyl ether, filtered and dried to obtain product P3. The yield of the product P3 is 84%, and the nuclear magnetic hydrogen spectrum is shown in FIG. 2.
Example 4
Raw materials
The preparation method comprises the following steps: 0.02mol of the starting material and boron trifluoride diethyl etherate (2.98 g,0.02 mol) were uniformly mixed in 15ml of ethylene glycol dimethyl ether in a glove box, and reacted at room temperature for 12 hours. The resulting mixed solution was dried under reduced pressure at 45℃and a vacuum of about-0.1 MPa to remove the solvent, to obtain an intermediate. Lithium ethoxide (1.04 g,0.02 mol) was dissolved in 10ml of ethanol and 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 of about-0.1 MPa, and the obtained solid was washed three times with isopropyl ether, filtered and dried to obtain product P4. The yield of product P4 was 84%.
Example 5
Raw materials
The preparation method comprises the following steps: under an argon atmosphere, 0.02mol of the starting material and boron trifluoride acetic acid complex (3.83 g,0.0204 mol) were uniformly mixed in 15ml of THF (tetrahydrofuran), and reacted at room temperature for 12 hours, and the resulting mixed solution was dried under reduced pressure at 50℃under a vacuum of about-0.1 MPa to remove the solvent, to obtain an intermediate. Sodium acetate (1.64 g,0.02 mol) was dissolved in 10ml of N, N-dimethylformamide and added to the intermediate, the reaction was stirred at 50℃for 8 hours, the resulting mixture was dried under reduced pressure at 80℃under a vacuum of about-0.1 MPa, and the obtained solid was washed three times with diphenyl ether, filtered and dried to give a product P5. The yield of product P5 was 89%.
Example 6
Raw materials
The P6 provided in this example was prepared from 0.02mol of the starting material by the method of example 1, and had a yield of 85% and a nuclear magnetic hydrogen spectrum as shown in FIG. 3.
Example 7
Raw materials
The P7 provided in this example was prepared from 0.02mol of starting material by the method of example 2 in 87% yield.
Example 8
Raw materials
The P8 provided in this example was prepared from 0.02mol of starting material by the method of example 3 in 89% yield.
Example 9
Raw materials
The P9 provided in this example was prepared from 0.02mol of starting material by the method of example 4 in 86% yield.
Example 10
Raw materials
The P10 provided in this example was prepared from 0.02mol of starting material by the method of example 3 in 87% yield.
Example 11
Raw materials
The P11 provided in this example was prepared from 0.02mol of starting material by the method of example 2 in 84% yield.
Example 12
Raw materials
The P12 provided in this example was prepared from 0.02mol of starting material by the method of example 1 in 86% yield.
Example 13
Raw materials
The P13 provided in this example was prepared from 0.02mol of the starting material by the method of example 2, and had a yield of 89% and a nuclear magnetic hydrogen spectrum as shown in FIG. 4.
Example 14
Raw materials
The P14 provided in this example was prepared from 0.02mol of starting material by the method of example 3 in 87% yield.
Example 15
The nitrogen-based boron trifluoride organic salt is mainly used as an additive and salt in batteries (including liquid batteries and solid batteries), and mainly plays a role in generating a passivation layer as the additive, and plays a role in supplementing consumed ions because ions can be dissociated, so that the first-week efficiency, the first-week discharge specific capacity, the long-cycle stability and the multiplying power performance of the battery are greatly improved; the salt in the electrolyte mainly plays a role of providing ion transmission and passivating the electrode, and the salt is used as a salt alone or is matched with the traditional salt to be used as double salt, so that the effect is good. The performance of the invention is illustrated in the following by way of tests.
1. As electrolyte additive
(1) Positive electrode plate
Adding an active material of a positive electrode main material, an electron conductive additive and a binder into a solvent according to a mass ratio of 95:2:3, wherein the solvent accounts for 65% of the total slurry, and uniformly mixing and stirring to obtain positive electrode slurry with certain fluidity; and coating the anode slurry on an aluminum foil, and drying, compacting and cutting to obtain the usable anode plate. The active material is selected from lithium cobalt oxide (LiCoO) 2 LCO, lithium nickel cobalt manganate (NCM 811), lithium nickel cobalt aluminate (LiNi) 0.8 Co 0.15 Al 0.05 O 2 Abbreviated NCA), lithium nickel manganate (LiNi 0.5 Mn 1.5 O 4 LNMO), na 0.9 [Cu 0.22 Fe 0.3 Mn 0.48 ]O 2 (abbreviated NCFMO), carbon Nanotubes (CNT) and SuperP are used as electron-conducting additives, polyvinylidene fluoride (PVDF) is used as binder, and N-methylpyrrolidone (NMP) is used as solvent.
(2) Negative pole piece
Adding a negative electrode main material active substance (except metal Li), an electron 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 electrode slurry with certain fluidity; and coating the negative electrode slurry on a copper foil, and drying and compacting to obtain the usable negative electrode plate. The active material used here is selected from graphite (C), silicon carbon (SiOC 450), lithium metal (Li), soft Carbon (SC), conductive agents CNT and super p, and binders carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR).
The positive and negative electrode systems selected in the invention are shown in table 1:
TABLE 1 Positive and negative electrode System Table
| Positive and negative electrode system of battery | Positive electrode material | Negative electrode material |
| A1 | LCO | SiOC450 |
| A2 | NCM811 | SiOC450 |
| A3 | NCM811 | Li |
| A4 | NCA | C |
| A5 | LNMO | C |
| A6 | LCO | Li |
| A7 | NCFMO | SC |
(3) The liquid electrolytes P1-P14, organic solvents, conventional salts and conventional additives are prepared and uniformly mixed to obtain the series electrolytes E1-E14, wherein the solvents used are methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene Carbonate (EC) and Propylene Carbonate (PC). The functional additives (i.e. conventional additives) are fluoroethylene carbonate (FEC), vinylene Carbonate (VC), trimethyl phosphate (TMP), ethoxypentafluoroethylcyclotriphosphazene (PFPN), vinyl sulfate (DTD); conventional salts are lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiODFB) oxalato borate, lithium bis (fluorosulfonyl) imide (LiLSI), lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethyl) sulfonimide (LiTFSI), sodium hexafluorophosphate (NaPF) 6 ). The specific components, proportions and the like are shown in Table 2.
TABLE 2 liquid electrolyte E formulated with Structure P provided by the invention as an additive
Note that: 1M means 1mol/L.
Comparison sample: according to the proportion of E1-E14, P1-P14 is changed into blank (i.e. P1-P14 is not added), and the corresponding conventional liquid electrolyte comparison samples L1-L14 can be obtained.
(4) Button cell assembly
The liquid electrolyte series E1-E14 containing the structure as an additive in the embodiment of the application and the conventional liquid electrolytes L1-L14 are assembled into a button cell, and the specific steps are as follows: negative electrode shell, negative electrode plate and PE/Al 2 O 3 The diaphragm, electrolyte, positive pole piece, stainless steel sheet, spring piece and positive pole shell are assembled into a button cell, and long-cycle test is carried out at room temperature, wherein the cycle mode is 0.1C/0.1C1 week, 0.2C/0.2C5 week and 1C/1C44 week (C represents multiplying power), the positive pole piece is a wafer with the diameter of 12mm, the negative pole piece is a wafer with the diameter of 14mm, the diaphragm is a wafer with the diameter of 16.2mm, and the diaphragm is commercial Al 2 O 3 PE porous separator.
The battery systems prepared by E1-E14 are batteries 1-14 respectively, and the battery systems prepared by L1-L14 are comparative batteries 1-14 respectively. The specific configuration and voltage ranges of the cells are shown in table 3.
The results of the first-week discharge specific capacity, the first-week efficiency, and the cycle 50 capacity retention rate at room temperature of the batteries 1 to 14 and the comparative batteries 1 to 14 are shown in table 4.
Table 3 example battery and comparative battery configuration and test mode
Table 4 comparative example battery and comparative battery test results
From the test results of the battery and the comparative battery, when the positive and negative electrode systems are the same in the button battery, the first-cycle efficiency, the first-cycle discharge specific capacity and the capacity retention rate of the battery using the structures P1 to P14 of the invention as the liquid electrolyte additive are all better than those of the battery without adding the additive, and the performance of the battery is better than that of the conventional additive at present. In addition, the use of boron-containing salt additives in the presence of conventional additives shows synergistic effects and the battery shows more excellent electrochemical performance.
2. As salt in liquid electrolytes
(1) Preparing liquid electrolyte
P1, P3, P6, P10 are uniformly mixed with an organic solvent, a conventional additive and a conventional salt to obtain a series of liquid electrolytes R1, R3, R6 and R10, the conventional salt, the organic solvent and the conventional additive are uniformly mixed to obtain a series of conventional liquid electrolytes Q1, Q3, Q6 and Q10, and the used solvents and functional additives comprise the solvents and functional additives described in the 'one' of the embodiment. Specific components, proportions, and the like of the liquid electrolyte are shown in table 5.
Table 5 synthetic substance P as salt formulated liquid electrolyte
(2) Battery assembly
The obtained series of liquid electrolytes R (shown in table 5) and the conventional liquid electrolytes Q (shown in table 5) were assembled into button cells, and the positive and negative electrodes, the separator size, the assembly method, and the cycle mode of the cells were the same as those of the button cells shown in "one" of this example, namely, the cells 1,3, 6, 10 and the corresponding comparative cells, respectively. The specific configuration, cycle mode and voltage ranges of the battery are shown in table 6, and the results of the first-week discharge specific capacity, the first-week efficiency and the cycle 50-week capacity retention rate of the battery and the comparative battery at room temperature are shown in table 7.
Table 6 example battery and comparative example battery configuration and test mode
Table 7 comparative example batteries and comparative battery test results shown in table 6
In summary, the boron-containing salt provided by the invention is taken as salt alone or forms double salts with conventional salt in a non-aqueous solvent, ions are easily solvated, higher ion conductivity is provided for a battery, and the stability is higher, and in a liquid battery system with LCO and NCM811 as positive electrodes and SiOC450 and Li as negative electrodes, the boron-containing salt has very excellent electrochemical performance, and the first-week efficiency, the first-week discharge specific capacity and the capacity retention rate are higher, and the performance of the boron-containing salt is equal to or better than that of a battery corresponding to the conventional salt.
3. As salt in solid electrolytes
(1) Preparation of Polymer electrolyte Membrane
In the environment with dew point lower than minus 60 ℃, the structure, the polymer and the inorganic filler provided by the invention are dissolved in DMF according to a proportion, and the polymer electrolyte membranes G1, G2, G6 and G13 and the polymer comparative electrolyte membranes G '1-G' 2 are obtained after stirring, mixing, coating to form a film, rolling and drying. The specific components, proportions and the like are shown in Table 8. The polymer is polyethylene oxide (PEO, molecular weight is 100 ten thousand), the inorganic filler is LLZO with 160nm, i.e. the crystal form with 160nm median particle diameter is cubic Li 7 La 3 Zr 2 O 12 An inorganic oxide solid electrolyte.
TABLE 8 specific Components and proportions of Polymer electrolyte Membrane
| Polymer electrolyte membrane | Polymer | Salt | Inorganic filler | The mass ratio of the former | Solvent(s) |
| G1 | PEO100 ten thousand | P1 | 160nmLLZO | 4.2：1：0.8 | DMF |
| G2 | PEO100 ten thousand | P2 | / | 4.2：1 | DMF |
| G6 | PEO100 ten thousand | P6 | 160nmLLZO | 4.2：1：0.8 | DMF |
| G13 | PEO100 ten thousand | P13 | / | 4.2：1 | DMF |
| G’1 | PEO100 ten thousand | LiTFSI | 160nmLLZO | 4.2：1：0.8 | DMF |
| G’2 | PEO100 ten thousand | LiTFSI | / | 4.2：1 | DMF |
(2) Preparation of positive and negative plates
In the environment with dew point lower than minus 60 ℃, the active material of the positive electrode main material, polymer+salt (the proportion is equal to that of the polymer electrolyte membrane), electron conductive additive and binder are mixed according to the mass ratio of 90:5:2.5:2.5 stirring and mixing the materials in a solvent, coating the materials on an aluminum foil, drying and rolling the materials to obtain the full-solid positive electrode plate. Lithium cobalt oxide (LiCoO 2, abbreviated LCO) and lithium nickel cobalt manganate (NCM 811) were used as active materials, superP was used as electron conductive additive, polyvinylidene fluoride (PVDF) was used as binder, and NMP was used as solvent.
A 50 μm thick lithium metal sheet was pressed onto a copper foil as a negative electrode sheet.
(3) Battery assembly and testing
And cutting the polymer electrolyte membrane and the positive and negative pole pieces to form the 1Ah all-solid-state soft-package battery, and carrying out 50 ℃ long-cycle test on the battery, wherein the cycle mode is 0.1C/0.1C2 week and 0.3/0.3C48 week. Specific assembly systems and test methods of the cells are shown in table 9, and test results are shown in table 10.
Table 9 example battery and comparative battery configuration and test mode
Table 10 comparison of test results for batteries and comparative batteries in table 9
| Example battery and comparative example battery | First week discharge capacity (Ah) | First week efficiency (%) | Cycle 50 week Capacity retention (%) |
| Battery 1 | 0.89 | 89.3 | 85.5 |
| Battery 2 | 0.90 | 90.1 | 85.1 |
| Battery 6 | 0.87 | 87.2 | 87.2 |
| Battery 13 | 0.85 | 85.6 | 87.4 |
| Comparative cell 1 | 0.88 | 88.3 | 67.6 |
| Comparative cell 2 | 0.85 | 85.5 | 68.7 |
From the data in tables 9 and 10, it can be seen that the batteries prepared from P1, P2, P6 and P13 have excellent long-cycle stability and performance superior to the cycle performance of the corresponding batteries of LiTFSI, probably because the nitrogen-based boron trifluoride salt of the present invention not only has excellent ion transmission performance, but also can form a more compact and stable passivation layer on the surface of the positive electrode to prevent the catalytic decomposition of the positive electrode active material on each component of the electrolyte, and in addition, the boron trifluoride salt of the present invention does not corrode the current collector, thereby exhibiting performance superior to that of the conventional salt.
In addition, some boron trifluoride nitrogen salt is selected as an additive, and an effect diagram of an embodiment of the salt is shown. FIGS. 5 to 8 are graphs showing the effect of the battery 1/2/5/13 produced by example 1/2/5/13 as an electrolyte additive, respectively, compared with the effect of the corresponding comparative battery 1/2/5/13 not containing example 1/2/5/13 of the present invention. FIGS. 9 to 10 are graphs showing the effect of the battery 1/3 produced as a liquid electrolyte salt in example 1/3 and the corresponding comparative battery 1/3 not containing example 1/3 of the present invention, respectively. Fig. 11 is a graph showing the effect of the battery 1 made of the salt as the solid electrolyte in example 1 compared with the comparative battery 1 made of LiTFSI as the salt. The structure of the present application has excellent effects as can be seen from fig. 5 to 11.
The performances such as the first cycle efficiency, the first cycle discharge specific capacity, the first cycle discharge capacity, the capacity retention rate and the like have direct and obvious influence on the overall performance of the battery, and directly determine whether the battery can be applied. Thus, improving these properties is a goal or direction for many researchers in the field, but in the field, improvement of these properties is very difficult, and generally improvement of about 3-5% is a major advance. In the early test data, the application has the surprise that the data are greatly improved compared with the conventional data, particularly when the data are used as additives of liquid electrolytes, the performance is improved by about 5-30%, and the additives in the application and the conventional additives are combined to be used to show better effects. More surprisingly, the component can also be used as salt in electrolyte, and has very good effect, and the component is superior to the prior component which is used more mature in test. In addition, the nitrogen-based boron trifluoride compound can be applied to not only liquid batteries but also solid batteries no matter being used as an additive or a salt, has excellent effect and has excellent application prospect. More importantly, the structure type of the application is greatly different from that of a conventional structure, so that a new direction and thought are provided for research and development in the field, a large space is also provided for further research, and the application can be used for multiple purposes of a structure; the meaning is extremely great.
In a word, the nitrogen-based boron trifluoride salt provided by the application can be used in a small amount in the electrolyte, and mainly has the effects of forming a passivation layer on the surface of the electrode after decomposition, and adding dissociable ions, so that ions provided by the electrode are less consumed in the process of forming the passivation layer, and the first cycle efficiency and the cycle performance of the battery are remarkably improved; the electrolyte salt can be used in an increased amount, and has the main effect of ion transmission after dissociation and the secondary effect of passivation electrode, and the electrolyte salt can be used as a salt alone or is matched with the traditional salt to be used as double salt, so that the electrolyte has good electrochemical performance. The nitrogen-based boron trifluoride salt can be applied to liquid batteries, solid-liquid hybrid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, and is beneficial to improving the energy density, the cycle stability and the service life of the batteries. And the raw materials are low in price, the synthesis and purification processes are simple, and the method has good economic benefit.
In the present invention, only a part of the structures are selected as representative examples to illustrate the preparation method, effect, etc. of the present application, and other structures not listed have similar effects. For example:
the effects are excellent and other structures similar to those described in any of the paragraphs herein are also preferable, but for reasons of length, the effects of the structures protected by the present invention will now be described by way of example only with examples 1-14. And the preparation methods of the examples 1-14 and the structures listed above are all that the boron trifluoride organic salt is obtained by the reaction of the raw material, the M source and the boron trifluoride compound, namely that the-NH in the raw material is changed into-NBF 3 M, M can be Li + 、Na + Etc., other structures are unchanged, see in particular examples 1-5. The structures not shown in the examples are all the same as the preparation method.
The raw materials used in the examples can be purchased or simply prepared, and the preparation process is also known in the art, so they are not described in detail in the specification.
It should be noted that, in some cases, the applicant performs a great deal of tests on the series of structures, and for better comparison with the existing system, there are cases where the same structure and system are used for performing more than one test, so that there may be a certain error in different tests.
Finally, it should be noted that: the embodiments described above are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. An electrolyte containing five-membered cyclic nitrogen-based salt structure is characterized by comprising boron trifluoride salt, wherein the structure of the boron trifluoride salt is shown as a general formula I:
general formula I
Wherein M is a metal cation;
R 1 、R 2 、R 3 、R 4 is a carbon atom or a heteroatom selected from S, N or O;
the N and R 1 Between and N and R 4 Is connected by single bond, R 1 And R is R 2 Between, R 2 And R is R 3 Between, R 3 And R is R 4 The two are connected through a single bond;
R 1 、R 4 is a carbon atom, and R 1 、R 4 Attached substituent R 5 Is =o;
m in the general formula I is Na + 、K + Or Li (lithium) + ；
The structure of the boron trifluoride salt is shown as any one of formulas P1-P13:
P1；/>P2；/>P3；/>P4；P5；/>P6；/>P7；/>P8；P9；/>P10；/>P11；/>P12；P13。
2. a method for producing an electrolyte having a five-membered cyclic nitrogen-based salt structure according to claim 1, wherein the nitrogen-based salt is obtained by reacting a raw material containing-NH with a boron trifluoride-based compound and an M source.
3. Use of the electrolyte containing a five-membered ring nitrogen based salt structure according to claim 1 or 2 in a secondary battery, characterized in that the use is: the boron trifluoride salt can be used both as an additive and as a salt of an electrolyte.
4. The use according to claim 3, characterized in that the use comprises use in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes independently comprising the electrolyte containing a pentabasic cyclic nitrogen-based salt structure according to claim 1 or 2.
5. The use according to claim 4, further comprising the use as a battery or battery pack comprising the electrolyte containing a pentabasic cyclic nitrogen-based salt structure according to claim 1 or 2, applicable to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, as well as a positive electrode, a negative electrode and a packaging case; the battery pack includes the battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011496920.9A CN114649581B (en) | 2020-12-17 | 2020-12-17 | Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011496920.9A CN114649581B (en) | 2020-12-17 | 2020-12-17 | Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114649581A CN114649581A (en) | 2022-06-21 |
| CN114649581B true CN114649581B (en) | 2024-04-12 |
Family
ID=81991564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011496920.9A Active CN114649581B (en) | 2020-12-17 | 2020-12-17 | Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114649581B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644644B (en) * | 2020-12-17 | 2024-01-30 | 北京卫蓝新能源科技有限公司 | Electrolyte containing nitrogen-based salt structure, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015138627A (en) * | 2014-01-21 | 2015-07-30 | 株式会社日本触媒 | Positive electrode elution inhibitor and lithium-ion secondary battery containing the same |
| CN105489935A (en) * | 2016-01-11 | 2016-04-13 | 东莞新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
| CN106946925A (en) * | 2017-03-31 | 2017-07-14 | 中国科学院青岛生物能源与过程研究所 | Fluoroalkyl trifluoro lithium borate salt and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6852446B2 (en) * | 2001-11-09 | 2005-02-08 | Yardney Technical Products, Inc. | Non-aqueous electrolytes for lithium electrochemical cells |
-
2020
- 2020-12-17 CN CN202011496920.9A patent/CN114649581B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015138627A (en) * | 2014-01-21 | 2015-07-30 | 株式会社日本触媒 | Positive electrode elution inhibitor and lithium-ion secondary battery containing the same |
| CN105489935A (en) * | 2016-01-11 | 2016-04-13 | 东莞新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
| CN106946925A (en) * | 2017-03-31 | 2017-07-14 | 中国科学院青岛生物能源与过程研究所 | Fluoroalkyl trifluoro lithium borate salt and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114649581A (en) | 2022-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4265622A1 (en) | Electrolyte containing nitrogen-based salt structure, preparation method therefor and use thereof | |
| CN114649581B (en) | Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof | |
| CN115215768A (en) | Polycyclic compound organic lithium supplement agent and preparation method and application thereof | |
| CN114649582A (en) | Electrolyte containing six-membered cyclic nitrogen-based salt structure and preparation method and application thereof | |
| CN114230584A (en) | Electrolyte containing aromatic ring structure and preparation and application thereof | |
| CN114649571A (en) | Ternary sulfenyl boron trifluoride salt electrolyte and preparation method and application thereof | |
| CN114605446A (en) | Electrolyte containing saturated carbon ring structure and preparation method and application thereof | |
| CN114230591A (en) | Polycyclic electrolyte and preparation and application thereof | |
| CN114605445A (en) | Electrolyte containing aromatic ring structure and preparation method and application thereof | |
| CN111682263A (en) | Application of Nitrile Compounds in Preparation of Electrolyte for High Voltage Battery System | |
| CN114649584A (en) | Electrolyte containing aromatic ring-type sulfur-based boron trifluoride salt and preparation method and application thereof | |
| CN114605444A (en) | Electrolyte containing polycyclic structure and preparation method and application thereof | |
| CN114621263A (en) | Electrolyte containing unsaturated carbon ring structure and preparation method and application thereof | |
| CN114649570B (en) | A polymerizable electrolyte and its preparation method and application | |
| CN114621265A (en) | Electrolyte containing saturated heterocyclic structure and preparation method and application thereof | |
| CN114649577A (en) | Sulfur-based saturated carbon chain electrolyte and preparation method and application thereof | |
| CN114605443A (en) | Electrolyte containing unsaturated heterocyclic structure and preparation method and application thereof | |
| CN114649573A (en) | Sulfur-based electrolyte containing saturated heterocycles and preparation method and application thereof | |
| CN114649578A (en) | Saturated heterochain sulfur-based electrolyte and preparation method and application thereof | |
| CN114649575A (en) | Electrolyte containing saturated carbon ring sulfur-based organic salt and preparation method and application thereof | |
| CN114621266A (en) | Electrolyte containing saturated heterochain structure and preparation method and application thereof | |
| CN114649574A (en) | Sulfur-based boron trifluoride salt electrolyte containing unsaturated carbon rings and preparation method and application thereof | |
| CN114621264A (en) | Electrolyte containing saturated carbon chain structure and preparation method and application thereof | |
| CN114573618A (en) | Saturated carbon ring ternary electrolyte and preparation and application thereof | |
| CN114573617A (en) | Ternary electrolyte containing saturated heterocycles, and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 108, 1st Floor, Building 4, No. 91 Pu'an Road, Doudian, Fangshan District, Beijing 102402 Patentee after: Beijing Weilan New Energy Technology Co.,Ltd. Country or region after: China Address before: No.1 Qihang West Street, Doudian Town, Fangshan District, Beijing Patentee before: BEIJING WELION NEW ENERGY TECHNOLOGY Co.,Ltd. Country or region before: China |